JP2012194359A - Method for manufacturing spectacle lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a spectacle lens having a high-durability hydrophilic film.SOLUTION: A method for manufacturing a spectacle lens in which an anti-fog layer is provided on a lens base material having an inorganic antireflection film with an SiOlayer formed on the outermost surface of the lens base material includes the following steps of: processing the SiOlayer of the inorganic antireflection film by a process liquid containing an inorganic alkali; and then forming a hydrophilic film. The hydrophilic film is preferably formed by processing organosilane having a hydrolyzable group which can be converted into a silanol group by hydrolysis.

Description

  The present invention relates to a method for manufacturing a spectacle lens.

  In the spectacle lens manufacturing process, there is a cleaning process for cleaning dirt such as excess resin, fingerprints, and dust attached to the plastic lens substrate before performing various surface coatings on the plastic lens substrate. And as a washing | cleaning method, the plasma process which processes a plastics lens base material using a plasma generator, and the alkali process processed with an alkaline process liquid are known (for example, refer patent document 1).

  On the other hand, as a method for imparting antifogging performance to the spectacle lens surface, organosilane or hydrolyzate thereof having a highly hydrophilic sulfonic acid group or sulfate group, or organosilane and hydrolyzate thereof is used. It is known to form a used hydrophilic thin film, that is, an antifogging film (see, for example, Patent Document 2). And in patent document 2, when forming an anti-fogging film | membrane in a spectacle lens, the cleaning and activation of the surface by the plasma processing of the spectacle lens base material are performed as pre-processing.

JP 2008-96986 A Japanese Patent Laid-Open No. 2005-224791

  However, Patent Document 1 describes cleaning by alkali treatment, but does not describe pretreatment for forming an antifogging film. Further, in the plasma processing generally used such as the method described in Patent Document 2, processing unevenness is likely to occur, and the lens surface may be damaged by impact. Further, the antifogging film described in Patent Document 2 improves the film strength by the components forming the film and is fixed to the lens surface, and cannot be said to have sufficient durability.

  Therefore, an object of the present invention is to provide a method for manufacturing a spectacle lens having a highly durable hydrophilic film.

As a result of intensive research, the present inventors have changed the conventional plasma treatment to an eyeglass lens base material whose outermost surface is SiO ₂ , by performing an alkali treatment, and then forming a hydrophilic film. The present inventors have found that the hydrophilic film has high durability and completed the present invention.

That is, the spectacle lens manufacturing method of the present invention is a spectacle lens manufacturing method in which an antifogging layer is provided on a lens base material on which an inorganic antireflection film having a SiO ₂ layer is formed on the outermost surface. The SiO ₂ layer of the inorganic antireflection film is treated with a treatment liquid containing an inorganic alkali, and then a hydrophilic film is formed.

According to this invention, a spectacle lens having a highly durable hydrophilic film as an antifogging layer can be produced. In the present invention, the inorganic anti-reflective film lens substrate is formed having a layer of SiO ₂ on the outermost surface, since a layer of SiO ₂ inorganic antireflection film alkaline treatment, SiO ₂ is activated, the activation It is considered that the SiO ₂ thus formed is chemically bonded to the hydrophilic film to be formed and fixed to the spectacle lens substrate by the chemical bond. Therefore, a highly durable hydrophilic film can be formed on the spectacle lens.

Here, since the outermost surface of the spectacle lens substrate is a layer of SiO ₂ , for example, compared with general soda-lime glass, it has more reaction sites and more bonds with the hydrophilic film. It is thought to occur. Therefore, it is considered that the adhesion of the hydrophilic film can be further increased, and as a result, the durability of the hydrophilic film can be improved.
In addition, the process by the process liquid containing an inorganic alkali is an alkali process performed in the procedure similar to a washing | cleaning process using the process liquid containing the inorganic alkali used in the washing process of an optical article.

And in the manufacturing method of the spectacle lens of this invention, it is preferable that the said hydrophilic film | membrane is formed by processing the organosilane which has a hydrolysable group which can be converted into a silanol group by hydrolysis.
According to this invention, the organosilane is converted into a silanol group by hydrolysis, and the silanol group and activated SiO ₂ react to form a chemical bond to form a hydrophilic film. Therefore, a highly durable hydrophilic film can be formed on the spectacle lens.

  Furthermore, in the method for producing a spectacle lens of the present invention, the hydrophilic film is a simple substance of organosilane or a hydrolyzate thereof containing at least one or more sulfur in a non-coupling site, or a condensate of dimer or more, It is preferably an organosilane containing at least one or more sulfur at the coupling site and a hydrolyzate alone or a dimer or more condensate.

  According to the present invention, at least one or more sulfur in the non-coupling site, or an organosilane or a hydrolyzate thereof containing at least one or more sulfur in the non-coupling site, or a condensate of the dimer or more. A dimer or higher condensate reacts between a dimer or higher condensate and a dimer or higher condensate between a single molecule and a single molecule, The site | part which bridge | crosslinks in a hydrophilic film | membrane will exist. Since this serves as a glue filling the gap, the strength of the membrane is increased, and as a result, the durability of the hydrophilic membrane can be improved.

In the eyeglass lens manufacturing method of the present invention, the treatment with the alkali-containing treatment liquid includes the inorganic alkali containing a lens base material on which an inorganic antireflection film having a SiO ₂ layer is formed on the outermost surface. It is preferable to immerse in the treatment liquid for 0.5 minutes or more and 30 minutes or less.
According to the present invention, the outermost SiO ₂ is sufficiently activated by the treatment liquid containing an alkali and becomes in a state capable of reacting with a silanol group. Therefore, when a hydrophilic film is subsequently formed, it reacts with a silanol group to form a chemical bond, so that a highly durable hydrophilic film can be formed.

Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.
The spectacle lens manufactured by the spectacle lens manufacturing method in the present embodiment is a plastic lens for spectacles. The spectacle lens includes a lens base material, a primer layer formed on the surface of the lens base material, a hard coat layer formed on the surface of the primer layer, and an antireflection formed on the surface of the hard coat layer. And an antifogging layer formed on the surface of the antireflection layer.

(1. Lens substrate)
The refractive index of the lens base material is not particularly limited. As such a lens material, polythiourethane type produced by reacting diethylene glycol bisallyl carbonate (CR-39), polycarbonate, or a compound having an isocyanate group or an isothiocyanate group with a compound having a mercapto group. Examples include plastic.

(2. Primer layer)
The primer layer is formed on the surface of the lens substrate and plays a role of improving the durability of the entire surface treatment film.
Such a primer layer is preferably formed using a coating composition containing an organic resin polymer having polarity and metal oxide fine particles containing titanium oxide. As the organic resin polymer, various resins such as a polyester resin, a polyurethane resin, an epoxy resin, a melamine resin, a polyolefin resin, a urethane acrylate resin, and an epoxy acrylate resin can be used.
In the application of the coating composition, the surface of the lens substrate is previously subjected to alkali treatment, acid treatment, surfactant treatment, peeling with inorganic or organic fine particles for the purpose of improving the adhesion between the lens substrate and the primer film. It is effective to perform polishing treatment or plasma treatment. As a method for applying / curing the coating composition, the coating composition is applied by a dipping method, a spin coating method, a spray coating method, a roll coating method, a flow coating method, or the like. The primer layer can be formed by heating / drying at a temperature for several hours.
The thickness of the primer layer is preferably in the range of 0.01 μm to 50 μm. If the primer layer is too thin, basic performances such as water resistance and impact resistance cannot be achieved. If it is too thick, surface smoothness will be impaired, or appearance defects such as optical distortion, white turbidity and cloudiness will occur. There is a case.

(3. Hard coat layer)
The hard coat layer is preferably formed using a coating composition containing metal oxide fine particles containing titanium oxide and an organosilicon compound represented by the formula (1).
R ¹ R ² _n SiX ¹ _3-n (1)
(In the formula, R ¹ is an organic group having a polymerizable reactive group, R ² is a hydrocarbon group having 1 to 6 carbon atoms, X ¹ is a hydrolytic group, and n is 0 or 1. is there.)
Titanium oxide preferably has a rutile crystal structure from the viewpoint of weather resistance and light resistance.
Examples of the organosilicon compound include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, and γ-glycid. Examples include xylpropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, and the like.

When producing a hard coat liquid, it is preferable to mix a sol in which metal oxide fine particles are dispersed with an organosilicon compound. The compounding amount of the metal oxide fine particles is determined by the hardness, refractive index, etc. of the hard coat layer, but it is 5% by mass or more and 80% by mass or less, particularly 10% by mass or more of the solid content in the hard coat liquid. It is preferable that it is 60 mass% or less.
As a coating liquid application / curing method, a coating composition is applied by a dipping method, a spin coating method, a spray coating method, a roll coating method, or a flow coating method, and then at a temperature of 40 ° C. or more and 200 ° C. or less. A hard coat film is formed by heating and drying for a period of time. In addition, it is preferable that the film thickness of a hard-coat layer is 0.05 micrometer or more and 30 micrometers or less. If the film thickness is less than 0.05 μm, the basic performance cannot be realized. On the other hand, if the film thickness exceeds 30 μm, the surface smoothness may be impaired, or optical distortion may occur.

(4. Antireflection layer)
The antireflection layer has a refractive index lower by 0.10 or more than the refractive index of the hard coat layer, and is composed of a single layer or multiple layers of an inorganic thin layer or an organic thin layer having a layer thickness of 50 nm or more and 150 nm or less, the outermost layer is a SiO _2.
For multilayer, in addition to SiO ₂ as the material of the inorganic thin layer other than the outermost _{layer, 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 , WO _{3 and the} like, and these can be used alone or in combination of two or more. In the case of a plastic lens, SiO ₂ , ZrO ₂ , TiO ₂ , and Ta ₂ O ₅ that can be vacuum-deposited at a low temperature are preferable.

(5. Anti-fogging layer)
The antifogging layer is obtained by treating SiO ₂ as the outermost layer of the antireflection layer with a treatment liquid containing inorganic alkali (also referred to as an alkali treatment liquid) and activating the antifogging agent described later. It is formed by applying to the surface.

(Alkali treatment method)
In the present embodiment, application of an ultrasonic cleaning method is preferable as the alkali treatment method. Further, if necessary, a method using a known physical force, for example, an immersion method, an immersion rocking method, a spray method, a hand wiping method, or the like can be used alone or in combination. Cleaning conditions such as temperature and cleaning time of the alkali treatment method are not particularly limited, and can be appropriately adjusted according to the type of lens material and the surface state. Specifically, for example, the temperature of the alkali treatment method is preferably 20 ° C. or more and 90 ° C. or less, and more preferably 35 ° C. or more and 80 ° C. or less for reducing the alkali treatment property and the evaporation amount. The processing time is about 0.5 minutes or more and 30 minutes or less. At this time, the ultrasonic oscillation frequency is preferably in the range of 20 kHz to 100 kHz.

  When the antifogging layer is formed after the alkali treatment, a general removal process may be performed in order to remove excess alkali treatment liquid remaining on the lens surface. As the removing liquid, ultrapure water, pure water, ion-exchanged water, distilled water, a water-soluble organic solvent alone or a mixture of two or more kinds can be used. In this removing step, the physical force is not particularly limited, and a commonly used process using a known physical force can be used. For example, various processes such as an immersion method, an ultrasonic cleaning method, an immersion rocking method, a spray method, and a hand wiping method can be used alone or in combination.

  Furthermore, the process by the above-mentioned physical force can be performed as a finishing process after the removal process. In this case, in order to improve the drying property, it is preferable to use a solvent having excellent volatility that is mixed with water and azeotroped. Specifically, isopropanol, acetone and the like are preferably used.

(Formation of antifogging layer) Thus, an antifogging layer is formed by apply | coating an antifogging agent to the base-material surface activated by the alkali treatment. Anti-fogging agent application methods include the dip coating method, spin coating method, barcode coating method, spray coating method, etc., but when importance is placed on productivity and uniformity after application, the dip coating method, spin coating method, etc. The method is preferred. And the base material which apply | coated the antifogging agent is heat-processed, and it dry-hardens. This step of drying and curing is performed to remove the solvent in the antifogging agent and complete the reaction of the organosilane. The conditions for the heat treatment are not particularly limited as long as the solvent evaporates and the reaction of the organosilane suitably occurs and does not affect the article itself. Preferably, heat treatment is performed at a temperature range of 50 ° C. to 300 ° C. for 1 minute to 24 hours. Since the reaction rate depends on the temperature, the lower the heating temperature, the longer the treatment. If the heating temperature exceeds 300 ° C, it should be avoided because organosilane or its hydrolyzate containing at least one sulfur in the non-coupling site, or organosilane and its hydrolyzate may be decomposed. Better. A heat treatment at 50 ° C. to 150 ° C. for 1 minute to 12 hours is still preferable in designing the process.

  A surfactant may be applied to the surface of the antifogging layer for the purpose of further improving the antifogging properties. Examples of the surfactant to be applied include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and a double-sided surfactant. Specifically, the surfactant described above can be used. One kind of surfactant or a mixture of two or more kinds of surfactants may be used. As the surfactant, any coating method may be used as long as it is a method applied to the surface of the antifogging article.

(Alkaline treatment liquid)
In the present embodiment, activation of SiO ₂ as the outermost layer of the antireflection layer by alkali treatment is preferably performed using an alkali treatment liquid described below.
The alkali treatment liquid of this embodiment contains 1% by mass or more and 50% by mass or less of an inorganic alkali, and one or more solvents selected from alcohols represented by the following formula (1) and water.
R ₁ (OR ₂ ) _n OH (1)
(Wherein, R ₁ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group, or phenethyl group, R ₂ represents a hydrogen atom .n is R ₁ which represents an alkylene group having 2 to 4 carbon atoms ) Represents an integer of 10 or less, and when R ₁ is other than a hydrogen atom, it represents 0 or an integer of 10 or less.)

  In this embodiment, the concentration of the inorganic alkali is preferably 1% by mass or more and 50% by mass or less. If it is less than 1% by mass, sufficient adhesion of the antifogging layer cannot be obtained, and if it exceeds 50% by mass, the smoothness of the lens surface may be impaired and fogging may occur. Specific examples of the inorganic alkali include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Usually, each can be used alone or in admixture of two or more thereof.

The alcohol represented by the formula (1) can be usually used alone or in admixture of two or more thereof.

Specific examples of the alcohol include alcohols having a linear or branched alkyl group such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, hexanol, and octanol; phenol, cresol, benzyl alcohol, and phenethyl. Aromatic alcohols such as alcohol; alicyclic alcohols such as cyclohexanol; ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, etc. It is done. Furthermore, it was obtained by reacting a C2-C4 alkylene oxide such as ethylene, propylene, butylene, etc., in liquid or gaseous form, alone or in plural, while heating under a catalyst such as sodium hydroxide. Diols such as: alcohols in which one terminal of the diol is substituted with a methoxy group, an ethoxy group, an isopropoxy group, or a butoxy group.
Alcohol can be used individually or in mixture of 2 or more types.

  In the present embodiment, the adhesion of the antifogging layer is further improved by further adding a nonionic surfactant and an anionic surfactant, or any one of them to the aforementioned alkali treatment liquid composition. be able to. Specific examples of the aforementioned nonionic surfactant are polyethylene glycol lauryl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, polyethylene glycol oleyl ether, polyethylene glycol nonyl phenyl ether, polyethylene glycol octyl phenyl ether, and the like. Or 2 or more types can be mixed and used. The HLB of the nonionic surfactant is preferably in the range of 5 to 18, particularly preferably in the range of 9 to 16.

  Specific examples of the aforementioned anionic surfactants include sodium oleate, sodium stearate, sodium alkyl sulfonate, sodium octyl sulfosuccinate, sodium linear alkyl benzene sulfonate, sodium branched alkyl benzene sulfonate, and the like. Or 2 or more types can be mixed and used. Moreover, the above-mentioned nonionic surfactant and anionic surfactant can also be used together.

  The content of any one of these nonionic surfactants and anionic surfactants is not particularly limited, but in order to express the combined effect, the alkaline treatment liquid of the present embodiment Preferably 0.1 mass% or more and 15 mass% or less are added, More preferably, 0.5 mass% or more and 10 mass% or less are added. 0.5 mass% or more is preferable from the point of the effect of combined use, and 10 mass% or less is preferable from the point that the viscosity of an alkali treatment liquid is moderate, it is excellent in handling property, and removability is also favorable.

  In the alkali treatment liquid of this embodiment, the surface treatment property is enhanced by adding an alcoholic tertiary amine in addition to the inorganic alkali, the alcohol of the formula (1), the nonionic surfactant, and the anionic surfactant. The adhesion of the antifogging layer can be improved.

  As a solvent for the alkaline treatment liquid of this embodiment, in addition to alcohol, ultrapure water, pure water, ion exchange water, distilled water, normal tap water, and the like can be used. Moreover, you may use the mixture of the above-mentioned alcohol and water as a solvent. In the alkaline treatment liquid of the present embodiment, additives such as sequestering agents, antiseptics, rust preventives, antifoaming agents, and antioxidants are used in combination as appropriate, as long as the effects of the present embodiment are not impaired. can do

(Anti-fogging agent)
The antifogging agent used in the present embodiment is preferably an organosilane having a hydrolyzable group that can be converted into a silanol group by hydrolysis, and further contains at least one sulfur in a non-coupling site in the antifogging agent. It is preferable to use an organosilane. The organosilane contains a simple substance and a condensate of a dimer or more. A condensate of a dimer or higher improves the density of hydrophilic groups in the antifogging layer. In addition to the immobilization of the base material and the layer, the organosilane existing alone reacts between the dimer or higher condensate, between the dimer or higher condensate and the single molecule, and between the single molecules, and the gap Plays the role of glue to fill up. Thereby, there exists an effect | action which expresses the adhesiveness with the intensity | strength of a layer, and the base-material surface. Furthermore, since the simple substance acting as a paste contains a hydrophilic group, it is possible to exhibit excellent antifogging properties without reducing the density of the hydrophilic group in the film.

  In addition, a dimer or higher condensate of organosilane containing at least one or more sulfur at the non-coupling site in the antifogging agent used in the present embodiment has a sufficient hydrophilic group as long as it is a dimer or higher. Density is obtained. In order to obtain a higher density of hydrophilic groups, it is desirable to include condensates with various condensation degrees of dimers or more, and more preferably, condensates with various degrees of condensation of dimers or more. It is preferable that more than the larger one is included and the filling rate in the layer does not decrease.

  Suitable hydrophilic organic solvents used in the antifogging agent used in this embodiment include alcohols such as methanol, ethanol, propanol and butanol, glycols such as ethylene glycol and propylene glycol, glycerin and propylene glycol monomethyl ether. Examples thereof include glycol ethers, ketones such as acetone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, and water. The hydrophilic organic solvent may be only one kind or a mixed solvent of two or more kinds.

  The content of organosilane containing at least one sulfur in the non-coupling site is preferably 0.1% by mass or more and 25% by mass or less. When the amount is less than 0.1% by mass, the antifogging layer becomes thin and there is a problem in durability. Even if it is used at a concentration exceeding 25% by mass, no change is observed in the thickness and performance of the antifogging layer, resulting in an economic disadvantage. In the case of spectacle lenses, depending on the layer thickness of the film formed on the surface, the reflection characteristics of the surface must be changed, the light reflectance and transmittance must be changed, and the optical characteristics must not be changed. In this case, the content is preferably 0.1% by mass or more and 2% by mass or less.

  Furthermore, the antifogging agent used in the present embodiment can be mixed with a surfactant in order to improve the uniformity and appearance of the antifogging layer. Surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants, double-sided surfactants, and reactive derivatives thereof can be mentioned. In view of the interaction, anionic surfactants are preferable, and anionic surfactants, in which the anionic group is sulfuric acid, sulfate, sulfonic acid, or sulfonate, are more preferable. The surfactant to be used may be one kind or a mixture of two or more kinds. The surfactant can be mixed within a range that does not impair the strength of the antifogging layer. Therefore, it is possible to mix organosilane containing at least one sulfur at the non-coupling site or its hydrolyzate, or organosilane and its hydrolyzate in the range of 1% by mass to 50% by mass. It is.

  Specifically, examples of the anionic surfactant include sodium lauryl sulfate, higher alcohol sodium sulfate, and alkyl sulfate sulfonates such as sodium lauryl sulfate triethanolamine; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; sodium alkylnaphthalenesulfonate Alkyl sulfosuccinates such as sodium dialkyl sulfosuccinate; Alkyl diphenyl ether disulfonates such as alkyl diphenyl ether disulfonate; Alkyl phosphates such as potassium alkyl phosphate; Polyoxyethylene lauryl ether sodium sulfate Polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, polyoxyethylene Polyoxyethylene alkyl (or alkylallyl) sulfate ester salts such as sodium ethylene alkylphenyl ether sulfate; special reaction type anionic surfactant; special carboxylic acid type surfactant; sodium salt of β-naphthalenesulfonic acid formalin condensate, special Naphthalene sulfonic acid formalin condensate such as sodium salt of aromatic sulfonic acid formalin condensate; special polycarboxylic acid type polymer surfactant; polyoxyethylene alkyl phosphate ester and the like.

  Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether such as polyoxyethylene higher alcohol ether, and polyoxyethylene nonyl. Polyoxyethylene alkyl aryl ethers such as phenyl ether; polyoxyethylene derivatives; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, Sorbitan fatty acid esters such as sorbitan distearate; polyoxyethylene sorbitan monolaurate, polyoxy Polyoxyethylene sorbitan such as Tylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate Fatty acid esters; Polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol tetraoleate; Glycerin fatty acid esters such as glycerol monostearate, glycerol monooleate, and self-emulsifying glycerol monostearate; Polyethylene glycol monolaurate, polyethylene glycol Monostearate, polyethylene glycol distearate, polyethylene glycol Polyoxyethylene fatty acid esters, such as oleate polyoxyethylene alkylamine; is alkyl alkanolamide and the like; polyoxyethylene hydrogenated castor oil.

  Examples of cationic surfactants and double-sided surfactants include alkylamine salts such as coconut amine acetate and stearylamine acetate; lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, distearyldimethylammonium chloride, alkyl pen Quaternary ammonium salts such as dimethyldimethylammonium chloride: alkylbetaines such as laurylbetaine, stearylbetaine, laurylcarboxymethylhydroxyethylimidazolinium betaine; amine oxides such as lauryldimethylamine oxide.

  In addition, an organosilane or a hydrolyzate thereof containing at least one sulfur at a non-coupling site in the antifogging agent used in the present embodiment, or a dimer or more condensate of organosilane and the hydrolyzate thereof. Is 1 mass% or more and less than 70 mass% of the total amount of organosilane. When it is less than 1% by mass, the hydrophilic group density in the layer is low, and sufficient antifogging properties cannot be obtained. On the other hand, when the content is 70% by mass or more, a single organosilane cannot play a sufficient role as a paste, and a sufficient film strength cannot be obtained. In order to obtain higher antifogging performance and layer strength, a simple substance of organosilane or a hydrolyzate thereof containing at least one sulfur in a non-coupling site, or a simple substance of organosilane and a hydrolyzate thereof And the abundance ratio of the condensate of dimer or higher is important. However, since there is an optimum ratio depending on the type of organosilane used, it cannot be limited, but it is more preferable that the condensate of the dimer or more is 5% by mass or more and less than 50% by mass.

  In addition, an organosilane or a hydrolyzate thereof containing at least one sulfur at a non-coupling site in the antifogging agent used in the present embodiment, or an organosilane containing at least one sulfur at a non-coupling site The hydrolyzate thereof contains at least one functional group selected from a sulfonic acid ester group, a thiol group, a sulfide group, a disulfide group, and a sulfonic acid group. The sulfonic acid ester group, thiol group, sulfide group, and disulfide group are preferably oxidized to form a sulfonic acid group or a sulfuric acid group.

  The sulfonic acid ester group, thiol group, sulfide group, and disulfide group may be present at any position on the organosilane or its hydrolyzate, but it was converted to a sulfonic acid or sulfuric acid group for easy expression of hydrophilicity. Sometimes it is preferred to be at the end. The reactive site of organosilane is a group that can be converted into silanol, such as chlorosilane, alkoxysilane, or silazane, and can be condensed and reacted with active groups on the surface of the article.

  Examples of organosilanes or hydrolysates thereof containing at least one sulfur in a non-coupling site include 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3- Mercaptopropyldimethylmethoxysilane, 2-mercaptopropyltriethoxysilane, 2-mercaptopropyltrimethoxysilane, 2-mercaptopropylmethyldimethoxysilane, 2-mercaptopropyldimethylmethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyldimethylmethoxysilane, 2- (2-chloroethylthioethyl) triethoxysilane , Mercaptomethyltrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 2- (2-aminoethylthioethyl) diethoxymethylsilane, dimethoxymethyl-3- (3-phenoxypropylthiopropyl) silane, 3- ( 2-acetoxyethylthiopropyl) dimethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3-trimethoxysilylpropanesulfonic acid isopropyl ester, bis [3- (triethoxysilyl) propyl] tetrasulfide, Examples thereof include bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] sulfide, and 3-trimethoxysilylpropylsulfonic acid.

  In addition, the coupling part of the organosilane containing at least one sulfur in the non-coupling part in the antifogging agent used in the present embodiment is slowly hydrolyzed at a low temperature in a hydrophilic organic solvent and sooner as the temperature becomes higher. And condensation proceeds. Below 0 ° C., the condensation is very slow, and it takes a very long time to produce a condensate of a dimer or higher, and the workability is not good. At temperatures above 70 ° C, the condensation proceeds very quickly and is difficult to control. Therefore, an organosilane containing at least one sulfur in a non-coupling site or a hydrolyzate thereof, or an organosilane and a hydrolyzate thereof are diluted in a hydrophilic organic solvent, and then 0 ° C. or more and 70 ° C. or less. It is preferable to hold for 1 hour or more and 200 hours or less. Furthermore, in order to more stably control the degree of condensation, it is preferable to hold at 0 ° C. or higher and 40 ° C. or lower for 2 hours or longer and 200 hours or shorter.

  When preparing a dimer or higher condensate of organosilane containing at least one or more sulfur in the non-coupling site, together with a method controlled by the storage environment, from acid catalyst, alkali catalyst, amine catalyst, metal compound catalyst You may combine the method of using the 1 or more types of catalyst chosen.

  In addition, an organosilane or a hydrolyzate thereof containing at least one sulfur at a non-coupling site in the antifogging agent used in the present embodiment, or an organosilane containing at least one sulfur at a non-coupling site And at least one non-coupling site by controlling the condensation and hydrolysis of the coupling site of the hydrolyzate thereof with at least one catalyst selected from an acid catalyst, an alkali catalyst, an amine catalyst, and a metal compound catalyst. It is possible to more easily produce an antifogging agent in which a condensate of dimer or higher of organosilane containing sulfur is 1% by mass or more and less than 70% by mass of the total amount of organosilane.

  Examples of the acid catalyst include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, tartaric acid, citric acid, and carbonic acid. Acids that do not have a carboxyl group, such as hydrochloric acid, sulfuric acid, nitric acid, and carbonic acid, have the effect of accelerating the hydrolysis of the organosilane, and the acid having a carboxyl group coordinates with the organosilane, thus suppressing condensation. effective. Therefore, when the acid having no carboxyl group is mixed with the carboxyl group, the degree of condensation can be controlled more easily.

  Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, calcium hydroxide, and an ammonium compound. Specific examples of the amine catalyst include ethylenediamine, N, -dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, n-butylamine, triethylamine, guanidine and other amino acids, glycine and other amino acids, 2-methylimidazole Any of imidazoles such as 2,4-diethylimidazole and 2-phenylimidazole may be used, but from the effect of hydrolyzing and forming a hydrogen bond to the condensate and controlling the condensation reaction, an amine containing a hydroxyl group can be used. preferable.

As the metal compound catalyst, aluminum acetylacetonate, titanium acetylacetonate, metal acetylacetonate such as chromium acetylacetonate, sodium acetate, zinc naphthenate, organic acid metal salts such as tin octylate, SnC _l4, TiC _l4, Examples include Lewis acids such as ZnCl ₂ and magnesium perchlorate. It is generally known that tertiary amines and organotin compound catalysts may be mixed and used in order to enhance the effect. The amount of the catalyst varies depending on the catalyst, so it cannot be generally stated. However, it is desirable to use the catalyst without inhibiting the antifogging property of the layer. Specifically, the amount of the catalyst is based on the solid content in the antifogging agent. , 75% or less is preferable.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

(Preparation of anti-fogging agent)
Preparation of anti-fogging agent A 0.01 mol of 3-trimethoxysilylpropanesulfonic acid isopropyl ester is dissolved in 60 ml of glacial acetic acid, and 35 g of 30% hydrogen peroxide solution is maintained at a liquid temperature of 25 ° C. or higher and 30 ° C. or lower. In the state, it was dripped over 1 hour. After completion of dropping, the mixture was stirred at 25 ° C. for a whole day and night. When this liquid was analyzed by FT-NMR, it was found that the sulfonic acid ester group was oxidized, the methoxy group was hydrolyzed, and trisiloxypropanesulfonic acid was synthesized. Moreover, it was 4 mass% when solid content concentration of the trisiloxypropanesulfonic acid solution was measured.

  This trisiloxypropanesulfonic acid solution was diluted to 0.2% with ethanol to 150 g. N-aminoethylethanolamine 0.1g was mixed here, and it stirred at 30 degreeC for 2 hours (A-1 liquid). When a part of this A-1 solution was diluted 20 times with pure water and analyzed by LC / MS, the presence of a condensate of dimer or higher was confirmed, and the ratio was 40% by mass in the total amount of compounds. It was confirmed that. Next, 50 ppm of sodium lauryl sulfate was added to the A-1 solution with respect to the total amount of the antifogging agent to obtain an antifogging agent A.

Preparation of antifogging agent B 0.01 mol of 3-mercaptopropyltrimethoxysilane was dissolved in 1.19 ml of ethanol, 0.238 g of 0.2N sulfuric acid was added thereto, and the mixture was stirred at 30 ° C. for 2 hours. Hydrolysis was performed. To this was added 77.54 g of 7.6% aqueous hydrogen peroxide, and the mixture was stirred for 24 H in an environment of 60 ° C. to carry out oxidation reaction of thiol group and condensation reaction of silanol group.

  When this liquid was analyzed by FT-NMR, it was found that the mercapto group was oxidized, the methoxy group was hydrolyzed, and trisiloxypropanesulfonic acid was synthesized. When a part of this liquid was diluted 200 times with pure water and analyzed by LC / MS, the presence of a dimer or higher condensate was confirmed, and the ratio was 42% by mass in the total solid content. It was confirmed. Moreover, it was 2.4 mass% when solid content concentration of the trisiloxypropanesulfonic acid solution was measured.

  This trisiloxypropanesulfonic acid solution was diluted with ethanol so that the solid content concentration became 0.15% by mass to obtain 150 g of a diluted solution. To this dilute solution, 100 ppm of sodium dilauryl sulfosuccinate (Nikko Chemicals Nikkor OTP-100) was added to the total amount of antifogging agent to obtain antifogging agent B.

Preparation of antifogging agent C 0.01 mol (4.75 g) of bis [3- (triethoxysilyl) propyl] disulfide was dissolved in 47.5 g of t-butanol, and 1.7 g of 0.1N nitric acid was added at 25 ° C. Stir for 2 hours. When this was analyzed by FT-NMR, it was found that the ethoxy group was hydrolyzed to form bis [3- (trisiloxysilyl) propyl] disulfide.

  1.5 g of this solution was diluted 100 times with ethanol to make a total amount of 150 g. Further, 0.1 g of 1N sodium hydroxide solution was mixed here and stirred at room temperature for 30 minutes (C-1 solution). When a part of this C-1 solution was diluted 20 times with pure water and analyzed by LC / MS, the presence of a condensate of a dimer or higher was confirmed, and the ratio was 30% of the total compound amount. I confirmed that there was. Next, 50 ppm of sodium lauryl sulfate was added to the C-1 solution with respect to the total amount of the antifogging agent to obtain an antifogging agent C.

(Example 1) As a lens material, a plastic lens for spectacles (“Seiko Super Sovereign” manufactured by Seiko Epson Corporation) having a hard coat layer and an antireflection layer (the outermost layer is a SiO ₂ layer) was prepared.
This plastic lens for spectacles was immersed in an isopropanol solution of 4% by mass of potassium hydroxide for 5 minutes and thoroughly washed with pure water. Subsequently, it was immersed in the anti-fogging agent A and applied at a lifting speed of 20 cm / min using a constant speed lifting device.

  Next, the plastic lens for spectacles coated with the anti-fogging agent A was held in a hot air circulating thermostat at 60 ° C. for 4 hours to complete the reaction with the base material to obtain an anti-fog spectacle lens. No defects in appearance such as cloudiness were confirmed in the obtained anti-fog spectacle lens.

(Examples 2-8, Comparative Examples 1-3)
Antifogging spectacle lenses were obtained in the same manner as in Example 1 except that in Examples 2 to 8 and Comparative Examples 1 to 3 were carried out using the antifogging agent and alkali treatment conditions shown in Table 1.

Next, the durability test was implemented about the anti-fogging layer formed in Examples 1-8 and Comparative Examples 1-3, and it evaluated based on the following evaluation method.
(Durability test)
A load of 500 g was applied to the surface of the substrate under flowing pure water, and the substrate was wiped 100 times with a sponge.
(Evaluation method)
(Evaluation 1: Contact angle)
A contact angle meter (DM-700 manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle, and the contact angle of pure water was measured by a droplet method. The contact angle is preferably 7 ° or less from the viewpoint of antifogging properties.
(Evaluation 2: Anti-fogging property)
The anti-fog spectacle lens was held in saturated steam at 40 ° C. for 3 minutes. After holding for 3 minutes, the state of the water film formed on the surface was visually evaluated according to the following evaluation criteria.
：: Uniform water film formation ○: Non-uniform portion of the water film is 10% or more and less than 50% Δ: Non-uniform portion of the water film is 50% or more x: Water droplets on the entire surface These results are shown in Table 1.
In Table 1, IPA represents isopropanol and EtOH represents ethanol.

As can be seen from Table 1, in Examples 1 to 8 and Comparative Examples 1 to 3, the initial contact angle and antifogging properties are both good, but after the durability test, the antifogging properties are reduced in the comparative examples. .
In the durability test, wiping with running water is performed. However, wiping with running water to reduce the antifogging property means that the reaction of the molecules constituting the antifogging agent with the substrate is insufficient. On the other hand, in Examples 1-8 which performed the alkali treatment, the fall of anti-fogging property was not seen after the endurance test. That is, the surface of the base material is activated by the alkali treatment, and the number of reaction sites with the molecules constituting the antifogging agent increases, whereby the molecules constituting the antifogging agent react and bind tightly on the substrate. It is thought that this is because of being fixed.
In Example 1, the antifogging property after the durability test is slightly lowered. This is thought to be because the alkali treatment time is shorter than in Example 2, the density of the silanol groups produced is reduced, and the number of reactive sites with the molecules constituting the antifogging agent is reduced. In addition, the alkali treatment time in Example 3 is longer than that in Example 2. As a result, the surface of the substrate is roughened to form a surface fragile layer (WBL), or the SiO ₂ layer is thinned, and the interference color is considered to have changed. In Example 6, when the solvent of the alkaline treatment liquid is water, the antifogging property after the durability test is slightly lowered. This is thought to be because the wettability of the solvent is poor compared to isopropanol and ethanol.

(Comparative Examples 4 to 9)
For Comparative Examples 4 to 9, soda lime glass (SCHOTT B270) or thiourethane resin plastic lens (“Seiko Super Sovereign” manufactured by Seiko Epson Corporation) was used as a lens material, and the antifogging agents and alkali treatment shown in Table 2 were used. Using conditions, an anti-fog spectacle lens was obtained in the same manner as in Example 1. The obtained anti-fog spectacle lens was evaluated by the evaluation method. The results are shown in Table 2.

As shown in Table 2, in the case of the glass substrate, when the alkali treatment time is increased, the initial antifogging property is improved, but the durability is inferior to that of the example. Further, the anti-fogging property was not expressed in the plastic lens even in the initial state.
As described above, the antifogging property in the case of using the glass substrate and the plastic substrate was inferior to that of the example. That is, the alkali treatment of the present invention is effective for a lens substrate having an antireflection film whose outermost layer is a SiO ₂ layer. The outermost layer of the lens substrate used in the examples is 100% SiO ₂ . On the other hand, since the glass substrate used in the comparative example is soda-lime glass, it contains about 30% of components other than SiO ₂ such as Na. It is considered that components other than SiO ₂ are not easily activated by alkali treatment, and it is difficult to form a bond with molecules constituting the antifogging agent, and as a result, the durability of the antifogging layer is not improved. .

Claims (4)

A method for producing a spectacle lens in which an antifogging layer is provided on a lens substrate on which an inorganic antireflection film having a layer of SiO ₂ is formed on the outermost surface,
The SiO ₂ layer of the inorganic antireflection film is treated with a treatment liquid containing an inorganic alkali,
Next, a method for producing a spectacle lens, comprising forming a hydrophilic film. In the manufacturing method of the spectacle lens according to claim 1,
The said hydrophilic film | membrane is formed by processing the organosilane which has a hydrolysable group which can be converted into a silanol group by hydrolysis, The manufacturing method of the spectacle lens characterized by the above-mentioned. In the manufacturing method of the spectacle lens of Claim 1 or Claim 2,
The hydrophilic membrane is composed of an organosilane or a hydrolyzate thereof containing at least one sulfur at a non-coupling site, or a condensate of at least one dimer, or at least one sulfur at a non-coupling site. A method for producing a spectacle lens, which is a simple substance or a condensate of a dimer or more of an organosilane and a hydrolyzate thereof. In the manufacturing method of the spectacle lens in any one of Claims 1-3,
In the treatment with the alkali-containing treatment liquid, the lens base material on which the inorganic antireflection film having the SiO ₂ layer is formed on the outermost surface is applied to the treatment liquid containing the inorganic alkali within 0.5 minutes to 30 minutes. A method for manufacturing a spectacle lens, comprising dipping.