JP6026085B2 - Method for producing coating liquid for film formation, and method for producing eyeglass lens - Google Patents

Description

  The present invention relates to a coating solution for film formation and a coating film.

For example, a technique for forming an organic antireflection film on the surface of a plastic lens such as an eyeglass lens is widely known. As a coating solution for forming an organic antireflection film, for example, a coating solution described in Patent Document 1 is known.
The coating liquid described in Patent Document 1 is manufactured as follows. First, an organosilicon compound having a fluorine atom is diluted with an organic solvent, and further an organosilicon compound having an epoxy group is added thereto. Then, if necessary, hydrolytic condensation polymerization is performed by adding water or dilute hydrochloric acid, acetic acid or the like. Next, a dispersion liquid in which silica-based fine particles having an average particle diameter of 1 to 150 nm are colloidally dispersed in an organic solvent is added. Thereafter, if necessary, a curing catalyst, a photopolymerization initiator, an acid generator, a surfactant, an ultraviolet absorber, an antioxidant and the like are added and sufficiently stirred. The coating liquid is manufactured as described above.
However, the present inventors have observed and tested an antireflection film formed using this coating solution, and found that silica-based fine particles are aggregated in the antireflection film. When such agglomeration of silica-based fine particles occurs, it is difficult to form a dense coating film, and there is a problem that water resistance, chemical resistance, heat resistance, and scratch resistance are lowered.

JP 2007-102096 A

  An object of the present invention is to provide a coating solution for film formation capable of forming a dense coating film and a dense coating film formed using the coating solution for film formation.

Such an object is achieved by the present invention described below.
The film-forming coating solution of the present invention comprises a binder component containing a siloxane oligomer having a crosslinked structure, and a plurality of silica-based fine particles grafted with the chain siloxane oligomer on the surface, and has a pH of 5.0 to 7 0.0.
Thereby, the coating liquid for film-forming which can form a dense coating film can be provided.

The film-forming coating liquid of the present invention is preferably used for forming an antireflection film.
Thereby, for example, a coating liquid for film formation for forming an antireflection film formed on a lens (plastic lens) such as an eyeglass lens is obtained.
In the coating liquid for film formation of the present invention, the silica-based fine particles are preferably hollow silica particles.
Thereby, it becomes the coating liquid for film-forming which can form a coating film with a low refractive index.

In the coating liquid for film formation of the present invention, acidic hydrolysis is carried out into a silane coupling agent containing at least one of a silane compound represented by the following general formula (1) and a halogenated silane represented by the following general formula (2). A catalyst is added, and at least one of the silane compound and the halogenated silane is hydrolyzed and polycondensed in an acidic environment to obtain a liquid containing a chain siloxane oligomer, and the silica-based fine particles are added to the liquid. In addition, it is preferably obtained by hydrolysis / condensation polymerization of the siloxane oligomer in an environment of pH 5.0 to 7.0.
R ¹ _n R ² _p SiZ _{4- (n + p)} (1)
^(Wherein, R 1, ^{R 2} are, .Z hydrolyzable group containing at least one epoxy group in the organic group having 1 to 16 carbon atoms .n, p is, 1 ≦ an integer of 0 to 2 n + p ≦ 3.)
X _m R ³ _3-m Si-Y-SiR ³ _3-m X _m (2)
(In the formula, R ³ is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Y is a divalent organic group containing one or more fluorine atoms. X is a hydrolyzable group. M is an integer of 1 to 3. .)
Thereby, the coating liquid for film formation can be manufactured easily.

In the coating solution for film formation of the present invention, the reaction speed of the condensation polymerization reaction is increased in the reaction in which the silica-based fine particles are added to the liquid and the siloxane oligomer is hydrolyzed / condensed in an environment of pH 5.0 to 7.0. It is preferable that this is faster than the rate of the hydrolysis reaction.
Thereby, more siloxane oligomer of a crosslinked structure can be produced | generated. Furthermore, aggregation of silica-based fine particles can be prevented or suppressed.

In the coating liquid for film formation of the present invention, the liquid contains a cyclic siloxane oligomer together with the chain siloxane oligomer, and the chain siloxane oligomer is more than the cyclic siloxane oligomer. It is preferably included.
Thereby, the coating liquid for film-forming which can form a denser coating film can be manufactured.

In the film-forming coating solution of the present invention, the silane coupling agent contains a silane compound represented by the general formula (1) and a halogenated silane represented by the general formula (2). preferable.
Thereby, it becomes a coating liquid for film formation which can form a film excellent in antireflection property, antifouling property and water repellency.
The coating film of the present invention is characterized by being formed using the coating solution for film formation of the present invention.
Thereby, a dense coating film can be provided.

It is typical sectional drawing which shows the coating film concerning suitable embodiment of this invention. It is the graph which showed the relationship between pH value of silica sol, and reaction rate. It is an optical microscope photograph of the coating film of an Example and a comparative example.

Hereinafter, the film-forming coating solution and coating film of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
FIG. 1 is a schematic cross-sectional view showing a coating film according to a preferred embodiment of the present invention, and FIG. 2 is a graph showing the relationship between the pH value of silica sol and the reaction rate. In the following, for convenience of explanation, the upper side in FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.

1. Film-forming coating solution The film-forming coating solution of the present invention comprises a binder component containing a crosslinked siloxane oligomer and silica-based fine particles grafted with a chain siloxane oligomer on the surface, and has a pH of 5.0. -7.0. The coating film (the coating film of the present invention) formed using such a coating solution for film formation becomes dense and has excellent adhesion, film strength, water resistance, chemical resistance, heat resistance and scratch resistance. Can demonstrate its sexuality.
Moreover, the refractive index of the coating film formed with the film-forming coating solution is not particularly limited, but is preferably 1.40 or less. Thereby, the coating film can exhibit excellent antireflection performance, and the coating film can be used as an antireflection film.

[Binder component]
The binder component may contain, for example, a linear siloxane oligomer in addition to the siloxane oligomer having a crosslinked structure. In this case, the content of the crosslinked structure siloxane oligomer in the binder component is preferably larger than the content of the linear siloxane oligomer. More specifically, the weight ratio of the crosslinked siloxane oligomer to the linear siloxane oligomer in the binder component (crosslinked siloxane oligomer: linear siloxane oligomer) is 7: 3 to 9.5: 0. It is preferably about 5. Thereby, the quantity of the siloxane oligomer of a crosslinked structure increases, and the coating film formed into a film using the film-forming coating liquid can be made dense.
Thus, by including the siloxane oligomer having a crosslinked structure as the binder component, the coating film formed using the coating liquid for film formation has excellent adhesion, film strength, and scratch resistance.

[Silica fine particles]
The silica-based fine particles are not particularly limited, but it is preferable to use hollow silica particles having cavities inside. The hollow silica particles are composed of SiO _2. Since such hollow silica particles have a low refractive index, the refractive index of the coating film 1 can be made sufficiently low, and can be suitably used as an antireflection film. Moreover, since such hollow silica particles are fine particles in the colloidal region and have excellent dispersibility, the silica-based fine particles can effectively prevent or suppress aggregation.

The average particle size of the silica-based fine particles is not particularly limited, but is preferably about 5 nm or more and 200 nm or less, and more preferably 10 nm or more and 100 nm or less. If the average particle size of the silica-based fine particles is smaller than the minimum value, it is difficult to obtain fine particles having a low refractive index, and the antireflection performance of the formed coating film may be insufficient. On the other hand, when the average particle diameter of the silica-based fine particles exceeds the maximum value, many unnecessary irregularities are formed on the surface of the coating film 1, and the haze value of the coating film may be increased.
The refractive index of the silica-based fine particles is preferably as low as possible. Specifically, it is preferably about 1.40 or less, and more preferably 1.35 or less. Thereby, the coating film which can exhibit the more superior antireflection performance can be formed using the coating liquid for film-forming.

  The content of the silica-based fine particles in the coating liquid for film formation is not particularly limited, but the content of the silica-based fine particles in the coating film formed using the coating liquid for film formation is 5.0 wt% as a solid content. % Is preferably about 3% to 30.0% by weight, and more preferably about 10.0% to 20.0% by weight. Thereby, the reflectance of a coating film can be made low and sufficient antireflection performance can be exhibited.

  A chain-like siloxane oligomer is grafted on the surface of such silica-based fine particles. Thereby, the affinity with respect to the binder component and solvent of a silica type fine particle can be made high, and a dispersibility can be improved. Therefore, aggregation of the silica-based fine particles can be prevented, and the silica-based fine particles can be uniformly dispersed in the coating liquid for film formation. Therefore, a coating film formed using such a coating solution for film formation becomes dense and has excellent adhesion, film strength, and scratch resistance.

2. Coating Film Next, the coating film 1 formed with the above-described coating liquid for film formation will be described.
As shown in FIG. 1, the coating film 1 is formed on, for example, a lens substrate (plastic lens) 100 such as a spectacle lens and used as an antireflection film having antireflection performance.
The lens substrate 100 includes a lens fabric 101, a primer layer 102 formed on the surface of the lens fabric 101, and a hard coat layer 103 formed on the surface of the primer layer 102. A coating film 1 is formed on the surface. The lens substrate 100 is not limited to this, and the primer layer 102 and the hard coat layer 103 may be omitted.

[Lens substrate 100]
(Lens fabric 101)
The lens fabric 101 is not particularly limited, and various plastic lenses can be used. More specifically, as the lens fabric 101, for example, a thiourethane plastic lens substrate (manufactured by Seiko Epson Corporation, trade name “Seiko Super Sovereign Fabric”, refractive index 1.67) can be used.

(Primer layer 102)
The primer layer 102 is interposed between the lens fabric 101 and the hard coat layer 103 and is a layer for improving the adhesion. This primer layer 102, for example, expresses the refractive index of the primer (A) having adhesion to both the lens fabric 101 and the hard coat layer 103, and acts as a filler to improve the crosslinking density of the primer layer 102. Then, the lens fabric 101 can be formed by coating a composition containing the component (B) for improving water resistance and weather resistance.

  As the component (A), for example, various resin materials such as polyester resin, polyurethane resin, epoxy resin, melamine resin, polyolefin resin, urethane acrylate resin, and epoxy acrylate resin can be used. On the other hand, as the component (B), for example, metal oxide fine particles containing titanium oxide can be used, and the average particle diameter thereof is, for example, about 1 nm to 200 nm.

(Hard coat layer 103)
The hard coat layer 103 is a layer for protecting the surface of the lens fabric 101. The hard coat layer 103 is not particularly limited, but can be formed by coating the primer layer 102 with a composition containing the following components (C) and (D).

As the component (C), metal oxide particles containing titanium oxide can be used, and the average particle size is, for example, about 1 nm to 200 nm. The titanium oxide contained in the metal oxide particles preferably has a rutile crystal structure. On the other hand, as the component (D), an organosilicon compound represented by the general formula: R ¹ SiX ¹ ₃ (wherein R ¹ is an organic group having 2 or more carbon atoms having a polymerizable reactor, X ¹ is Represents a hydrolyzable group).
The example of the lens substrate 100 has been described above. In addition, before forming the coating film 1 on the lens substrate 100, it is preferable to perform plasma treatment (atmospheric plasma) on the lens substrate 100.

[Coating film 1]
The coating film 1 is obtained by applying a coating solution such as a film formation on the lens substrate 100 and drying it. The method for applying the film forming coating solution is not particularly limited, and for example, a coating method such as a spin coating method, a dip coating method, a roll coating method, a slit coater method, or a transfer method can be used. Among these, it is preferable to use a spin coat method, and this makes the coating film 1 have excellent film thickness uniformity and low dust generation.

The thickness of the coating film 1 is not particularly limited, but is preferably about 50 nm or more and 200 nm or less, more preferably about 80 nm or more and 120 nm or less, and further preferably about 100 nm.
The thermal expansion coefficient of the coating film 1 is preferably substantially equal to the thermal expansion coefficient of the lens fabric (base material) 101. Thereby, when the lens substrate 100 on which the coating film 1 is formed rises in temperature, the lens fabric 101 and the coating film 1 expand to the same extent, so that it is possible to prevent unintended stress from being applied to the coating film 1. it can. Therefore, breakage of the coating film 1, specifically, the generation of cracks can be effectively prevented or suppressed.

The Young's modulus of the coating film 1 is preferably larger than the Young's modulus of the lens fabric 101. Thereby, when the lens cloth 101 is bent by an external force, the coating film 1 can also be easily bent following the bending of the lens cloth 101, so that it is possible to prevent unintentional stress from being applied to the coating film 1. be able to. Therefore, breakage of the coating film 1, specifically, the generation of cracks can be effectively prevented or suppressed.
The refractive index of the coating film 1 is not particularly limited, but is preferably 1.40 or less. Thereby, the outstanding antireflection performance can be exhibited.

3. Next, a method for producing a coating liquid for film formation will be described.
The manufacturing method of the coating liquid for film-forming has the following 1st process and 2nd process.
[First step]
In the first step, an acidic hydrolysis catalyst is added to a silane coupling agent containing a silane compound represented by the following general formula (1) and a halogenated silane represented by the following general formula (2), and a pH of 3.0 to This is a step of obtaining a liquid A containing a chain siloxane oligomer by hydrolyzing and condensation-polymerizing a silane compound and a halogenated silane in an acidic environment of 5.0.

R ¹ _n R ² _p SiZ _{4- (n + p)} (1)
(In formula, R < ¹ >, R < ² > is a C1-C16 organic group and at least one contains an epoxy group. Z is a hydrolysable group. N and p are integers of 0-2, 1 ≦ n + p ≦ 3.)
X _m R ³ _3-m Si-Y-SiR ³ _3-m X _m (2)
(In the formula, R ³ represents a hydrocarbon group having 1 to 6 carbon atoms, Y represents a divalent organic group containing one or more fluorine atoms, and X represents a hydrolyzable group. , M is an integer of 1 to 3.)

The silane compound represented by the formula (1) is appropriately selected according to the purpose such as adhesion to the substrate, hardness and low reflectivity of the resulting coating film, and the life of the composition. Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltriethoxysilane, β-glycid Xylpropyltrimethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, (3,4 -Epoxycyclohexyl) methyltrimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane Emissions, .gamma.-glycidoxypropyl phenyl diethoxy silane, .delta. (3,4-epoxycyclohexyl) butyl triethoxy silane, and the like.
Among these, the silane compound represented by the formula (1) is preferably n + p = 1, that is, a trifunctional silane compound having three (—SiZ groups). Thereby, the chain | strand-shaped siloxane oligomer mentioned later can be produced | generated efficiently.
The content of the silane compound is preferably 0.1 wt% or more and 50.0 wt% or less with respect to the total amount of the silane coupling agent, and is 4.0 wt% or more and 15.0 wt% or less. Is more preferable. Thereby, the coating film 1 can exhibit more excellent antireflection properties, antifouling properties, water repellency, scratch resistance, chemical resistance, and the like.

The halogenated silane represented by the formula (2) is not particularly limited, but the number of fluorine atoms is preferably 4 or more and 50 or less, and more preferably 4 or more and 24 or less. Thereby, the coating film formed using the coating liquid for film formation can exhibit excellent antireflection properties, antifouling properties, water repellency, scratch resistance, chemical resistance, and the like.
When the number of fluorine atoms contained in the halogenated silane represented by the formula (2) is less than the lower limit, depending on the content of the halogenated silane, the above-described effects may not be exhibited sufficiently. There is. On the other hand, when the number of fluorine atoms exceeds the upper limit, depending on the content of the halogenated silane and the like, the density of the coating film may decrease.

As Y in said Formula (2), the thing of the following structure is preferable, for example.
_{-CH 2 CH 2 (CF 2)} n CH 2 CH 2 -
_{-C 2 H 4 -CF (CF 3} ) - (CF 2) n -CF (CF 3) -C 2 H 4 -
(N is an integer of 2 to 20.)
Moreover, as R < ³ > in said Formula (2), what is necessary is just a C1-C6 alkyl group, for example, alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, etc. And a phenyl group. Among these, R ³ is preferably a methyl group for the purpose of obtaining excellent scratch resistance.
Moreover, m in the formula (2) is an integer of 1 to 3, but is preferably 2 or 3, more preferably 3. Thereby, the coating film 1 can be made harder.

X in the formula (2) represents a hydrolyzable group. Specific examples include halogen atoms such as Cl, organooxy groups represented by ORX (RX is a monovalent hydrocarbon group having 1 to 6 carbon atoms), particularly methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy. An alkoxy group such as an isopropenoxy group, an acyloxy group such as an acetoxy group, a ketoxime group such as a methylethylketoxime group, and an alkoxyalkoxy group such as a methoxyethoxy group. Among these, an alkoxy group is preferable, and a silane compound having a methoxy group or an ethoxy group is particularly preferable because it is easy to handle and the reaction during hydrolysis is easily controlled. Examples of such X include the following structures.
_{(CH 3 O) 3 Si-} C 2 H 4 -C 4 F 8 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 -C 6 F 12 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 -C 8 F 16 -C 2 H 4 -Si (OCH 3) 3
_{(C 2 H 5 O) 3} Si-C 2 H 4 -C 4 F 8 -C 2 H 4 -Si (OC 2 H 5) 3
_{(C 2 H 5 O) 3} Si-C 2 H 4 -C 6 F 12 -C 2 H 4 -Si (OC 2 H 5) 3
_{(C 2 H 5 O) 2} (CH 3) Si-C 2 H 4 -C 6 F 12 -C 2 H 4 -Si (CH 3) (OC 2 H 5) 2

  The content of the halogenated silane is preferably 50.0% by weight or more and 99.9% by weight or less with respect to the total amount of the silane coupling agent, and is 85.0% by weight or more and 96.0% by weight. The following is more preferable. Thereby, the coating film formed using the coating liquid for film formation can exhibit more excellent antireflection properties, antifouling properties, water repellency, scratch resistance, chemical resistance, and the like.

  The acidic hydrolysis catalyst comprises a silane compound represented by the formula (1) and a halogenated silane represented by the formula (2) in an acidic environment (preferably in an acidic environment having a pH of 3.0 to 5.0). ) For hydrolysis / condensation polymerization. Examples of such an acid hydrolysis catalyst include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as oxalic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and lactic acid. Can be used.

  Hydrolysis and polycondensation of the silane compound represented by the formula (1) and the halogenated silane represented by the formula (2) yields a chain siloxane oligomer and a cyclic siloxane oligomer. A liquid A containing is obtained. Although not particularly limited, the chain and cyclic siloxane oligomers are about the silane compound represented by the formula (1) or the trimer to pentamer of the halogenated silane represented by the formula (2). The size is preferred.

The liquid A preferably contains more chain-like siloxane oligomer than cyclic siloxane oligomer. Specifically, the weight ratio of the chain siloxane oligomer to the cyclic siloxane oligomer in the liquid A is not particularly limited, but the chain siloxane oligomer: cyclic siloxane oligomer is 8: 2 to 9.5: It is preferably about 0.5. Thereby, the coating liquid for film formation which can form the denser coating film 1 can be obtained. Specifically, by reducing the number of cyclic siloxane oligomers as much as possible, the amount of gaps formed in the ring can be reduced, and as a result, a denser coating film 1 can be formed. .
The reaction time for hydrolysis / condensation polymerization in the first step is not particularly limited, but is preferably about 100 hours or more and 150 hours or less at room temperature, more preferably about 120 hours.

[Second step]
In the second step, silica-based fine particles are added to the liquid A obtained in the first step, and the chain siloxane oligomer contained in the liquid A is hydrolyzed and polycondensed in an environment of pH 5.0 to 7.0. It is a process.
Such silica-based fine particles can be added to the liquid A in a state of being dispersed in a dispersion medium. Thereby, aggregation of the silica-based fine particles can be effectively prevented, and the pH of the mixture with the liquid A can be adjusted to 5.0 to 7.0 by the mutual effect with the dispersion medium.

The dispersion medium for dispersing the silica-based fine particles is not particularly limited, but is preferably neutral or basic. Thereby, pH of the mixture with the liquid A can be 5.0-7.0 comparatively easily.
Examples of such a dispersion medium include water, an organic solvent, or a mixed solvent thereof. Specifically, water such as pure water, ultrapure water, and ion exchange water, alcohols such as methanol, ethanol, isopropanol, n-butanol, and methyl isocarbinol, acetone, 2-butanone, ethyl amyl ketone, diacetone Ketones such as alcohol, isophorone, cyclohexanone, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H- Ethers such as pyran, glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxy Glycol ether acetates such as tilacetate, methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, esters such as ethylene carbonate, aromatic hydrocarbons such as benzene, toluene, xylene, hexane, heptane, iso- Aliphatic hydrocarbons such as octane and cyclohexane, halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane and chlorobenzene, sulfoxides such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, N- Examples include pyrrolidones such as octyl-2-pyrrolidone.

The pH of the dispersion liquid in which the silica-based fine particles are dispersed is not particularly limited as long as the pH of the mixture can be adjusted to 5.0 to 7.0 when mixed with the liquid A. However, the pH is about 7.0. preferable.
By adding such a dispersion to the liquid A, silica-based fine particles are supplied into the liquid A, and the pH of the mixture of the liquid A and the dispersion is set to 5.0 to 7.0. The chain siloxane oligomer contained in the liquid A is hydrolyzed and polycondensed. Thus, a binder component such as a siloxane oligomer having a crosslinked structure formed by bonding a plurality of chain siloxane oligomers or a linear siloxane oligomer, and silica-based fine particles having a chain siloxane oligomer grafted on the surface thereof are included. Liquid B is obtained. As for the binder component, in particular, more siloxane oligomers having a crosslinked structure can be produced.

Hereinafter, the reason why the liquid B is obtained by the second step will be described.
FIG. 2 is a graph showing the relationship between the pH value of silica sol and the reaction rate (Surface Technology Vol. 50, No. 2, pages 161-164, “Simple overview of sol-gel method and its use”, Motoyuki Toki, see ).
As shown in FIG. 2, in the range of pH 5.0 to 7.0, the condensation polymerization reaction rate is faster than the hydrolysis reaction rate. Therefore, by the hydrolysis / condensation polymerization, a binder component such as a siloxane oligomer having a crosslinked structure formed by bonding a plurality of chain siloxane oligomers or a linear siloxane oligomer, and a chain siloxane oligomer are grafted on the surface. Silica-based fine particles are produced.
In addition, although it does not specifically limit as a rate of a hydrolysis reaction about hydrolysis / condensation polymerization, it is preferable that it is 30% or less of the rate of a condensation polymerization reaction.

The reaction time for hydrolysis / condensation polymerization is not particularly limited, but it is preferably about 20 hours to 30 hours at a low temperature of 0 ° C. or more and 20 ° C. or less, preferably about 24 hours at 10 ° C. Is more preferable. As described above, since the polycondensation reaction of the siloxane oligomer is relatively fast in an environment of pH 5.0 to 7.0, the above reaction can be reliably and sufficiently performed by setting the time as described above. it can.
Thereby, the coating liquid for film formation for forming the coating film 1 is obtained. In addition, you may mix a solvent with such a coating liquid for film-forming as needed. Thereby, the coating film 1 can be formed easily.

3. Method for Forming Coating Film 1 Using Film-Forming Coating Solution Coating film 1 can be formed, for example, as follows.
[Coating process]
First, a film-forming coating solution is applied onto the lens substrate 100 (hard coat layer 103). The coating method is not particularly limited, and for example, a coating method such as spin coating, dip coating, roll coating, slit coater, or transfer can be used. Among these, it is preferable to use a spin coating method, and this makes the coating film thickness uniform and low dust generation excellent.

[Baking]
Next, the film-forming coating solution applied on the lens substrate 100 is temporarily fired at a temperature of about 90 ° C. to 110 ° C. for about 1 minute to 10 minutes. The pre-baking can be performed in a nitrogen gas atmosphere or an air atmosphere as an inert gas.
Next, the pre-baked film forming coating solution is finally fired. The main baking is performed at a temperature of about 110 ° C. to 130 ° C. for about 1 hour to 2 hours. The main baking can be performed in an atmosphere of nitrogen gas as an inert gas or in an air atmosphere.
Through the above-described steps, the coating film 1 formed using the film-forming coating solution is formed.
The film forming coating solution and the coating film of the present invention have been described above, but the present invention is not limited to this.

1. Production of coating liquid for film formation (Example 1)
In a stainless steel container, 2.8 parts by weight of an alkoxysilane (silane compound) represented by the following formula (A), 27.8 parts by weight of a halogenated silane represented by the following formula (B), and 0.1 × ^102.9 mol / L nitric acid aqueous solution (152.9 parts by weight) was added and mixed well to obtain a mixed solution having a pH of 4.0 at 25 ° C. This mixed solution was stirred at 25 ° C. for 120 hours to obtain a liquid having a solid content of 10.0% by weight.

  This liquid and a hollow silica-isopropanol dispersion sol (manufactured by Catalytic Chemical Industry Co., Ltd .; solid content concentration 20% by weight, average primary particle diameter 35 nm, outer shell thickness 8 nm) were liquid / hollow silica with a solid content ratio of 70/30. The resulting mixture was mixed well to obtain a mixed solution having a pH of 5.5 at 25 ° C. This mixed solution was stirred at 10 ° C. for 24 hours to obtain a coating solution for film formation having a solid content of 6.3% by weight.

(Comparative Example 1)
In a stainless steel container, 2.8 parts by weight of the silane compound represented by the above formula (A), 27.8 parts by weight of the halogenated silane represented by the above formula (B), and 0.1 mol / L hydrochloric acid 152.9 parts by weight of an aqueous solution was added and mixed well to obtain a mixed solution having a pH of 1.0 at 25 ° C. This mixed solution was stirred at 25 ° C. for 120 hours to obtain a liquid having a solid content of 10.0% by weight.

  This liquid and a hollow silica-isopropanol dispersion sol (manufactured by Catalytic Chemical Industry Co., Ltd .; solid content concentration 20% by weight, average primary particle diameter 35 nm, outer shell thickness 8 nm) were liquid / hollow silica with a solid content ratio of 70/30. The resulting mixture was mixed well to obtain a mixed solution having a pH of 1.0 at 25 ° C. This mixed solution was stirred at 25 ° C. for 24 hours to obtain a coating solution for film formation having a solid content of 6.3% by weight.

2. Coating Film Formation A coating liquid was obtained by adding 420 parts of propylene glycol monomethyl ether to the film-forming coating liquids of Example 1 and Comparative Example 1 described above and diluting them. Next, the coating liquid was applied onto the lens substrate by a spin coating method, and this was temporarily fired at 100 ° C. for 10 minutes in the air. Next, the main calcination was performed in the air at 120 ° C. for 1.5 hours. This formed the coating film. The thickness (average thickness) of this coating film was 100 nm.
The lens substrate was obtained as follows.

(1) Preparation of primer composition In a stainless steel container, 3700 parts by weight of methyl alcohol, 250 parts by weight of water, and 1000 parts by weight of propylene glycol monomethyl ether were added and stirred sufficiently, followed by titanium oxide, zirconium oxide, silicon oxide. 2800 parts by weight of a composite fine particle sol (anatase type crystal structure, methanol dispersion, total solid concentration 20% by weight, Catalytic Kasei Kogyo Co., Ltd., trade name Optlake 1120Z U-25 / A8) was added and mixed. . Next, 2200 parts by weight of polyurethane resin was added and stirred and mixed, then 2 parts by weight of a silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name L-7604) was added and stirring was continued all day and night, and then a 2 μm filter. Filtration was performed to obtain a primer composition.

(2) Preparation of hard coat composition Take 1000 parts by weight of butyl cellosolve in a stainless steel container, add 1200 parts by weight of γ-glycidoxypropyltrimethoxysilane, stir well, and then add 300 moles of 0.1 mol / liter hydrochloric acid. Part was added and stirring was continued for a whole day and night to obtain a silane hydrolyzate. To this silane hydrolyzate, 30 parts by weight of a silicone surfactant (manufactured by Nippon Unicar Co., Ltd .; trade name L-7001) was added and stirred for 1 hour, and then mainly composed of titanium oxide, tin oxide and silicon oxide. 7300 parts by weight of a composite fine particle sol (rutile crystal structure, methanol dispersion, manufactured by Catalyst Kasei Kogyo Co., Ltd .; trade name OPTRAIQUE 1120Z 8RU-25, A17) was added and mixed with stirring for 2 hours. Next, 250 parts by weight of an epoxy resin (manufactured by Nagase Kasei Co., Ltd., trade name Denacol EX-313) was added and stirred for 2 hours, and then 20 parts by weight of iron (III) acetylacetonate was added and stirred for 1 hour. Filtration with a filter gave a hard coat composition.

(3) Formation of primer layer and hard coat layer A thiourethane plastic lens substrate (manufactured by Seiko Epson Corporation, trade name Seiko Super Sovereign Fabric, Refractive Index 1.67) was prepared. Then, the prepared lens base material was subjected to an alkali treatment (immersion in a 2.0 N aqueous potassium hydroxide solution maintained at 50 ° C. for 5 minutes, followed by washing with pure water, and then to 0.5 N sulfuric acid maintained at 25 ° C. It was immersed for 1 minute to neutralize), washed with pure water, dried and allowed to cool. And it is immersed in the primer composition prepared in (1), and the lifting speed is 30 cm / min. And baked at 80 ° C. for 20 minutes to form a primer layer on the lens substrate surface. And the lens base material in which the primer layer was formed was immersed in the hard coat composition prepared in (2), and the lifting speed was 30 cm / min. And baked at 80 ° C. for 30 minutes to form a hard coat layer on the primer layer. Then, it heated for 3 hours in the oven set to 125 degreeC, and obtained the plastic lens in which the primer layer and the hard-coat layer were formed. The formed primer layer had a thickness of 0.5 μm, and the hard coat layer had a thickness of 2.5 μm.
Then, a plastic lens on which a primer layer and a hard coat layer are formed and subjected to plasma treatment (atmospheric plasma) was used as the lens substrate.

3. Evaluation (3-1) Hot Water Resistance After the lens substrate (coating film formed with the coating liquid for film formation in Example 1 and Comparative Example 1) was tumbled in accordance with the shape of the spectacle frame, hot water at 60 ° C. It was immersed in it for 20 days. Thereafter, the lens was taken out from the warm water, cooled with water, scraped off water droplets, and then the state of film peeling of the coating film was visually evaluated according to the following criteria A to D. The results are shown in Table 1 below.
A: No film peeling (peeling area ratio 0%)
B: Almost no film peeling (peeling area ratio of 1 to 19%)
C: Slight peeling (peeling area ratio 20 to 49%)
D: Film peeling occurs (peeling area ratio of 50% or more)

  As is clear from Table 1, the coating film of Example 1 was superior to the coating film of Comparative Example 1 in hot water resistance. Thereby, it is clear that the coating film of Example 1 (coating film of the present invention) is a dense film compared to the coating film of Comparative Example 1 (conventional coating film).

(3-2) Silica-based fine particle cohesiveness The coating film formed with the coating liquid for film formation of Example 1 and Comparative Example 1 was observed using an optical microscope (system biological microscope BX50 manufactured by Olympus Corporation). The result is shown in FIG. 3A shows Example 1, and FIG. 3B shows Comparative Example 1.
As is clear from FIG. 3, the coating film of Example 1 has very few points A that appear white compared to the coating film of Comparative Example 1. Specifically, in the range of 0.71 mm (vertical) × 0.95 mm (horizontal), 118 points A were generated in the coating film of Example 1, and were generated in the coating film of Comparative Example 1. The number of points A was 727. That is, in the coating film of Example 1, the point A decreased by 83.8% compared to the coating film of Comparative Example 1.

  Here, the point A is a secondary particle in which silica particles are aggregated. Further, the point A is relatively large, and a part of the point A protrudes from the surface of the coating film to the outside in many cases. Therefore, there is a high possibility that the secondary particles are peeled off from the coating film when the coating film is wiped with a cloth or the like. When such secondary particles are peeled off, cracks are generated from the portions, scratches are spread, and liquid or the like easily enters the film. That is, the more secondary particles, the lower the heat resistance and scratch resistance. Therefore, it is clear that the coating film of Example 1 is superior in heat resistance and scratch resistance as compared with the coating film of Comparative Example 1.

  DESCRIPTION OF SYMBOLS 1 ... Coating film 100 ... Lens substrate 101 ... Lens cloth 102 ... Primer layer 103 ... Hard-coat layer

Claims (9)

A method of manufacturing a film coating solution,
The film-forming coating liquid contains a binder component containing a siloxane oligomer having a crosslinked structure, and a plurality of silica-based fine particles grafted with a chain siloxane oligomer on the surface, and has a pH of 5.0 to 7.0. Yes,
An acidic hydrolysis catalyst is applied to the silane coupling agent containing at least one of the silane compound represented by the following general formula (1) and the halogenated silane represented by the following general formula (2). In addition, by hydrolyzing and polycondensating at least one of the silane compound and the halogenated silane in an acidic environment, a liquid containing a chain siloxane oligomer is obtained, and the silica-based fine particles are added to the liquid, The manufacturing method of the said film-forming coating liquid obtained by hydrolyzing and condensation-polymerizing the said siloxane oligomer in the environment of pH 5.0-7.0.
R ¹ _n R ² _p SiZ _{4- (n + p)} (1)
^(Wherein, R 1, ^{R 2} are, .Z hydrolyzable group containing at least one epoxy group in the organic group having 1 to 16 carbon atoms .n, p is, 1 ≦ an integer of 0 to 2 n + p ≦ 3.)
X _m R ³ _3-m Si-Y-SiR ³ _3-m X _m (2)
(In the formula, R ³ is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Y is a divalent organic group containing one or more fluorine atoms. X is a hydrolyzable group. M is an integer of 1 to 3. .) In the reaction in which the silica-based fine particles are added to the liquid and the siloxane oligomer is hydrolyzed / condensed in an environment of pH 5.0 to 7.0, the speed of the polycondensation reaction is faster than the speed of the hydrolysis reaction. The manufacturing method of the coating liquid for film-forming of Claim 1 . Wherein the liquid, together with the chain-like siloxane oligomers are included cyclic siloxane oligomer, to claim 1 or 2 toward the chain-like siloxane oligomers are contained more than siloxane oligomer of the cyclic The manufacturing method of the coating liquid for film formation as described. The film-forming coating according to claim 1 or 2 , wherein the silane coupling agent contains a silane compound represented by the general formula (1) and a halogenated silane represented by the general formula (2). Liquid manufacturing method. The method for producing a film-forming coating liquid according to claim 1, wherein the film-forming coating liquid is for forming an antireflection film. The method for producing a coating liquid for film formation according to any one of claims 1 to 5, wherein the silica-based fine particles are hollow silica particles. A method for producing a spectacle lens having a coating film on a lens substrate,
The step of forming the coating film by applying a coating liquid for film formation on a lens substrate and drying it,
The film-forming coating liquid contains a binder component containing a siloxane oligomer having a crosslinked structure, and a plurality of silica-based fine particles grafted with a chain siloxane oligomer on the surface, and has a pH of 5.0 to 7.0 . A method for manufacturing the spectacle lens. The method for manufacturing a spectacle lens according to claim 7, wherein the film-forming coating solution is used for forming an antireflection film. The method for manufacturing a spectacle lens according to claim 7 or 8, wherein the silica-based fine particles are hollow silica particles.

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