JP2008073883A - Antistaining article and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistaining article keeping a good durable antistaining layer overlying it and its manufacturing method. <P>SOLUTION: In the antistaining article, the antistaining layer, which is composed the first antistaining layer of a low-molecular weight comprising a fluorine-containing silane compound with a molecular weight of 100-700, and the second antistaining layer of a high-molecular weight overlying the first antistaining layer and comprising a fluorine-containing silane compound with a molecular weight of 1,000-10,000, overlies an organic layer formed of a composition containing a silane compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antifouling article having an antifouling layer formed on a substrate, and a method for producing the antifouling article.

  Conventionally, an optical article having an antireflection layer formed on a surface is known (see, for example, Patent Document 1).

  The thing of this patent document 1 is the optical member which formed the organic antireflection layer which consists of silica type microparticles | fine-particles which have an internal cavity, and an organosilicon compound on transparent base materials, such as a plastic lens.

JP 2005-43572 A

  By the way, when an antifouling layer is formed on an optical member as described in Patent Document 1, the surface state of the organic antireflection layer is rough and the density of active hydrogen groups on the surface is low. The bond interval by the active hydrogen group is widened with the components of the antifouling layer. For this reason, it is difficult to form a bond between the organic antireflection layer and the antifouling layer, and there is a problem that the strength of the antifouling layer is reduced and durability such as dry wiping resistance and alkali resistance is reduced. In particular, the organic antireflection layer formed of a fluorine-containing composition has poor adhesion to the antifouling layer that also contains fluorine, and the problem of durability of the antifouling layer becomes more prominent.

  In view of the above problems, an object of the present invention is to provide an antifouling article on which a favorable and durable antifouling layer is formed, and a method for producing the antifouling article.

The antifouling article of the present invention is a base material having an organic layer formed from a composition of a silane-containing compound, and an antifouling article having a two-layer antifouling layer formed on the organic layer. The antifouling layer is provided on the surface of the organic layer, and is provided on the surface of the first antifouling layer formed of a fluorine-containing silane compound having a molecular weight of 100 to 700, and the first antifouling layer. And a second antifouling layer formed of a fluorine-containing silane compound having a molecular weight of 1000 to 10,000.
According to this invention, the first antifouling layer is formed using the low molecular weight fluorine-containing silane compound having a molecular weight of 100 to 700 on the organic layer formed of the composition containing the silane compound of the antifouling article. Further, a second antifouling layer is formed on the first antifouling layer using a high molecular weight fluorine-containing silane compound having a molecular weight of 1000 to 10,000.
As a result, the first antifouling layer having a low molecular weight enters the concave portion of the organic layer, and active hydrogen groups can be formed at a high density on the surface. The durability is improved by improving the adhesion between the organic layer and the first antifouling layer. Property is improved. In addition, since a high molecular weight second antifouling layer is provided on the first antifouling layer, the active hydrogen group and the antifouling component of the second antifouling layer can be reacted firmly, Peeling of the second antifouling layer can be prevented well, and the antifouling property can be improved satisfactorily by the high antifouling second antifouling layer. Therefore, the adhesion between the organic layer and the antifouling layer is improved, and the durability of the antifouling layer can be improved without reducing the antifouling property of the antifouling article.

In the antifouling article of the present invention, the organic layer is preferably an organic antireflection layer and / or a hard coat layer.
According to the present invention, since the organic layer is an organic antireflection layer or a hard coat layer, the substrate on which the organic antireflection layer or the hard coat layer is formed, for example, an optical member such as a lens is more favorable for the antifouling layer. It becomes possible to prevent contamination. At this time, as described above, since the antifouling layer adheres well to the organic antireflection layer and the hard coat layer, a favorable durable antifouling layer can be formed.

Further, in the method for producing an antifouling article of the present invention, an antifouling layer in which a two-layer antifouling layer is formed on the organic layer of a substrate having an organic layer formed from a composition of a silane-containing compound. A first antifouling layer formed of a fluorine-containing silane compound having a molecular weight of 100 to 700 is formed on the surface of the organic layer, and then the surface of the first antifouling layer is formed. It is preferable to form a second antifouling layer formed of a fluorine-containing silane compound having a molecular weight of 1000 to 10,000.
According to this invention, the first antifouling layer is formed on the organic layer formed of the composition having the silane-containing compound of the antifouling article using the low molecular weight fluorine-containing silane compound having a molecular weight of 100 to 700. The antifouling layer is formed by forming a second antifouling layer on the first antifouling layer using a high molecular weight fluorine-containing silane compound having a molecular weight of 1000 to 10,000.
Thereby, similarly to the said invention, a low molecular-weight 1st antifouling layer can be made to approach into the recessed part of an organic layer, and an active hydrogen group can be formed with high density, and adhesion of an organic layer and a 1st antifouling layer is possible. The durability can be improved by improving the degree. In addition, since a high molecular weight second antifouling layer is provided on the first antifouling layer, the active hydrogen group and the antifouling component of the second antifouling layer can be reacted firmly, Peeling of the second antifouling layer can be prevented well, and the antifouling property can be improved satisfactorily by the high antifouling second antifouling layer. Therefore, as in the above invention, the adhesion between the organic layer and the antifouling layer becomes good, and the durability of the antifouling layer can be improved without reducing the antifouling property of the antifouling article.

Here, in the method for producing an antifouling article of the present invention, the first antifouling layer and the second antifouling layer constituting the antifouling layer are formed by vacuum deposition to form the first antifouling layer. It is preferable to use as a vapor deposition source a mixed composition in which a fluorine-containing silane compound having a molecular weight of 100 to 700 and a fluorine-containing silane compound having a molecular weight of 1000 to 10,000 forming the second antifouling layer are mixed.
According to this invention, a vapor deposition source is prepared in which a fluorine-containing silane compound having a molecular weight of 100 to 700 that forms the first antifouling layer and a fluorine-containing silane compound having a molecular weight of 1000 to 10,000 that forms the second antifouling layer are prepared in advance. By using this vapor deposition source, the low molecular weight fluorine-containing silane compound first evaporates and reaches the organic layer to form the first antifouling layer. The second antifouling layer is continuously formed at the same time when the first antifouling layer is formed by evaporation. Therefore, two layers of the first antifouling layer and the second antifouling layer can be easily formed on the organic layer by one deposition treatment, and the boundary between the first antifouling layer and the second antifouling layer is formed. Therefore, the durability of the antifouling layer can be further improved.

Further, in the method for producing an antifouling article of the present invention, the first antifouling layer and the second antifouling layer constituting the antifouling layer are formed by vacuum deposition to form the first antifouling layer. After forming a first antifouling layer on the organic layer using a fluorine-containing silane compound having a molecular weight of 100 to 700 alone as a deposition source, the fluorine containing silane compound having a molecular weight of 1000 to 10,000 is formed. It is also conceivable to form the second antifouling layer on the surface of the first antifouling layer using a silane compound alone as a deposition source.
According to this invention, after forming the first antifouling layer on the organic layer by vacuum vapor deposition, the second antifouling layer is formed on the first antifouling layer by vacuum vapor deposition. Thereby, a 1st antifouling layer can be reliably formed on an organic layer, and the adhesion degree of an organic layer and a 1st antifouling layer can be improved reliably. Moreover, since a 2nd antifouling layer is formed reliably on a 1st antifouling layer, a favorable antifouling characteristic can be acquired reliably by this high molecular weight 2nd antifouling layer.

  Hereinafter, the plastic lens as the antifouling article according to the present embodiment will be described in detail. In the present embodiment, a plastic lens for spectacles is exemplified as an antifouling article, but the present invention is not limited to this. For example, other lenses such as a camera lens, various parts such as a model part, etc. It is possible to apply to any substrate in which an antifouling layer is formed on a substrate having a surface layer.

  The plastic lens of the present embodiment is configured by stacking a plastic lens base material, a primer layer, a hard coat layer, and an antifouling layer in layers.

[1. (Plastic lens substrate)
The plastic lens base material (hereinafter also referred to as “lens base material”) is not particularly limited, but includes (meth) acrylic resin, styrene resin, carbonate resin, allyl resin, diethylene glycol bisallyl carbonate resin (CR-39). Allyl carbonate resin such as vinyl resin, polyester resin, polyether resin, urethane resin obtained by reaction of isocyanate compound and hydroxy compound such as diethylene glycol, thiourethane resin obtained by reacting isocyanate compound and polythiol compound, intramolecular Examples thereof include transparent resins obtained by curing a polymerizable composition containing a (thio) epoxy compound having one or more disulfide bonds. Among these plastic lens substrates, a polymerizable composition containing a thiourethane resin obtained by reacting an isocyanate compound and a polythiol compound and a (thio) epoxy compound having one or more disulfide bonds in the molecule is cured. The obtained transparent resin is preferable as a plastic lens substrate having a high refractive index. As a specific example of a thiourethane resin obtained by reacting an isocyanate compound with a polythiol compound, for example, a plastic lens base material used in Seiko Super Sovereign (trade name, refractive index: 1.67 manufactured by Seiko Epson Corporation), Seiko Super The plastic lens base material used for Lucius (the Seiko Epson Corporation make, brand name, refractive index 1.60) can be illustrated. Moreover, as a specific example of the transparent resin obtained by curing a polymerizable composition containing a (thio) epoxy compound having one or more disulfide bonds in the molecule, for example, Seiko Prestige (manufactured by Seiko Epson Corporation, trade name, A plastic lens substrate for a refractive index of 1.74) can be exemplified.

[2. (Primer layer)
The primer layer is formed on the outermost surface of the lens substrate and is present at the interface between both the lens substrate and the hard coat layer described later, and has the property of exhibiting adhesion to both the lens substrate and the hard coat layer. It plays a role of improving the durability of the entire surface treatment film. Furthermore, it also has the property as an external shock absorbing layer and has the property of improving impact resistance.

  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.

  The organic resin polymer expresses adhesion to both the lens substrate and the hard coat layer. The metal oxide fine particles can act as a filler to improve the crosslinking density of the primer layer, thereby improving water resistance, weather resistance and light resistance. 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. Among these, a polyester resin can be preferably used from the viewpoint of adhesion to a lens substrate containing a sulfur atom and dispersibility of metal oxide fine particles serving as a filler.

  On the other hand, as the metal oxide fine particles containing titanium oxide, it is preferable to use a composite type containing titanium oxide having a rutile crystal structure from the viewpoint of light resistance. The average particle diameter of the metal oxide fine particles is preferably 1 to 200 nm, more preferably 5 to 30 nm.

  In applying the coating composition (coating solution), the surface of the lens substrate is previously treated with an alkali treatment, acid treatment, surfactant treatment, inorganic or organic for the purpose of improving the adhesion between the lens substrate and the primer film. It is effective to perform peeling / polishing treatment with fine particles and plasma treatment. The coating composition is applied / cured by applying a coating composition by dipping, spin coating, spray coating, roll coating, flow coating, or the like, The primer layer can be formed by heating / drying at a temperature for several hours.

  Moreover, the film thickness of a primer layer is 0.01-50 micrometers, Especially the range of 0.1-30 micrometers is preferable. If the primer layer is too thin, basic performances such as water resistance and impact resistance cannot be achieved. Conversely, if the primer layer is too thick, surface smoothness may be impaired, and appearance defects such as optical distortion, cloudiness, and cloudiness may occur. Sometimes. In addition, in order to avoid generation | occurrence | production of an interference fringe, it is preferable to match | combine the refractive index of a primer layer with the refractive index of a lens base material.

[3. Hard coat layer)
The hard coat layer is formed on the primer layer formed on the lens substrate surface. 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 following 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, and R ² is a hydrocarbon having 1 to 6 carbon atoms.
A containing group, X ¹ is a hydrolyzable group, n is 0 or 1. )

  Titanium oxide preferably has a rutile crystal structure from the viewpoint of weather resistance and light resistance.

The organosilicon compound represented by the formula (1) is a so-called silane coupling agent and serves as a binder resin for the hard coat layer. In Formula (1), R ¹ is an organic group having a polymerizable reactive group, and has 2 or more 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. R ² represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, or a cyclohexyl group, a phenyl group, or the like. It can be illustrated. A methyl group is preferred for obtaining good scratch resistance.

  Examples of the organosilicon compound include vinyl trialkoxysilane, 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. Two or more of these “B component” organosilicon compounds may be used in combination.

  And when manufacturing the hard-coat liquid for forming a hard-coat layer, it is preferable to mix the sol in which the metal oxide microparticles | fine-particles were disperse | distributed, and an organosilicon compound. The compounding amount of the metal oxide fine particles is determined by the hardness and refractive index of the hard coat layer, and is 5 to 80% by mass, particularly 10 to 60% by mass, based on the solid content in the hard coat liquid. 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.

  In addition, it is very useful to contain a polyfunctional epoxy compound in the hard coat layer. The polyfunctional epoxy compound can improve the adhesion of the hard coat layer to the primer layer, and can improve the water resistance of the hard coat layer and the impact resistance as a plastic lens. Examples of the polyfunctional epoxy compound include aliphatic epoxy compounds such as 1,6-hexanediol diglycidyl ether and ethylene glycol diglycidyl ether, isophoronediol diglycidyl ether, and bis-2,2-hydroxycyclohexylpropane diglycidyl ether. And aromatic epoxy compounds such as resorcin diglycidyl ether, bisphenol A diglycidyl ether, and cresol novolac polyglycidyl ether.

  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.

  The coating composition (coating liquid) for forming a hard coat layer thus obtained can be diluted with a solvent and used as necessary. Solvents such as alcohols, esters, ketones, ethers and aromatics are used as the solvent. If necessary, light resistance of small amounts of metal chelate compounds, surfactants, antistatic agents, ultraviolet absorbers, antioxidants, disperse dyes, oil-soluble dyes, pigments, photochromic compounds, hindered amines, hindered phenols, etc. A heat stabilizer or the like can be added to improve the coating property, the curing speed, and the coating performance after curing.

  In addition, 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 to 200 ° C. 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 0.05-30 micrometers. 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 smoothness of the surface may be impaired, or optical distortion may occur. The refractive index of the hard coat layer is preferably matched to the refractive indexes of the lens substrate and the primer layer in order to avoid generation of interference fringes.

[4. Organic antireflection layer
The organic antireflection layer is composed of a single-layer organic film, has a refractive index lower by 0.10 or more than the hard coat layer, and has a film thickness of 50 to 150 nm.

  The refractive index of the organic antireflection layer 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 layer contains the following components (D) and (E).
Component (D): R ³ R ⁴ nSiX ² _3-n (2)
(In the formula (2), R ³ is an organic group having a polymerizable reactive group, R ⁴ is a hydrocarbon group having 1 to 6 carbon atoms, X ² is a hydrolytic group, and n is 0. Or an organosilicon compound as a silane compound represented by 1))
Component (E): Silica-based particles having internal cavities

The organic group having a polymerizable reactive group of R ³ 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 ⁴ in 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 layer 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.

  In addition, although the example in which the single-layer organic antireflection layer is formed is shown, when a lens base material with a low refractive index is used, for example, when the refractive index of the lens base material is 1.60 or less, for example, it is good. In order to obtain antireflection characteristics, an organic antireflection layer may be formed from two organic thin films.

  In this case, the organic antireflection layer is formed of a high refractive index layer located on the lens substrate side and a low refractive index layer located on the atmosphere side. That is, the refractive index of the layer located on the lens substrate side is configured to be higher than the refractive index of the layer located on the atmosphere side.

  The high refractive index layer is preferably formed from a coating composition containing metal oxide fine particles containing titanium oxide and an organosilicon compound.

  Here, as the titanium oxide, for example, metal oxide fine particles having an average particle diameter of 1 to 200 nm including a composite oxide having a rutile type crystal structure composed of titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide. (Composite fine particles).

  As for the organosilicon compound, the organosilicon compound used in the above-described hard coat layer and the organic antireflection layer in a single layer is preferably used.

  The low refractive index layer is preferably formed from a coating agent containing silica-based fine particles having internal cavities (hereinafter also referred to as “hollow silica-based fine particles”) and an organosilicon compound.

  Here, the hollow silica-based fine particles are used because the internal cavity contains a gas or solvent having a refractive index lower than that of silica, so that the refractive index is reduced compared with silica-based fine particles without cavities. This is because a lower refractive index of the refractive index layer is achieved. Silica-based fine particles having internal cavities can be produced by the method described in JP-A-2001-233611, but in the present invention, the average particle diameter is in the range of 1 to 150 nm and the refractive index. Is preferably in the range of 1.16 to 1.39. When the average particle diameter of the particles is less than 1 nm, the void ratio inside the particles becomes small and a desired low refractive index cannot be obtained. On the other hand, when the average particle diameter exceeds 150 nm, the haze of the low refractive index layer increases, which is not preferable. A preferable average particle diameter can be calculated by the following formula.

  Further, the organic silicon compound may be the same as the organic silicon compound used for constituting the hard coat layer, the organic antireflection layer in a single layer, and the high refractive index layer. Furthermore, a fluorine-containing compound may be used as the organosilicon compound.

[5. Antifouling layer)
As described above, the plastic lens in which the primer layer, the hard coat layer and the organic antireflection layer are formed on the lens substrate is further provided with the antireflection layer for the purpose of improving the water and oil repellency performance of the plastic lens surface. An antifouling layer comprising a fluorine-containing silane compound is formed on the substrate. The antifouling layer includes a first antifouling layer formed of a composition containing a low molecular weight fluorine-containing silane compound and a second antifouling layer formed of a composition containing a high molecular weight fluorine-containing silane compound. And two layers.

  A 1st antifouling layer is formed in the air | atmosphere side surface of an organic antireflection layer with the composition containing the fluorine-containing silane compound A with a molecular weight of 100-700. Here, when the molecular weight of the fluorine-containing silane compound A is larger than 700, the fluorine-containing silane compound A cannot enter the recesses on the surface of the organic antireflection layer. For this reason, the bonding interval by the active hydrogen group is wide between the component of the organic antireflection layer and the component of the first antifouling layer, and as a result, it is difficult to form a bond. The strength in the direction substantially perpendicular to the surface of the prevention layer is reduced, and the durability is also reduced. On the other hand, when the molecular weight of the fluorine-containing silane compound is 100 to 700 as described above, the components of the first antifouling layer enter well into the recesses on the surface of the organic antireflection layer, and the active hydrogen group The coupling interval is narrowed. Thereby, the first antifouling layer and the organic antireflection layer are more firmly adhered to each other, the bond strength is increased, and the durability is improved.

  Here, examples of the low molecular weight fluorine-containing silane compound A composing the first antifouling layer include 3,3,3-trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, and heptafluorodecyltrimethoxy. Silane, n-trifluoro (1,1,2,2-tetrahydro) propylsilazane, n-heptafluoro (1,1,2,2-tetrahydro) pentylsilazane, n-nonafluoro (1,1,2,2- Tetrahydro) hexylsilazane, n-tridecafluoro (1,1,2,2-tetrahydro) octylsilazane, n-heptadecafluoro (1,1,2,2-tetrahydro) decylsilazane, octadecyltriethoxysilane, octadecyltrimethoxy Silane, phenyltriethoxysilane, phenyltrimethoxy Silane, heptyl methyldichlorosilane, isobutyl trichlorosilane, octadecyl methyl dimethyl Toshiki silane, and the like hexamethyldisilazane. Furthermore, KP-801 (manufactured by Shin-Etsu Chemical Co., Ltd.), LS-1090 (manufactured by Shin-Etsu Chemical Co., Ltd.), LS-4875 (manufactured by Shin-Etsu Chemical Co., Ltd.), LS-4480 (Shin-Etsu Chemical Industry ( LS-2750 (Shin-Etsu Chemical Co., Ltd.), LS-1640 (Shin-Etsu Chemical Co., Ltd.), LS-410 (Shin-Etsu Chemical Co., Ltd.), LS-7150 (Shin-Etsu Chemical) Industrial Co., Ltd.), TSL-8257 (GE Toshiba Silicone Co., Ltd.), TSL-8233 (GE Toshiba Silicone Co., Ltd.), TSL-8185 (GE Toshiba Silicone Co., Ltd.), TSL-8186 ( Examples include commercially available products such as GE Toshiba Silicone Co., Ltd., TSL-8183 (GE Toshiba Silicone Co., Ltd.), and XC95-A9715 (GE Toshiba Silicone Co., Ltd.).

  The second antifouling layer is formed on the air-side surface of the first antifouling layer with a composition containing a fluorine-containing silane compound B having a molecular weight of 1000 to 10,000. Here, when the molecular weight of the fluorine-containing silane compound B is larger than 10,000, the viscosity increases and the solubility is remarkably lowered, so that it is difficult to use industrially, and it is difficult to form the second antifouling layer. On the other hand, when the molecular weight of the fluorine-containing silane compound B is less than 1000, the strength of the surface of the antifouling layer is lowered and good durability cannot be obtained, and good antifouling properties cannot be obtained. On the other hand, by forming the second antifouling layer with a composition containing a fluorine-containing silane compound having a molecular weight of 1000 to 10,000, the surface strength of the antifouling layer is increased and the antifouling properties of the antifouling layer are also good. It becomes.

  Here, the high molecular weight fluorine-containing silane compound B composing the second antifouling layer is a fluorine-containing silane compound B represented by the following formula (3). Examples of the fluorine-containing silane compound B having such a composition include trade name “OPTOOL DSX” manufactured by Daikin Industries, Ltd.

In the above formula (3), Rf ¹ represents a perfluoroalkyl group. Z represents a fluorine or trifluoromethyl group. a, b, c, d, and e each independently represent an integer of 0 or 1 or more. Here, a + b + c + d + e is at least 1 or more, and the existence order of each repeating unit enclosed by a, b, c, d, e is not limited in the formula. Y represents hydrogen or an alkyl group having 1 to 4 carbon atoms. X ³ represents hydrogen, bromine or iodine. R ⁵ represents a hydroxyl group or a hydrolyzable substituent. R ⁶ represents hydrogen or a monovalent hydrocarbon group. l represents 0, 1 or 2. m represents 1, 2 or 3. n represents an integer of 1 or more.

Rf ¹ represented by the above formula (3) is not particularly limited as long as it is a perfluoroalkyl group constituting an organic fluorine-containing polymer, and examples thereof include linear or branched ones having 1 to 16 carbon atoms. be able to. CF _3- , C ₂ F _5- , and C ₃ F _7- are preferable.

  In the formula (3), a, b, c, d and e represent repeating units of the perfluoropolyether chain constituting the main skeleton of the fluorine-containing silane compound, and as described above, 0 or an integer of 1 or more Yes, it is not particularly limited as long as a + b + c + d + e is 1 or more, but it is particularly preferably 0 to 200 each independently. Furthermore, considering the molecular weight of the fluorine-containing silane compound, it is more preferably 0 to 50 independently. a + b + c + d + e is preferably 1 to 100.

  Further, the order of existence of each repeating unit enclosed by a, b, c, d, e is not limited to the order of the above formula (3), and the order of existence of each of these repeating terminals depends on the configuration of the perfluoropolyether chain. May be different.

  Furthermore, in the above formula (3), Y is not particularly limited as long as it is an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Or may be branched.

Furthermore, in the above formula (3), X ³ represents hydrogen, bromine, or iodine as described above, but when X ³ is bromine or iodine, the radical reactivity of the fluorine-containing silane compound is increased. Therefore, it becomes more convenient to bind other compounds by chemical bonds.

Further, l in the above formula (3) is the number of carbon atoms of an alkylene group present between carbon constituting the perfluoropolyether chain and silicon bonded thereto, and is preferably 0. Furthermore, m represents the number of bonds of the substituent R ⁵ bonded to silicon.

R ⁵ in the above formula (3) is a hydroxyl group or a hydrolyzable substituent as described above, and preferably, for example, halogen, —OR ¹¹ , —OCOR ¹¹ , —OC (R ¹¹ ) ═C ( R ¹² ) ₂ , -ON = C (R ¹¹ ) ₂ , -ON = CR ^{13 and the} like. However, R ¹¹ represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R ¹² represents hydrogen or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ¹³ represents 3 to 6 carbon atoms. Of the divalent aliphatic hydrocarbon group. More preferably, _chlorine, -OCH 3, is _-OC 2 _{H 5.}

R ⁶ in the above formula (3) is hydrogen or a monovalent hydrocarbon group as described above, and preferable examples include methyl, ethyl, propyl, butyl and the like. It may be branched or branched.

  And n in the above formula (3) has no particular upper limit, but is preferably an integer of 1 to 10.

  Further, as the high molecular weight fluorine-containing silane compound B, a fluorine-containing silane compound (perfluoropolyalkylene ether-modified silane) represented by the following formula (4) may be used. Examples of the fluorine-containing silane compound B having such a composition include trade name “KY-130” manufactured by Shin-Etsu Chemical Co., Ltd.

However, in the above formula (4), Rf ² includes a unit represented by the formula: — (C _k F _2k ) O— (wherein k is an integer of 1 to 6), and has no branch. It is a divalent group having a linear perfluoropolyalkylene ether structure. R ⁷ is a monovalent carbon hydrogen group having 1 to 8 carbon atoms. X ⁴ is a hydrolyzable group or a halogen atom. s is an integer of 0 to 2, t is an integer of 1 to 5, and h and i are integers of 2 or 3.

Here, as Rf ² group, what is shown with the following general formula can be illustrated, for example, However, It is not limited to these illustrations. That is, as Rf ² group, -CF2CF2O (CF2CF2CF2O) jCF2CF2- (where j is an integer of 1 or more, preferably 1-50, more preferably 10-40), -CF2 (OC2F4) p- (OCF2) q- (wherein p and q are each 1 or more, preferably 1-50, more preferably 10-40, and p + q is 10-100, preferably 20-90, more preferably 40-80. And the sequence of the repeating units (OC2F4) and (OCF2) is random).

Further, X ⁴ be a hydrolyzable group, it can be exemplified for example, the following. That is, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, an alkoxyalkoxy group such as a methoxydimethoxy group, a methoxyethoxy group, and an ethoxyethoxy group, an allyloxy group, an alkenyloxy group such as an isopropenoxy group, or an acetoxy group, An acyloxy group such as propionyloxy group, butylcarbonyloxy group, benzoyloxy group, or a ketoxime group such as dimethyl ketoxy group, methyl ethyl ketoxime group, diethyl ketoxime group, cyclopentoxime group, cyclohexanoxime group, or N- Amino groups such as methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino group, N, N-diethylamino group and N-cyclohexylamino group; Includes an amide group such as an N-methylacetamide group, an N-ethylacetamide group and an N-methylbenzoamide group, or an aminooxy group such as an N, N-dimethylaminooxy group and an N, N-diethylaminooxy group. . Further, when X ⁴ is a halogen atom, examples thereof include a chlorine atom, a bromine atom, and an iodine atom. Of these, methoxy group, ethoxy group, isopropenoxy group, and chlorine atom are preferable as X ⁴ .

R ⁷ is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group, or a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a phenyl group. And aryl groups such as tolyl group and xylyl group, or aralkyl groups such as benzyl group and phenethyl group, or alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group. Among these, a methyl group is preferable.

  The antifouling layer as described above is formed by a vacuum deposition method. That is, for example, a pellet containing a composition containing the fluorine-containing silane compound A forming the first antifouling layer is impregnated into a vapor deposition source and set in a vacuum vapor deposition machine. Then, a plastic lens on which a primer layer, a hard coat layer, and an organic antireflection layer are formed is introduced into a vacuum deposition machine, and a first antifouling layer is formed on the organic antireflection layer by vacuum deposition. Thereafter, a composition containing the fluorine-containing silane compound B forming the second antifouling layer is impregnated into, for example, pellets and dried to form a vapor deposition source, which is set in a vacuum vapor deposition machine. Then, the plastic lens having the first antifouling layer formed thereon is introduced into a vacuum vapor deposition machine, and the second antifouling layer is formed by vacuum vapor deposition.

  In addition, you may use the method of using the mixed solution with which the fluorine-containing silane compound A and the fluorine-containing silane compound B were mixed as a vapor deposition source. Even in this case, set the vapor deposition source to dry the pellets impregnated with the above mixed solution in a vacuum vapor deposition machine, and introduce a plastic lens with a primer layer, hard coat layer, and organic antireflection layer into this vacuum vapor deposition machine And vacuum deposition. In this case, the low molecular weight fluorine-containing silane compound A is first evaporated to form a first antifouling layer on the organic antireflection layer of the plastic lens. Thereafter, the fluorine-containing silane compound B is gradually evaporated to form a second antifouling layer. In such a method, the first antifouling layer is formed on the surface of the organic antireflection layer, and as it is separated from the organic antireflection layer, a mixed layer of the first antifouling layer and the second antifouling layer is formed, Furthermore, an antifouling layer is formed in the layer form in which a 2nd antifouling layer is formed as it separates from an organic antireflection layer. Even in such a case, since the first antifouling layer is formed adjacent to the organic antireflection layer and the second antifouling layer is formed on the atmosphere side, the degree of adhesion between the organic antireflection layer and the antifouling layer is high. It is possible to form an antifouling layer that is good and excellent in durability and has good antifouling properties.

  In the plastic lens of the present embodiment as described above, as described above, the low molecular weight fluorine-containing silane compound A having a molecular weight of 100 to 700 is formed on the surface of the organic antireflection layer formed from the composition containing the silane compound. A first antifouling layer formed of a composition containing, and a surface of the first antifouling layer formed of a composition containing a high molecular weight fluorine-containing silane compound B having a molecular weight of 1000 to 10,000. A second antifouling layer is formed. For this reason, the low molecular weight fluorine-containing silane compound A enters the concave portion on the surface of the organic antireflection layer, and active hydrogen groups can be formed at a high density with the components of the organic antireflection layer. Accordingly, the degree of adhesion between the organic layer and the first antifouling layer is improved, and these two layers are firmly bonded, so that the durability can be improved. Further, since the second antifouling layer formed from the composition having the high molecular weight fluorine-containing silane compound B is formed on the first antifouling layer, these second antifouling layers are A second antifouling layer having good antifouling properties can be formed on the first antifouling layer, which can be reacted with the active hydrogen groups having a high density. Therefore, an antifouling layer having good durability and good antifouling properties can be formed on the organic antireflection layer.

  Further, the antifouling layer is formed by forming a first antifouling layer by vacuum vapor deposition using a composition having a fluorine-containing silane compound A on the surface of the organic antireflection layer as a vapor deposition source, and thereafter having a fluorine-containing silane compound B. A second antifouling layer is formed on the first antifouling layer by vacuum vapor deposition using the composition as an evaporation source. For this reason, the first antifouling layer can be reliably formed on the surface of the organic antireflection layer, the adhesion between the antifouling layer and the organic reflection layer can be improved, and the durability can be improved. it can. Moreover, since a 2nd antifouling layer can be reliably formed in the surface which contact | connects air | atmosphere on the surface of a 1st antifouling layer, a favorable antifouling characteristic can be acquired. The antifouling layer may be formed by vacuum deposition using a composition having a mixture of fluorine-containing silane compound A and fluorine-containing silane compound B on the surface of the organic antireflection layer as a deposition source. Even in this case, since the low molecular weight fluorine-containing silane compound A evaporates first and the high molecular weight fluorine-containing silane compound B is deposited later, the first antifouling layer is separated from the surface of the organic antireflection layer, The antifouling layer can be formed in the order of the second antifouling layer. Therefore, similarly to the above, the adhesion between the antifouling layer and the organic reflective layer can be improved, the durability can be improved, and good antifouling properties can be obtained. Moreover, since it is not necessary to perform vacuum evaporation twice, an antifouling layer can be formed more easily.

[Modification of Embodiment]
The present invention has been described with reference to preferred embodiments. However, the present invention is not limited to these embodiments, and various improvements and design changes can be made without departing from the scope of the present invention. Is possible.

  For example, in the said embodiment, although the plastic lens in which the antifouling layer was formed on the organic antireflection layer formed with the composition of a silane-containing compound is illustrated, it is not limited to this. For example, in the above example, the plastic lens having the organic antireflection layer has been described. However, for example, a plastic lens in which the organic antireflection layer is not formed may be used. In this case, the plastic lens is formed of a composition having a fluorine-containing silane compound. It is also possible to form the antifouling layer as described above on the hard coat layer. Furthermore, in the plastic lens in which the organic antireflection layer, the hard coat layer, and the primer layer are not formed, the antifouling layer as described above is formed on the plastic lens substrate formed of the composition having a fluorine-containing silane compound. It may be.

  Moreover, in the said embodiment, although the plastic lens was illustrated as an antifouling | stain-proof article, it is applicable to what is a goods which has the surface layer formed of the composition containing a silane compound.

  Next, examples and comparative examples based on the embodiment of the present invention will be described. Specifically, a plastic spectacle lens was manufactured by the method described below, and various evaluations such as reflectance and heat resistance were performed.

(Example 1)
(1) Lens substrate A plastic lens substrate having a refractive index of 1.67 (manufactured by Seiko Epson Corporation, trade name “Seiko Super Sovereign (SSV)”) was used as the lens substrate.

(2) Primer layer 77 g of commercially available aqueous polyester “A-160P” (manufactured by Takamatsu Yushi Co., Ltd., solid content concentration 25%), 220 g of methanol, 31.5 g of propylene glycol nomomethyl ether (PGME), 91.8 g of water, Methanol-dispersed titanium dioxide-zirconium dioxide-silicon dioxide composite fine particle sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration 20% by weight) 78.8 g, silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “L”) -7604 ") 0.1 g was added and stirred for 2 hours to obtain a primer composition solution. For applying the primer composition liquid, an immersion method (pickup speed: 20 cm / min) was used, and the applied lens substrate was heat-cured at 80 ° C. for 20 minutes. The formed primer layer had a thickness of 0.5 μm and a refractive index of 1.67.

(3) Hard coat layer 62.5 g of butyl cetosolve and 67.1 g of γ-glycidoxypropyltrimethoxysilane were mixed. To this mixed solution, 30.7 g of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours and then aged overnight. In this liquid, 325 g of methanol-dispersed titanium dioxide-zirconium dioxide-silicon dioxide composite fine particle sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration 20% by weight), glycerol diglycidyl ether (manufactured by Nagase ChemteX Corp., trade name “ After adding 12.5 g of Denacol Ex-313 "), 1.36 g of Fe (III) acetylacetonate and 0.15 g of a silicone surfactant (product name" L-7001 "manufactured by Nihon Unicar Co., Ltd.) The mixture was added and stirred for 4 hours, and then aged for a whole day and night to obtain a hard coat composition liquid. The hard coat composition liquid was applied by a dipping method (pulling speed of 35 cm / min), followed by heat curing at 80 ° C. for 30 minutes, and further heat curing at 125 ° C. for 180 minutes. The formed hard coat layer had a thickness of 2.0 μm and a refractive index of 1.67.

(4) Organic antireflective film 312.4 parts by weight of methanol is added to 47.8 parts by weight (0.08 mol) of a silane compound represented by the following formula (5), and 4.7 gamma-glycidoxypropyltrimethoxysilane is added. Part by weight (0.02 mol) and 36 parts by weight of a 0.1 mol / liter hydrochloric acid aqueous solution were added and mixed by stirring to obtain a mixed solution. This mixed liquid was stirred for 2 hours in a thermostatic bath at 25 ° C. to obtain a silicone resin having a solid content of 10% by weight.
(CH3O) 3Si-C2H4-C6F12-C2H4-Si (OCH3) 3 (5)
This silicone resin and hollow silica-isopropanol dispersion sol (manufactured by Catalytic Chemical Industry Co., Ltd., solid content concentration 20% by weight, average primary particle system 35 nm, outer shell thickness 8 nm) were obtained by the following formula. Then, 935 parts by weight of propylene glycol monomethyl ether was added and diluted to obtain an organic antireflection composition liquid having a solid content concentration of 3% by weight. Application | coating of the organic anti-reflective composition liquid was performed by the immersion method (pulling speed 10cm / min). At this time, the liquid temperature was 25 ° C. After application of the organic antireflection composition liquid, an annealing treatment was performed at 125 ° C. for 90 minutes. The formed organic antireflection layer had a thickness of 100 nm and a refractive index of 1.37.

(5) Antifouling layer Fluorine-containing silane compound (A) having a molecular weight of 497.5 (Shin-Etsu Chemical Co., Ltd., trade name “KP-801”) and fluorine-containing silane compound (B) having a molecular weight of 2500 (Shin-Etsu Chemical) Co., Ltd., trade name “KY-130”) is dissolved in a fluorine-based solvent (Sumitomo 3M Co., Ltd., trade name “Novec HFE-7200”) and diluted to a solid content concentration of 3%. Thus, an antifouling composition solution was prepared. The antifouling composition liquid was adjusted so that the ratio of (weight Wa of fluorine-containing silane compound (A)) / (weight Wb of fluorine-containing silane compound (B)) was 80/20. A porous ceramic pellet impregnated with 1 g of this antifouling composition solution and dried was set as a deposition source in a chamber in a vacuum deposition apparatus. Then, exhaust is performed until the ultimate pressure of the chamber of the vacuum vapor deposition device is in the range of 1.0 to 0.4 × 10 −2 Pa, and the primer layer, the hard coat layer, and the organic antireflection layer are formed in this chamber. The plastic lens was introduced, the pellet was heated to 400 ° C. to 500 ° C. to evaporate the fluorine-containing silane compound, and an antifouling layer was formed on the surface of the organic antireflection layer. After completion of the vapor deposition, the inside of the vacuum vapor deposition chamber was gradually returned to atmospheric pressure, and the plastic lens was taken out. After that, the plastic lens is put into a constant temperature and humidity chamber maintained at a temperature of 90 ° C. and a relative humidity of 90%, held for 2 hours, and then heated in an oven maintained at 100 ° C. for 2 hours to prepare a primer layer and a hard coat A plastic lens having a layer, an organic antireflection layer, and an antifouling layer was obtained.

(Example 2)
A plastic lens on which a primer layer, a hard coat layer, and an organic antireflection layer were formed was obtained by the treatments of (1) to (4) in Example 1.

  Thereafter, a fluorine-containing silane compound (A) having a molecular weight of 497.5 (Shin-Etsu Chemical Co., Ltd., trade name “KP-801”) was converted to a fluorine-based solvent (manufactured by Sumitomo 3M Ltd., trade name “Novec HFE-7200”). The first antifouling composition liquid was adjusted so that the solid content concentration became 3% solution.

  Next, a fluorine-containing silane compound (B) having a molecular weight of 2500 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KY-130”) is used as a fluorine-based solvent (manufactured by Sumitomo 3M Ltd., trade name “Novec HFE-7200”). The antifouling composition liquid was adjusted so that the solid concentration was 3% solution.

  After that, 1 g of the first antifouling composition liquid was impregnated into a porous ceramic pellet and dried, and set as a deposition source in a chamber in a vacuum deposition machine. Then, exhaust is performed until the ultimate pressure of the chamber of the vacuum vapor deposition device is in the range of 1.0 to 0.4 × 10 −2 Pa, and the primer layer, the hard coat layer, and the organic antireflection layer are formed in this chamber. The plastic lens was introduced, the pellet was heated to 400 ° C. to 500 ° C. to evaporate the fluorine-containing silane compound (A), and a first antifouling layer was formed on the surface of the organic antireflection layer.

  After that, 1 g of the second antifouling composition liquid was impregnated into a porous ceramic pellet and dried, and then set as a deposition source in a chamber in a vacuum deposition machine. Then, evacuation is performed until the ultimate pressure of the chamber of the vacuum vapor deposition device is in the range of 1.0 to 0.4 × 10 −2 Pa, and the plastic lens in which the first antifouling layer is formed is introduced into the chamber. The pellet was heated to 400 ° C. to 500 ° C. to evaporate the fluorine-containing silane compound (B), and a second antifouling layer was formed on the surface of the first antifouling layer to form an antifouling layer.

  After the vapor deposition, the plastic lens is taken out, put into a constant temperature and humidity chamber maintained at a temperature of 90 ° C. and a relative humidity of 90%, held for 2 hours, and then placed in an oven maintained at 100 ° C. By heating for a time, a plastic lens having a primer layer, a hard coat layer, an organic antireflection layer, and an antifouling layer was obtained.

(Comparative Example 1)
A plastic lens on which a primer layer, a hard coat layer, and an organic antireflection layer were formed was obtained by the treatments of (1) to (4) in Example 1.

  Thereafter, a fluorine-containing silane compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KY-130”) and a fluorine-containing silane compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KP-801”) are mixed in a solid content ratio. It mix | blended so that it might become 80/20, it diluted with perfluorohexane, and prepared the antifouling layer coating composition liquid of solid content concentration 0.3 weight%. Subsequently, the plastic lens on which the primer layer, the hard coat layer, and the organic antireflection layer were formed was immersed in this antifouling layer coating composition solution, and dip-coated at a lifting speed of 150 mm / min. After that, it was baked at 90 ° C. for 10 minutes, and then the plastic lens was put into a constant temperature and humidity chamber maintained at a temperature of 90 ° C. and a relative humidity of 90%, held for 2 hours, and then in an oven maintained at 100 ° C. By heating for 2 hours, a plastic lens having a primer layer, a hard coat layer, an organic antireflection layer, and an antifouling layer was obtained.

(Evaluation methods)
The physical properties of the plastic lenses obtained in Examples 1 and 2 and Comparative Example 1 were evaluated by the following methods. Evaluation items are two items, alkali resistance and dry wiping property.

(1) Alkali resistance The lens was immersed in an aqueous 0.1 N sodium hydroxide solution at 20 ° C. for 1 hour, taken out of the lens, washed with water, and then subjected to the following adhesion test. After the surface of the lens is cross-cut into 100 bases at intervals of approximately 1 mm, an adhesive tape (made by Nichiban Co., Ltd., trade name Cello Tape (registered trademark)) is strongly pasted on the cross-cut portion, and then rapidly The adhesive tape was peeled off, and the film peeling state of the substrate after the adhesive tape was peeled off was evaluated according to the following five levels a to e.
a: No film peeling at all (number of film peeling eyes = 0/100)
b: Almost no film peeling (number of film peeling eyes = 1-5 / 100)
c: Some film peeling occurred (number of film peeling eyes = 6 to 20/100)
d: occurrence of film peeling (number of film peeling eyes = 21 to 50/100)
e: Adhesion failure (number of peeled films = 50 to 100/100)

(2) Dry wipeability (scratches)
Using a cotton cloth, the convex surface of the lens was reciprocated 3000 times while applying a weight of 100 g, and then the state of scratches that entered the lens surface was visually evaluated at the following five levels A to E.
A: No scratches B: 1 to 5 scratches are confirmed C: 6 to 20 scratches are confirmed D: There are 21 or more scratches but it is not visible in cloudy E: Many Scratched and almost cloudy

(3) Dry wiping property (wiping property)
Using a cotton cloth, the lens convex surface was reciprocated 3000 times while applying a weight of 100 g, and after drawing a straight line of about 4 cm with a black oil marker ("Himackey Care", manufactured by Zebra Corporation), it was left for 5 minutes. . And the mark part of the lens after leaving was wiped off with wipe paper ("Kay Dry", manufactured by Crecia Co., Ltd.), and the ease of wiping was determined by the following evaluation method at the initial stage and after the test.
○: Completely removed by wiping 10 times or less. △: Completely removed by wiping 11 to 20 times. X: Part not removed even after wiping 20 times.

  (result)

  From the results in Table 1, it can be seen that the eyeglass lenses of Examples 1 and 2 are both excellent in alkali resistance and dry wiping properties. On the other hand, Comparative Example 1 had poor adhesion between the organic antireflection layer and the antifouling layer, and peeling of the antifouling layer was observed in the dry wiping test.

  In addition to optical components such as plastic lenses used for eyeglasses, the present invention has a surface layer formed of a composition containing a silane compound, and any article having an antifouling layer formed on the surface layer Can be applied to.

Claims (5)

A base material having an organic layer formed from a composition of a silane-containing compound, and an antifouling article provided with an antifouling layer comprising two layers formed on the organic layer,
The antifouling layer is provided on the surface of the organic layer, and a first antifouling layer formed of a fluorine-containing silane compound having a molecular weight of 100 to 700,
A second antifouling layer provided on the surface of the first antifouling layer and formed of a fluorine-containing silane compound having a molecular weight of 1000 to 10,000. The antifouling article according to claim 1,
The organic layer is an organic antireflection layer and / or a hard coat layer. A method for producing an antifouling article, wherein an antifouling layer comprising two layers is formed on the organic layer of a substrate having an organic layer formed from a composition of a silane-containing compound,
Forming a first antifouling layer formed of a fluorine-containing silane compound having a molecular weight of 100 to 700 on the surface of the organic layer;
Thereafter, a second antifouling layer formed of a fluorine-containing silane compound having a molecular weight of 1000 to 10,000 is formed on the surface of the first antifouling layer. It is a manufacturing method of the antifouling article according to claim 3,
The first antifouling layer and the second antifouling layer constituting the antifouling layer are formed by vacuum deposition,
A mixed composition obtained by mixing a fluorine-containing silane compound having a molecular weight of 100 to 700 to form the first antifouling layer and a fluorine-containing silane compound having a molecular weight of 1000 to 10,000 to form the second antifouling layer is used as a deposition source. A method for producing an antifouling article characterized by the above. It is a manufacturing method of the antifouling article according to claim 4,
The first antifouling layer and the second antifouling layer constituting the antifouling layer are formed by vacuum deposition,
After forming the first antifouling layer on the organic layer using a fluorine-containing silane compound having a molecular weight of 100 to 700 alone as a deposition source to form the first antifouling layer,
The second antifouling layer is formed on the surface of the first antifouling layer using a fluorine-containing silane compound having a molecular weight of 1000 to 10,000 alone as a deposition source. A method for producing an antifouling article.