JP2007232872A - Product having antireflection layer, and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a product that can be dyed, having an antireflection layer, such as lens. <P>SOLUTION: The lens 10 formed with a primer layer 2 and an antireflection preventive layer 4 of an organic system via a hard coat layer 3 on a lens base material 1 is provided. The antireflection layer 4 includes a layer 41 of an intermediate refractive index that serves as a base layer formed by a first composition, containing polyester resin or polyurethane resin and metal oxide particles, a layer 42 of a high refractive index, and a layer 43 of a low refractive index, formed of a second composition including organic oxide particles and porous silica particles. The lens 10 can be dyed, even after production, since its antireflection layer 4 has dye affinity. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a product having an antireflection layer used for eyeglasses, etc., which is made of plastic or glass and can be dyed.

Some eyeglass lenses for color correction such as vision correction lenses and sunglasses dye a plastic lens constituting a substrate or a substrate. Patent Document 1 discloses a method of forming a dyed layer on a plastic lens substrate, providing a hard coat on the dyed layer, and coloring the dyed layer through the hard coat. This method is excellent in that it can be dyed after the hard coat layer is formed, and can be stocked at the stage where the dyed lens is formed to the hard coat.
JP 2001-295185 A JP 2003-222703 A

  Providing a dyed lens without dyeing the lens substrate can move the dyeing process to a later stage of the lens manufacturing process, that is, a stage close to factory shipment and a stage that can be handled by a dealer. Excellent in terms. Furthermore, when selecting a lens base material, the dyeing requirement can be removed, so that it is possible to select a lens base material that further meets other requirements, and the total performance of the dyed lens can be improved.

  On the other hand, in the technique of Patent Document 1, it is required to add a layer exhibiting dyeability to the lens. Adding a layer that is optically unnecessary or less useful for dyeing and selecting a dyeable lens substrate causes a trade-off problem involving various factors. By providing a dyeable lens without adding an optically unnecessary layer and without making the lens substrate dyeable, this trade-off problem can be solved.

  In Patent Document 2, a layer having a refractive index lower by 0.10 or more than the refractive index of the outermost layer of the base material is formed as a single layer on a plastic lens base material by a wet method, and used as an organic antireflection layer. It is disclosed to use.

  One embodiment of the present invention is a product having an antireflection layer that is laminated directly or via at least one functional layer on the surface of a substrate, the antireflection layer including a polyester resin or a polyurethane resin, and a metal oxide Formed by the second composition containing the base layer formed of the first composition containing the product fine particles, the organosilicon compound, and the porous silica fine particles, and disposed on the opposite side of the base layer from the base material. And a low refractive index layer having a lower refractive index than the base layer.

  The product having the antireflection layer has an organic antireflection layer having a multilayer structure, that is, a two-layer structure including at least a base layer and a lower refractive index layer. The base layer has dyeing performance (coloring performance). Therefore, a product having an antireflection layer having dyeing performance can be provided. If this product has a base material that performs an optically main function such as a lens base material and an antireflection layer, a product having dyeing performance can be provided even if the base material is not dyeable. The antireflection layer is indispensable for many optical products. By making the antireflection layer dyeable, the dyeing performance can be improved without adding an optically unnecessary or unusable layer. We can provide products with For plastic lenses, a hard coat is required in many cases, and it is conceivable to make this hard coat dyeable. However, a hard coat is not required for glass lenses. In the product having the antireflection layer, a product having a dyeing property can be provided regardless of the presence or absence of the hard coat and the presence or absence of the dyeing property of the lens substrate.

  The organic antireflection layer basically has a single layer structure and can realize a low refractive index. Therefore, it is not required to have multiple layers. By multilayering in the same manner as the inorganic antireflection layer, it is possible to further widen the transmission frequency band. For that purpose, a high refractive index sol, a low refractive index sol, This can be realized in combination with a silane coupling agent. On the other hand, in the product having the antireflection layer according to one embodiment of the present invention, the antireflection layer includes a dyeable base layer containing a polyester resin or a polyurethane resin and metal oxide fine particles, an organosilicon compound, and And a low refractive index layer containing porous silica fine particles. The base layer is organic and has adhesion and strong dyeability. Therefore, by combining the base layer having the function and dyeability as this primer with the organic and low refractive index layer, the thin layer combines the functions of dyeability and transparency. A highly durable organic antireflection layer is realized.

  The antireflection layer desirably includes a high refractive index layer having a higher refractive index than the base layer between the base layer and the low refractive index layer. An antireflection layer having a low refractive index-high refractive index-medium refractive index can be formed from the side opposite to the substrate, and transparency in a wide frequency range can be ensured.

  The high refractive index layer is preferably formed of a third composition containing a polyester resin or polyurethane resin and metal oxide fine particles. By forming a layer having a high refractive index with this third composition, it becomes possible to give a strong dyeability to the layer having a high refractive index, and the dyeing performance of the antireflection layer can be improved.

  It is also preferable to form the high refractive index layer by a fourth composition containing metal oxide fine particles, an organosilicon compound, and an epoxy resin. By forming the high refractive index layer with this fourth composition, the dyeing property of the high refractive index layer is slightly lowered, but the strength of the high refractive index layer can be improved, and the durability of the antireflection layer can be improved. It can be improved.

  Moreover, it is desirable that the second composition forming the low refractive index layer further contains an epoxy resin. The strength of the low refractive index layer can be improved. Since the low refractive index layer is the outermost layer of the product in many cases, excluding the antifouling layer, it is suitable for improving the durability of the antireflection layer.

  The product having the antireflection layer desirably has a stainproof layer having water repellency on the antireflection layer in order to prevent contamination.

  Another embodiment of the present invention is a method for producing a product having an antireflection layer, which includes a step of laminating an antireflection layer directly on a substrate or via at least one functional layer. The step of laminating the antireflection layer includes a step of forming a base layer with a first composition containing a polyester resin or polyurethane resin and metal oxide fine particles, an organosilicon compound, and porous silica fine particles. Forming a low refractive index layer that is disposed on the opposite side of the base layer from the base material and has a lower refractive index than the base layer.

  A product having an antireflection layer manufactured by this manufacturing method has a dyeable antireflection layer. Therefore, it is possible to further provide a step of dyeing the antireflection layer, and it is possible to dye the product on which the antireflection layer is formed.

  Further, the multilayer organic antireflection layer has a base layer made of a first composition containing a polyester resin or polyurethane resin and metal oxide fine particles, and the base layer has an adhesiveness to the substrate. Since it is high, anti-reflection processing can be performed on a substrate that is difficult to adhere.

  Before or after the dyeing step, a step of forming an antifouling layer on the antireflection layer can be provided. The antireflection layer can be dyed through the antifouling layer, and a product having an antireflection layer such as a lens almost completed can be selected as a dyeing target.

  The product having the antireflection layer includes a spectacle lens capable of being dyed into a finished product. Moreover, the product provided with the base material without dyeability and the product provided with the hard coat without dyeability are included.

  FIG. 1 shows the configuration of a spectacle lens according to an embodiment of the present invention. In addition, since it becomes a symmetrical structure with respect to a lens base material, the structure of one surface is shown as a representative with respect to a lens base material. This spectacle lens 10 has a plastic lens substrate 1, and a primer layer 2, a hard coat layer 3, an antireflection layer 4, and an antifouling layer 5 are sequentially laminated on the surface thereof. . The antireflection layer 4 has a three-layer structure, and in order from the hard coat layer 3 side, that is, the lens base material 1 side, a medium refractive index layer (medium bending layer) 41 as a base layer and a high refractive index. Three layers of a refractive index layer (high refractive layer) 42 and a low refractive index layer (low refractive layer) 43 are provided. The layer thickness of each layer varies depending on the refractive index of each layer, but the basic configuration is that each layer is laminated in the range of about 50 to 200 nm.

  The three-layer structure balances the resin composition of each layer so that the entire antireflection layer has sufficient dyeability, adhesion, and transparency in realizing a dyeable organic antireflection layer. This is a preferred example. Even with the two-layer structure of the middle bending layer 41 and the low bending layer 43, an antireflection layer having dyeability, transparency and adhesion can be realized. Further, an antireflection layer having dyeability, transparency and adhesion can be realized even with a structure of four or more layers.

  The intermediate bending layer 41 closest to the substrate 1 is formed of a first composition containing a polyester resin or polyurethane resin and metal oxide fine particles. The first composition contains, for example, 20 to 80 wt%, desirably 40 to 60 wt% of a polyester resin. Suitable metal oxide fine particles are rutile-type titanium oxide fine particles, and the refractive index can be adjusted by the content of the metal oxide fine particles. An example of the content of the rutile-type titanium oxide fine particles is 20 to 80 wt%, and more preferably 40 to 60 wt%. By making the base layer 41 in a middle shape, it is possible to reduce the content of metal oxide fine particles (sol) and to adopt a composition giving priority to dyeability and adhesion.

  The highly bent layer 42 can be formed of a third composition containing a polyester resin or polyurethane resin and metal oxide fine particles, similar to the bent layer 41. The highly bent layer 42 of this third composition has a structure giving priority to dyeability and adhesion, and the refractive index can be adjusted by the content of metal oxide fine particles, preferably rutile-type titanium oxide fine particles. An example of the content of rutile-type titanium oxide fine particles (metal oxide fine particles) is 40 to 70 wt%, and desirably 50 to 60 wt%.

  The highly bent layer 42 can also be formed of a fourth composition containing metal oxide fine particles, an organosilicon compound, and an epoxy resin. In addition to the dyeability, this structure gives priority to strength and durability (weather resistance). The fourth composition contains, for example, 5 to 50 wt%, preferably 10 to 40 wt% of the organosilicon compound, and 5 to 40 wt%, preferably 5 to 30 wt% of the polyfunctional epoxy compound. Furthermore, it contains 40 to 70 wt%, desirably 50 to 60 wt% of metal oxide fine particles, preferably rutile type titanium oxide fine particles.

  The low bending layer 43 is formed of a second composition containing an organosilicon compound and porous silica fine particles. The second composition contains, for example, 40 to 85 wt%, preferably 50 to 80 wt% of porous silica fine particles (hollow silica sol), and 5 to 60 wt%, preferably 20 to 40 wt% of an organosilicon compound. Furthermore, the second composition desirably contains 5 to 30 wt% of the polyfunctional epoxy compound, and is suitable for improving strength and durability.

(Polyester resin)
The polyester resin contained in the first composition and the third composition forming the middle bending layer 41 and the high bending layer 42, respectively, has a hydroxyl group or an epoxy group attached to an ester bond and a side chain in the resin as a plastic lens. Interacts with substrate surface molecules easily and exhibits high adhesion. On the other hand, the pH of the polyester resin often shows weak acidity and often coincides with the pH at which the metal oxide fine particles serving as the filler can stably exist. Therefore, the metal oxide fine particles are uniformly dispersed in the resin without being localized, and the crosslink density is stabilized or improved, and the water resistance and light resistance are improved.

  Examples of the polyester resin include polyester-based thermoplastic elastomers. The polyester-based thermoplastic elastomer is a multi-block copolymer using polyester as a hard segment and polyether or polyester as a soft segment. The weight ratio of the hard segment (H) and the soft segment (S) is H / S = 30/70 to 90/10, preferably 40/60 to 80/20.

  The polyester as a hard segment constituent component is basically composed of dicarboxylic acids and a low molecular glycol. Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid, carbon atoms such as succinic acid, adipic acid, azelaic acid, decamethylene dicarboxylic acid, and octadecanedicarboxylic acid. -20 linear saturated aliphatic dicarboxylic acids, aliphatic oxocarboxylic acids such as ε-oxycaproic acid, dimer acids (dibasic acids obtained by dimerizing an aliphatic monocarboxylic acid having a double bond), and the like, and These ester-forming derivatives are mentioned. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are desirable when used.

  Examples of the low molecular weight glycol include ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol and other aliphatic glycols, 1,6-cyclohexane. Examples include aliphatic glycols such as dimethanol, and ester-forming derivatives thereof. Among these, ethylene glycol and 1,4-butanediol are desirable when used.

  The polyester as a soft segment constituent component is composed of dicarboxylic acids and long-chain glycols, and examples of the dicarboxylic acids include those described above. Examples of the long chain glycol include poly (1,2-butadiene glycol), poly (1,4-butadiene glycol) and hydrogenated products thereof. Also, ε-caprolactone (C6), enanthlactone (C7), and caprolilolactone (C8) are useful as the polyester component. Of these, ε-caprolactone is desirable for use.

  Polyethers as soft segment constituents include poly (alkylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol and the like poly (alkylene) Oxide) glycols, among which poly (tetramethylene oxide) glycol is desirable for use.

  As a method for producing a polyester-based thermoplastic elastomer, for example, a lower alkyl ester of a dicarboxylic acid is heated at a temperature of 150 to 200 ° C. in the presence of a catalyst such as an aliphatic long-chain glycol and an excess low-molecular glycol such as tetrabutyl titanate, First, a low polymer is formed by performing a transesterification reaction, and the low polymer is further heated and stirred at 220 to 280 ° C. under high vacuum to perform polycondensation to obtain a polyester-based thermoplastic elastomer. The low polymer can also be obtained by a direct esterification reaction of a dicarboxylic acid with a long chain glycol and a low molecular glycol.

  The polyester-based thermoplastic elastomer can be used by mixing with other polymers. For example, a normal ester-based resin (PBT, PET, etc.), an amide-based resin, and an amide-based thermoplastic elastomer are optional. Usually, the proportion of the total polymer is less than 50% by weight, desirably less than 30% by weight.

  The polyester-based thermoplastic elastomer can be prepared as a solution-type primer composition. However, it is desirable to use it as a primer composition of an aqueous emulsion from the viewpoint of processability and environmental protection. This aqueous emulsification can be carried out by a conventional method. Specifically, a forced emulsification method in which a polymer is forcibly emulsified by applying high mechanical shear in the presence of a surfactant (external emulsifier) is desirable. .

(Polyurethane resin)
The polyurethane resin (urethane-based resin composition) contained in the first composition and the third composition that respectively form the middle-bending layer 41 and the high-bending layer 42 includes a polyol compound or a long-chain dithiol compound. desirable. Suitable polyol compounds include polypropylene glycol, polyethylene glycol bisphenol A ether, polypropylene glycol bisphenol A ether, polyethylene glycol-polypropylene glycol bisphenol A ether, and the like.

  Polypropylene glycol (PPG) is desirably contained in the range of 5 to 10% by weight. Further, at least one of polypropylene glycol (PPG), polyethylene glycol bisphenol A ether (DA), polypropylene glycol bisphenol A ether (DB), and polyethylene glycol-polypropylene glycol bisphenol A ether (DAB), 5 wt% to 30 wt%. It is desirable to contain in the range of weight%.

  Suitable long chain dithiol compounds include 1,10-decanedithiol, 1,6-hexanedithiol and the like.

(Epoxy resin)
Examples of the epoxy resin contained in the second composition and the fourth composition forming the low bending layer 43 and the high bending layer 42, respectively, may include polyfunctional epoxy resins. Examples of the polyfunctional epoxy compound include the following. Polyolefin epoxy resins synthesized by the peroxidation method, cyclopentadiene oxide, cyclohexene oxide, cycloaliphatic epoxy resins such as polyglycidyl esters obtained from hexahydrophthalic acid and epichlorohydrin, polyhydric phenols such as bisphenol A, catechol, and resorcinol Or (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, sorbitol and other polyglycidyl ethers obtained from epichlorohydrin, epoxidized vegetable oil, novolak type Epoxy novolak obtained from phenolic resin and epichlorohydrin, obtained from phenolphthalein and epichlorohydrin Epoxy resins, copolymers, and further epoxy acrylates obtained by glycidyl MotoHiraki ring reaction of the epoxy compound and monocarboxylic acid-containing (meth) acrylic acid such as glycidyl methacrylate and methyl methacrylate acrylic monomer or styrene that.

  Furthermore, the following are mentioned as a polyfunctional epoxy compound. 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene Glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ether of neopentyl glycol hydroxyhybalate, trimethylolpropane diglycidyl Ether, trimethylol group Pantriglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether , Dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, isophoronediol Diglycidyl ether, bis-2,2-hydroxy Alicyclic epoxy compounds such as rohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolac polyglycidyl ether, cresol Aromatic epoxy compounds such as novolac polyglycidyl ether.

(Organic silicon compound)
Examples of the organosilicon compound contained in the fourth composition and the second composition that form the high yield layer 42 and the low yield layer 43, respectively, include organosilicon compounds represented by the following general formula (A). Can do.
R ¹ R ² _n SiX ¹ _3-n (A)
(In the formula, n is 0 or 1.)

Here, R ¹ is an organic group having a polymerizable reactive group or a hydrolyzable functional group. Specific examples of the polymerizable reactive group include the following. Examples include vinyl group, allyl group, acrylic group, methacryl group, epoxy group, mercapto group, cyano group, amino group, etc. Specific examples of hydrolyzable functional groups include methoxy group, ethoxy group, methoxyethoxy group, etc. An alkoxy group, a halogen group such as a chloro group and a bromo group, and an acyloxy group.

R ² is a hydrocarbon group having 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, a butyl group, a vinyl group, and a phenyl group.

X ¹ is a hydrolyzable functional group, and examples thereof include the following. Alkoxy groups such as methoxy group, ethoxy group and methoxyethoxy group, halogen groups such as chloro group and bromo group, and acyloxy groups.

Specific examples of X ¹ include the following. Vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, methacryloxypropyl dialkoxymethylsilane, γ-glycid Oxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldi Alkoxysilane, tetramethoxysilane, γ-glycidoxypropyltrimethoxysilane. X ¹ may be a mixture of two or more of these functional groups. Moreover, X ¹ is is more effective preferable to use since the hydrolysis.

(Metal oxide fine particles)
Examples of the metal oxides contained in the first composition and the third or fourth composition forming the middle bending layer 41 and the high bending layer 42, respectively, include the following. Methanol-dispersed antimony oxide-coated titanium oxide-containing composite oxide sol, or one or more metal oxides selected from Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti Containing fine particles or composite fine particles, fine particles obtained by modifying the outermost surface of metal oxide fine particles with an organosilicon compound, a mixture thereof, a solid solution state, or another composite state. The titanium oxide may be amorphous, anatase, rutile, brookite, or perovskite titanium compounds. Among them, rutile type titanium oxide is most desirable.

  Metal oxides are those colloidally dispersed in a dispersion medium such as water, alcohols or other organic solvents. Further, the surface of the composite oxide fine particles may be modified by treatment with an organosilicon compound or an amine compound. Examples of the organosilicon compound used in this case include monofunctional silane, bifunctional silane, trifunctional silane, and tetrafunctional silane. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. In addition, after the treatment, it is preferable that the hydrolyzable group reacts with the —OH group of the fine particles, but there is no problem in stability even if a part of the hydrolyzable group remains. Amine compounds include ammonium or alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, alkanolamines such as monoethanolamine and triethanolamine. There is. It is necessary to add these organosilicon compounds and amine compounds within a range of about 1 to 15% with respect to the weight of the fine particles. In any case, the particle size is preferably about 1 to 300 millimicrons.

(Porous silica fine particles)
As a suitable thing of the porous silica fine particle contained in the 2nd composition which forms the low bending layer 43, for example, water, alcohol type, or other which made the dispersion medium the fine particle silica with an average particle diameter of 1 nm-100 nm Examples thereof include a silica sol dispersed in an organic solvent in a colloidal form.

  Further, it is desirable that the silica-based fine particles have an internal cavity (gap). By using silica-based fine particles having internal cavities, a gas or solvent having a refractive index lower than that of silica is included in the internal cavities of the silica-based fine particles, and the refractive index is reduced as compared with silica-based fine particles having no cavities. Low refractive index is achieved.

(staining)
Examples of the dye capable of dyeing the organic antireflection layer according to this embodiment include the following.

  As the dye, it is desirable to use a disperse dye in order to suppress color unevenness. In the dyeing step, it is desirable to perform dip dyeing by immersing the lens in a dye bath in which the disperse dye is dispersed in water. A dye having high fastness is preferable. Examples of usable dyes include disperse dyes such as anthraquinone dyes, quinophthalone dyes, nitrodiphenylamine dyes, and azo dyes. Specific examples of the disperse dye include the following. p-anisidine, aniline, p-aminoacetanilide, p-aminophenol, 1-chloro-2,4-dinitrobenzene, 2-chloro-4-nitroaniline, o-chloronitrobenzene, diphenylamine, m-nitroaniline, p- Nitroaniline, N, N-bis (2-hydroxyethyl) aniline, 1-phenyl-3-methyl-5-pyrazolone, benzene-based intermediates such as phenol, p-cresidine (6-methoxy-m-toluidine), m -Cresol, p-cresol, m-toluidine, 2-nitro-p-toluidine, toluene-based intermediates such as p-nitrotoluene, 1-naphthylamine, naphthalene-based intermediates such as 2-naphthol, 1-amino-4-bromo Anthraquinone-2-sulfonic acid (bromamic acid), 1-anthraquinonesulfone 1,4-diaminoanthraquinone, 1,5-dichloroanthraquinone, 1,4-dihydroxyanthraquinone (quinizarin), 1,5-dihydroxyanthraquinone (anthralphine), 1,2,4-trihydroxyanthraquinone (purpurin), 2 -Phthalic anhydride such as methyl anthraquinone and anthraquinone intermediates. Moreover, you may use a disperse dye individually or in mixture of 2 or more types. The disperse dye is usually dispersed in water to form a dye bath. You may use together organic solvents, such as methanol, ethanol, and benzyl alcohol, as a solvent.

  A surfactant can also be added to the dyeing bath as a dispersant for the dye. Examples of the surfactant include the following. Anionic surfactants such as alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfosuccinate, aromatic sulfonic acid formalin condensate, lauryl sulfate, polyoxyethyl alkyl ether, alkyl amine ether, polyoxyethylene sorbitan fatty acid Nonionic surfactants such as esters. These surfactants are preferably used in the range of 5 to 200% by weight based on the amount of dye used depending on the color density of the lens. In the dip dyeing, a disperse dye and a surfactant are dispersed in water or a mixture of water and an organic solvent to prepare a dye bath, and a plastic lens is immersed in the dye bath and dyed at a predetermined temperature for a predetermined time. . The dyeing temperature and time vary depending on the desired color density. Usually, it may be about 95 ° C. or less and several minutes to 30 minutes, and the dye concentration in the dyeing bath is preferably 0.01 to 5% by weight.

  In the following, some specific examples and comparative examples will be described.

Example 1
In Example 1, a spectacle lens sample S1 was manufactured as follows. First, a lens base material was prepared, and a primer layer 2 and a hard coat layer 3 were formed on the lens base material 1.

  As the lens substrate 1, a Seiko super sovereign lens fabric (hereinafter abbreviated as SSV) manufactured by Seiko Epson Corporation was used. This is a plastic lens substrate 1 having a refractive index of 1.67.

  As a primer coating solution, 100 parts of a commercially available polyester resin “Pesresin A-160P” (manufactured by Takamatsu Resin Co., Ltd., water dispersion emulsion, solid content concentration 27%) is added to a rutile type titanium oxide composite sol (catalyst chemical industry ( Co., Ltd., trade name: OPTRAIQUE 1120Z) 150 parts, 350 parts of methyl alcohol as a diluting solvent, 0.2 parts of a silicone surfactant (trade name L-7604, manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent Then, a liquid stirred until a uniform state was prepared. This liquid was applied to the lens substrate 1 by a dipping method (pulling speed of 15 cm per minute). After application, the lens was air-dried at 80 ° C. for 20 minutes to obtain a lens with primer layer 2 having a thickness of about 600 nm.

  As a coating solution for hard coating, 44 parts of 0.1N hydrochloric acid aqueous solution was added dropwise to 95 parts of γ-glycidoxypropyltrimethoxysilane with stirring, and the mixture was further stirred for 4 hours and aged overnight, and then propylene glycol methyl ether 45 413 parts of a rutile type titanium oxide composite sol (catalyst chemical industry Co., Ltd., trade name OPTRAIQUE 1120Z), 1.4 parts of Fe (III) acetylacetonate, silicone surfactant (Toray Dow A liquid to which 0.2 part of Corning (trade name FZ-2164) was added was prepared. This solution was applied to the lens with the primer by a dipping method (pickup speed: 45 cm / min). After coating, the substrate was air-dried at 80 ° C. for 30 minutes, and then annealed at 120 ° C. for 90 minutes. A lens in which a hard coat layer 3 having a thickness of 2.1 μm was formed on the primer layer 2 was obtained.

  An organic antireflection layer 4 having a three-layer structure (medium bending, high bending, low bending) was formed on the hard cord layer 3.

  A coating liquid M1 for a medium refractive index layer was prepared. Commercially available polyester resin “Pesresin A-160P” (manufactured by Takamatsu Resin Co., Ltd., water dispersion emulsion, solid content concentration 27%) in 55 parts as metal oxide fine particles, rutile type titanium oxide composite sol (Catalyst Chemical Industries, Ltd.) ), Trade name OPTRAIQUE 1120Z) 80 parts, 1400 parts of methyl alcohol as a diluent solvent, 0.3 part of a silicone surfactant (trade name FZ-2164, manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent Stir until uniform.

  This medium refractive index layer coating solution M1 was applied to the lens on which the hard coat layer was formed by a dipping method (pulling speed of 15 cm per minute). Then, after application, the layer 41 having a medium refractive index (refractive index of 1.64) of about 80 nm thickness was formed by air drying at 80 ° C. for 20 minutes.

  A coating liquid H1 for a high refractive index layer was prepared. As an organosilicon compound, 7 parts of a 0.1N hydrochloric acid aqueous solution was added dropwise to 14 parts of γ-glycidoxypropyltrimethoxysilane while stirring, and the mixture was further stirred for 4 hours and aged overnight, then 1340 parts of propylene glycol methyl ether, metal As oxide fine particles, 124 parts of rutile-type titanium oxide composite sol (catalyst chemical industry Co., Ltd., trade name OPTRAIQUE 1120Z), and as polyfunctional epoxy resin, glycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name) After mixing 10 parts of Denacol EX313), 0.6 part of Fe (III) acetylacetonate and 0.45 part of a silicone-based surfactant (trade name FZ-2164, manufactured by Toray Dow Corning Co., Ltd.) were added.

  The coating liquid H1 for the high refractive index layer was applied to the lens on which the intermediate bending layer was formed by a dipping method (pulling speed of 15 cm per minute). By air drying at 80 ° C. for 20 minutes after coating, a high refractive index (refractive index 1.67) layer 42 having a thickness of about 160 nm was formed on the medium refractive index layer 41.

  A coating liquid L1 for the low refractive index layer was prepared. As an organosilicon compound, 5 parts of a 0.1N hydrochloric acid aqueous solution was added dropwise to 10 parts of γ-glycidoxypropyltrimethoxysilane while stirring, and the mixture was further stirred for 4 hours and then aged overnight. In this mixture, 1400 parts of propylene glycol methyl ether, 75 parts of hollow silica sol (manufactured by Catalytic Chemical Industry Co., Ltd., trade name Oscar special product) as porous silica fine particles, glycerol polyglycidyl ether (Nagase Kasei Chemical) as a polyfunctional epoxy resin Kogyo Co., Ltd., trade name Denacol EX313) 7.5 parts, magnesium perchlorate 0.4 parts, silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., trade name L-7001) 0.45 parts Added.

  The coating liquid L1 for the low refractive index layer was applied to the lens on which the highly bent layer 42 was formed by a dipping method (pulling speed of 15 cm per minute). After coating, the film was air-dried at 80 ° C. for 20 minutes, and a low-refractive index (refractive index 1.36) layer 43 having a thickness of about 100 nm was formed on the high-refractive index layer 42.

  Thereafter, by annealing at 120 ° C. for 90 minutes, the organic antireflection layer 4 having a three-layer structure in which the middle-bending layer 41, the high-bending layer 42, and the low-bending layer 43 are sequentially laminated on the hard coat layer 3 is obtained. We were able to manufacture the lens we had.

  Further, this lens with an antireflection layer was subjected to water repellency treatment with a fluorine-based silane compound to obtain a lens sample S1 with an antifouling layer (water repellent layer) 5.

(Example 2)
In Example 2, a spectacle lens sample S2 was manufactured as follows. The process is the same as in Example 1 until the primer layer 2 and the hard coat layer 3 are formed on the lens substrate 1.

  First, the same middle bending application liquid M1 as in Example 1 was applied to the lens by a dipping method (pulling speed of 15 cm per minute). After application, the film was air-dried at 80 ° C. for 20 minutes to form a layer having a medium refractive index (refractive index of 1.64) having a thickness of about 80 nm.

  Next, a coating solution H2 for a high bending rate layer was prepared. Commercially available polyester resin “Pesresin A-160P” (manufactured by Takamatsu Resin Co., Ltd., water dispersion emulsion, solid content concentration 27%) as metal oxide fine particles as rutile titanium oxide composite sol (Catalyst Chemical Industries, Ltd.) ), Trade name OPTRAIKE 1120Z) 90 parts, 800 parts of methyl alcohol as a diluent solvent, 0.3 part of a silicone surfactant (trade name FZ-2164, manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent Stir until uniform.

  The coating liquid H2 for the high refractive index layer was applied to the lens on which the intermediate bending layer was formed by the dipping method (pickup speed 15 cm / min). By air-drying at 80 ° C. for 20 minutes after coating, a high refractive index (refractive index 1.67) layer 42 having a thickness of about 160 nm was formed on the medium refractive index layer 41.

  Next, a coating liquid L2 for a low refractive index layer was prepared. As an organosilicon compound, 10 parts of a 0.1N hydrochloric acid aqueous solution was added dropwise to 22 parts of γ-glycidoxypropyltrimethoxysilane while stirring, and the mixture was further stirred for 4 hours and then aged overnight. In this mixed solution, 1390 parts of propylene glycol methyl ether, 75 parts of hollow silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name Oscar special product), 0.4 parts of magnesium perchlorate, silicone-based surface activity as porous silica fine particles 0.45 part of an agent (trade name L-7001, manufactured by Toray Dow Corning Co., Ltd.) was added.

  The coating liquid L2 for the low refractive index layer was applied to the lens on which the highly bent layer was formed by a dipping method (pickup speed 15 cm / min). After coating, the film was air-dried at 80 ° C. for 20 minutes, and a low-refractive index (refractive index 1.36) layer 43 having a thickness of about 100 nm was formed on the high-refractive index layer 42.

  Thereafter, by annealing at 120 ° C. for 90 minutes, the organic antireflection layer 4 having a three-layer structure in which the middle-bending layer 41, the high-bending layer 42, and the low-bending layer 43 are sequentially laminated on the hard coat layer 3 is obtained. We were able to manufacture the lens we had.

  Further, this lens with an antireflection layer was subjected to water repellency treatment with a fluorine-based silane compound to obtain a lens sample S2 with an antifouling layer (water repellent layer) 5.

(Comparative Example 1)
In Comparative Example 1, a spectacle lens sample SR1 was manufactured as follows. The process is the same as in Example 1 until the primer layer 2 and the hard coat layer 3 are formed on the lens substrate 1.

  A low-bending coating liquid L2 containing no epoxy resin was applied to the lens formed up to the hard coat layer by a dipping method (pulling speed of 15 cm per minute). After coating, the film was air-dried at 80 ° C. for 20 minutes to laminate a low refractive index (refractive index 1.36) layer having a thickness of about 100 nm. Thereafter, annealing was performed at 120 ° C. for 90 minutes.

  Further, this lens with an antireflection layer was subjected to water repellent treatment with a fluorine-based silane compound to obtain a lens sample SR1 with a water repellent layer.

(Evaluation)
Several evaluation was performed about each sample lens manufactured in said Example 1, 2 and the comparative example 1. FIG. The results are summarized in FIG.

(Evaluation of dyeability)
Each sample lens manufactured in Examples 1 and 2 and Comparative Example 1 was immersed in a disperse dye bath at 94 ° C. for 10 minutes for dyeing. The transmittance of this lens was measured with a spectrophotometer (manufactured by Hitachi, Ltd., U-3500), and the average transmittance in the visible light region (400 nm to 800 nm) was evaluated. A transmittance of 80% or less was evaluated as “◎” (well dyed), 90% or less as “◯” (dyed), and a sample exceeding 90% as “×” (not dyed).

(Evaluation of antireflection effect)
The antireflection effect was tested and evaluated by measuring the surface reflectance of each sample lens manufactured in Examples 1 and 2 and Comparative Example 1 with a spectrophotometer (U-3500, manufactured by Hitachi, Ltd.). The average reflectance (one side) in the visible light region (400 nm to 800 nm) was evaluated. In this evaluation, “◎” indicates that the average reflectance is 2% or less, which indicates that the antireflection effect is very large. “◯” indicates that the average reflectance is 3.5% or less, indicating that there is a sufficient antireflection effect. “X” indicates that the average reflectance exceeds 3.5%, indicating that there is almost no antireflection effect.

(Evaluation of adhesion)
The surface of each sample lens manufactured in Examples 1 and 2 and Comparative Example 1 was cross-cut in a grid pattern at intervals of about 1 mm, and an adhesive tape (manufactured by Nichiban Co., Ltd. After affixing name cello tape (registered trademark) strongly, the adhesive tape was peeled off rapidly, and the film peeling state of the grid 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 = 51 to 100/100)

(Evaluation of interference color)
The surface reflection color was observed for each sample lens manufactured in Examples 1 and 2 and Comparative Example 1 under sunlight.

(Evaluation results)
As shown in FIG. 2, the samples S1 and S2 of Examples 1 and 2 were all good in evaluation results of dyeability, antireflection effect and adhesion, and the interference color was the most preferred “green”. . Therefore, the samples S1 and S2 of Examples 1 and 2 can be colored even in a state almost completed as a lens after the antifouling layer is formed. It is possible to provide the user with a lens that the user prefers or is suitable for the user in a color based on the user's desire.

  On the other hand, sample SR1 of Comparative Example 1 had good antireflection effect and adhesion, but did not obtain dyeability. The interference color was magenta.

  As can be seen from these evaluations, the lens having the three organic antireflection layers produced in Examples 1 and 2 could be sufficiently dyed after the antifouling layer was formed. Compared with Comparative Example 1, since the hard coat layer is manufactured under the same conditions, it can be seen that the three organic antireflection layers have dyeability.

  In the above description, the substrate is a plastic lens, but the same effect can be obtained even if it is a glass lens. Furthermore, in the above, the plastic lens used for the spectacles is manufactured as a dyeing lens. However, since the antireflection layer has a dyeability in the present invention, the applicable range is very wide. For example, the product provided with the antireflection layer of the present invention is not limited to a spectacle lens, but a wide variety of lenses for cameras, other optical elements such as a prism, and a recording medium such as a DVD, This includes a wide variety of items such as glass for windows.

Schematic of a plastic lens provided with an organic antireflection layer. The figure which shows evaluation of the lens of an Example and a comparative example.

Claims (9)

A product having an antireflection layer laminated directly or via at least one functional layer on the surface of a substrate,
The antireflection layer is
A base layer formed of a first composition comprising a polyester resin or polyurethane resin and metal oxide fine particles;
A low refractive index layer formed of a second composition comprising an organosilicon compound and porous silica fine particles, disposed on the opposite side of the base layer from the base material and having a lower refractive index than the base layer; Including products with an anti-reflection layer.   2. The product according to claim 1, wherein the antireflection layer includes an antireflection layer including a high refractive index layer having a higher refractive index than the base layer between the base layer and the low refractive index layer.   3. The product having an antireflection layer according to claim 2, wherein the high refractive index layer is formed of a third composition containing a polyester resin or a polyurethane resin and metal oxide fine particles.   3. The product having an antireflection layer according to claim 2, wherein the high refractive index layer is formed of a fourth composition containing metal oxide fine particles, an organosilicon compound, and an epoxy resin.   5. The product according to claim 1, wherein the second composition for forming the low refractive index layer further includes an epoxy resin and has an antireflection layer.   The product having an antireflection layer according to any one of claims 1 to 5, wherein the antireflection layer is provided on a surface of the antireflection layer. A method for producing a product having an antireflection layer, comprising the step of laminating an antireflection layer directly on the surface of a substrate or via at least one functional layer,
The step of laminating the antireflection layer includes:
Forming a base layer with a first composition comprising a polyester resin or polyurethane resin and metal oxide fine particles;
A step of forming a low refractive index layer that is disposed on the opposite side of the base layer from the base and has a lower refractive index than the base layer by a second composition containing an organosilicon compound and porous silica fine particles. A method for producing a product having an antireflection layer.   8. The method for manufacturing a product having an antireflection layer according to claim 7, further comprising a step of dyeing the antireflection layer.   9. The method for producing a product having an antireflection layer according to claim 8, further comprising a step of forming an antifouling layer on the antireflection layer before or after the dyeing step.

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