JP2010102234A - Method for manufacturing polarizing element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a polarizing element, which enables manufacture in a simple process, and which is free from peeling of a polarizing layer in the manufacturing process. <P>SOLUTION: The method for manufacturing a polarizing element includes steps of: preparing an alignment film coating liquid by heating a mixture containing alkoxy silane and/or hexalkoxy disiloxane (A), water (B) and alcohols (C) at 40 to 120°C for 0.5 to 24 hours; forming a sol-gel film by depositing the alignment film coating liquid prepared in the above step on a substrate; forming an alignment layer having polishing traces in a uniaxial direction by polishing the sol-gel film in the uniaxial direction; forming a polarizing layer by aligning and depositing a dichroic dye on the alignment layer; and forming a protective layer for fixing the dye on the polarizing layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a polarizing element. More specifically, the present invention relates to a method for manufacturing a polarizing element that can be manufactured by a simple process and that does not cause peeling of the polarizing layer in the manufacturing process.

Conventionally, in a polarizing element such as a polarizing lens, when a polarizing layer is formed by arranging and depositing dichroic dyes on an array film on a substrate surface, a silica (SiO ₂ ) vapor deposition film has been suitable as the array film. . For example, a polarizing element having a polarizing layer and a protective layer on the surface of a transparent substrate and having an inorganic intermediate layer as an alignment film between the transparent substrate and the polarizing layer has been proposed (see Patent Document 1). . The inorganic intermediate layer is made of a combination of silicon oxide, metal oxide, or a mixture thereof.

  Also, as a method without vacuum deposition, the flat plate and the lens are arranged with their axes shifted, the polarizing liquid is spin-coated around the flat plate, and the polarizing liquid on the curved surface of the lens flows in a shearing manner. A method of forming a polarizing coating on a lens curved surface by curing the liquid has been proposed (see, for example, Patent Document 2).

International Publication No. 06/081006 Pamphlet Special table 2007-520739

When the alignment film is formed of only an inorganic material as in Patent Document 1, the hardness of the alignment film can be increased. However, the hardness makes it difficult to process, and a layer made of an inorganic material is formed. In this case, it is necessary to perform vacuum deposition, and there is a problem in that the process becomes complicated and the cost increases in manufacturing the polarizing element.
In addition, since the difference in thermal expansion coefficient with the base material is large in a layer containing only an inorganic substance, a crack due to the thermal expansion difference occurs due to the heat treatment in the manufacturing process, and this causes fogging of a polarizing element such as a lens. There was a problem that occurred.

  In the method disclosed in Patent Document 2, an adhesive primer layer made of a composition based on polyethylene glycol (meth) acrylate or the like is provided on the curved surface of the lens before spin coating of the polarizing liquid. The primer layer is a composition consisting essentially of organic components, and as pointed out in Patent Document 1, when the film or base material of the polarizing layer is mainly composed of organic matter, In the manufacturing process, there is a problem that the polarizing layer is easily peeled off.

  The present invention has been made under such circumstances, and it is an object of the present invention to provide a method for manufacturing a polarizing element that can be manufactured in a simple process and that does not cause separation of the polarizing layer in the manufacturing process. is there.

  As a result of intensive studies to achieve the above object, the inventors of the present invention were obtained by heat-treating a mixture containing alkoxysilane and / or hexaalkoxydisiloxane, water and alcohols under specific conditions. It has been found that the above problem can be solved by forming an alignment layer of a polarizing element using an alignment film coating solution. The present invention has been completed based on such findings.

That is, this invention provides the manufacturing method of the polarizing element which has the following process I-process V.
Step I: 40 mixture containing alkoxysilane represented by the following general formula (1) and / or hexaalkoxydisiloxane (A), water (B) and alcohols (C) represented by the following general formula (2) Step of preparing an alignment film coating solution by performing a heat treatment at ~ 120 ° C for 0.5 to 24 hours Si (OR ¹ ) _a (R ² ) _4-a (1)
_{^{(R 3 O) 3 Si-}} O-Si (OR 4) 3 (2)
(Wherein R ¹ , R ³ and R ⁴ are each independently an alkyl group having 1 to 5 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, and a is 3 or 4. .)
Step II: A process of depositing the alignment film coating solution prepared in Step I on the base material to form a sol-gel film Step III: A uniaxial polishing treatment is applied to the sol-gel film formed in Step II Step VI: forming a polarizing layer by depositing dichroic dyes on the alignment layer formed in Step III and forming a polarizing layer Step V: forming in Step VI Forming a protective layer for fixing the dye on the polarizing layer

  ADVANTAGE OF THE INVENTION According to this invention, it can manufacture with a simple process and can provide the manufacturing method of the polarizing element which does not produce peeling in a polarizing layer in a manufacturing process.

Hereinafter, the present invention will be described in detail.
The structure of the polarizing element obtained in the present invention will be described with reference to FIG. The polarizing element of the present invention has an alignment layer 5 and a polarizing layer 6 on a substrate 1. The polarizing layer 6 is formed by depositing and arranging dichroic dyes, and usually has a protective layer 7 for fixing the dyes thereon. Furthermore, the polarizing element in the present invention has a function such as a water repellent film on the hard coat layer 2, the adhesion layer 3, or the protective layer 7 on the substrate 1 as in the example of FIG. May have a conductive film 8. As a suitable example of a polarizing element, the polarizing lens which uses a lens base material as the base material 1 is mentioned, for example.

The manufacturing method of the polarizing element in this invention has the following process I-process V.
Step I: 40 mixture containing alkoxysilane represented by the following general formula (1) and / or hexaalkoxydisiloxane (A), water (B) and alcohols (C) represented by the following general formula (2) Step of preparing an alignment film coating solution by performing a heat treatment at ~ 120 ° C for 0.5 to 24 hours Si (OR ¹ ) _a (R ² ) _4-a (1)
_{^{(R 3 O) 3 Si-}} O-Si (OR 4) 3 (2)
(Wherein R ¹ , R ³ and R ⁴ are each independently an alkyl group having 1 to 5 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, and a is 3 or 4. .)
Step II: A process of depositing the alignment film coating solution prepared in Step I on the base material to form a sol-gel film Step III: A uniaxial polishing treatment is applied to the sol-gel film formed in Step II Step VI: forming a polarizing layer by depositing dichroic dyes on the alignment layer formed in Step III and forming a polarizing layer Step V: forming in Step VI Forming a protective layer for fixing the dye on the polarizing layer

  In Step I, first, alkoxysilane represented by the following general formula (1) and / or hexaalkoxydisiloxane (A), water (B) and alcohols (C) represented by the following general formula (2) are contained. Prepare the mixture. The method for preparing the mixture is not particularly limited, and can be carried out by weighing out a predetermined amount of each component and sufficiently stirring and mixing them. In addition, the addition order of each component is not specifically limited.

(A) The alkoxysilane represented by the following general formula (1) and / or the hexaalkoxydisiloxane represented by the following general formula (2) forms a continuous skeleton structure in the film and imparts film curability. In addition, it is used to suppress peeling of the polarizing layer.
Si (OR ¹ ) _a (R ² ) _4-a (1)
(R ³ O) ₃ Si—O—Si (OR ⁴ ) ₃ (2)
Here, R ¹ in the general formula (1) and R ^{3 to} R ⁴ in the general formula (2) are each independently an alkyl group having 1 to 5 carbon atoms, and are linear, branched, or cyclic. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group and the like can be mentioned. It is done. Among these, a methyl group and an ethyl group are preferable.
R < ² > in the said General formula (1) is a C1-C10 alkyl group, The C1-C5 alkyl group, hexyl group, heptyl group, octyl group, and 2-ethylhexyl group which were illustrated above. Etc. In this, a methyl group, an ethyl group, a propyl group, and a butyl group are preferable. A in the general formula (1) is 3 or 4.

Examples of the tetraalkoxysilane represented by the general formula (1) (wherein a = 4) include tetraethoxysilane (TEOS), tetramethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, and tetra-n. -Butoxysilane tetra-sec-butoxysilane, tetra-tert-butoxysilane and the like.
Examples of trialkoxysilanes represented by the general formula (1) (wherein a = 3) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-propoxysilane, and methyltri-n. -Butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane and the like.
The hexaalkoxydisiloxane represented by the general formula (2) is not particularly limited, and examples thereof include hexamethoxydisiloxane and hexaethoxydisiloxane.

Of these, preferably tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetraisopropoxysilane, methyltriisopropoxysilane, hexaethoxydisiloxane, and hexamethoxydisiloxane, more preferably Tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and more preferably tetraethoxysilane. These can be used singly or in combination of two or more. In the present invention, as an alkoxysilane compound other than the component (A), for example, a functional group-containing alkoxysilane can be used in combination with the component (A) as long as the effects of the present invention are not impaired. From the viewpoint of reducing peeling of the polarizing layer in the process, it is preferably not contained. Specific examples of the functional group-containing alkoxysilane include glycidoxy group-containing trialkoxysilanes, epoxyalkylalkoxysilanes, amino group-containing alkoxysilanes, and the like exemplified later as materials used for the protective layer.
In the present invention, it is preferable to use a tetraalkoxysilane represented by the general formula (1) (wherein a = 4) alone or more than other silane compounds among the silane compounds.

(A) Alkoxysilane and / or hexaalkoxydisiloxane undergoes a hydrolysis reaction in the presence of water. The amount of water (B) added to the system is preferably in the range of 0.5 to 3 molar equivalents, and 1 to 2 molar equivalents relative to the alkoxysilane and hexaalkoxydisiloxane added as component (A). The range of is more preferable. If the amount of water added is 0.5 molar equivalent or more with respect to component (A), a film having a hardness that can withstand the use of a plastic lens can be formed without any alkoxy groups remaining during the hydrolysis reaction. If it is 3 molar equivalents or less, film curing due to polymerization of the components (A) occurs more than necessary, and one molecule of polysiloxane formed by curing becomes large, resulting in a rough film, resulting in In addition, there is no worry that sufficient hardness as a film for plastic lenses cannot be obtained.
There is no restriction | limiting in particular as the addition method of water (B), In order to accelerate | stimulate a hydrolysis reaction, you may add as the aqueous solution of the acid or alkali catalyst normally added.

The alcohol (C) is used as a solvent soluble in alkoxysilane and / or hexaalkoxydisiloxane (A) and water (B).
Examples of alcohols (C) include methanol, ethanol, isopropanol, butanol, 2-methoxyethanol, diacetone alcohol, and 1-methoxy-2-propanol. Among these, methanol, ethanol, and isopropanol are preferable from the viewpoint of the solubility of silanes and siloxanes in alcohols.
The usage-amount of alcohol (C) becomes like this. Preferably it is the range of 20-500 mass% with respect to (A) component, More preferably, it is the range of 50-400 mass%. If the amount of the alcohol (C) used is 20% by mass or more with respect to the component (A), sufficient force to dissolve the component (A) can be secured, and if it is 500% by mass or less, (A) It is possible to keep the reactivity of the components.
As long as the effect of the present invention is not impaired, amides such as dimethylformamide, glycol ethers such as propylene glycol monomethyl ether, and the like can be used as desired as the solvent.

Next, the mixture containing the components (A) to (C) prepared above is subjected to heat treatment at 40 to 120 ° C. for 0.5 to 24 hours, and in the alkoxysilane material by the sol-gel method. An alignment film coating solution can be prepared through hydrolysis and condensation polymerization of alkoxy groups.
The temperature of the heat treatment is in the range of 40 to 120 ° C., preferably in the range of 50 to 110 ° C., from the viewpoint of sufficiently allowing the hydrolysis reaction to proceed without causing precipitation or gelation of the component (A). The range of 70-100 degreeC is more preferable. Further, from the viewpoint of obtaining a sufficient reaction rate, it is preferable to perform heat treatment with stirring while maintaining as high a temperature as possible. For this purpose, in the heat treatment, the mixture containing the components (A) to (C) is heated to reflux. It is preferable to do.
The heat treatment time is in the range of 0.5 to 24 hours. Moreover, it is preferable that the temperature is controlled so as to be continuously maintained within a range of the heating temperature. If it is kept at a high temperature for a long time, problems such as precipitation of component (A) and gelation occur as described above. From these viewpoints, the range of 1 to 15 hours is preferable.
By using the alignment film coating solution prepared by heat treatment as described above, it becomes possible to improve the adhesion between the alignment layer and the polarizing layer to be formed in a later step, and the peeling of the polarizing layer is effective. Can be reduced.

Furthermore, in order to reduce peeling and fogging of the polarizing layer, it is preferable to add an aluminum chelate (D) to the mixture obtained after the heat treatment, if necessary, and further heat-treat. Examples of the aluminum chelate (D) include aluminum acetylacetonate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate) , Aluminum tris (acetylacetonate), and aluminum monoisopropoxymonooleoxyethyl acetoacetate. These can be used singly or in combination of two or more.
The amount of the aluminum chelate (D) used is preferably in the range of 0.05 to 5% by mass, more preferably in the range of 0.1 to 3% by mass with respect to the component (A). If the amount of the aluminum chelate (D) used is 0.05% by mass or more with respect to the component (A), the effect of reducing peeling and fogging can be imparted, and if it is 5% by mass or less, aluminum is used. There is no problem of decrease in adhesion and transparency due to excessive content.
As temperature of heat processing, Preferably it is the range of 40-120 degreeC, More preferably, it is the range of 50-100 degreeC. The heat treatment time is preferably in the range of 0.5 to 24 hours. The heat treatment is preferably performed with stirring.
The amount of the solid component of the array film coating solution is preferably 0.2 to 20% by mass, more preferably 1 to 10% by mass. The amount of the solid component of the coating liquid can be adjusted using a solvent such as the alcohols exemplified above so as to be in a desired range. In addition, the solid component of a coating liquid can be calculated by the method as described in the Example mentioned later.

In step II, the alignment film coating solution prepared in step I is deposited on the base material to form a sol-gel film (see FIG. 1A). In this process, since it is not necessary to use a large-scale vacuum vapor deposition equipment necessary for forming a conventional layer made of an inorganic substance such as SiO ₂ , the complexity can be eliminated and the manufacturing process can be simplified. .

(Base material)
The substrate used in the present invention is not particularly limited, and examples thereof include a plastic substrate and an inorganic glass substrate. The material of the plastic substrate is, for example, methyl methacrylate homopolymer, copolymer of methyl methacrylate and one or more other monomers, diethylene glycol bisallyl carbonate homopolymer, diethylene glycol bisallyl carbonate and one or more other Copolymers with monomers, sulfur-containing copolymers, halogen copolymers, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane, polythiourethane, and polymers having epithio groups Etc.
Although the surface shape of a base material is not specifically limited, It can be set as arbitrary shapes, such as planar shape, concave shape, or convex shape.

  In the polarizing element of the present invention, an alignment layer is formed on a substrate. The alignment layer may be directly laminated on the substrate, and may have a hard coat layer or a primer layer between the substrate and the alignment layer.

The hard coat layer formed as necessary between the substrate and the alignment layer is not particularly limited, and a coating composition comprising a known organosilicon compound and inorganic oxide colloidal particles can be used. Examples of the organosilicon compound and the inorganic oxide colloidal particles include those described in paragraphs [0071] to [0074] of JP-A-2007-77327. The coating composition for the hard coat layer can be prepared by a conventionally known method.
Examples of the method for forming the hard coat layer on the substrate include a method of applying the coating composition to the substrate. As a coating means, a commonly performed method such as a dipping method, a spin coating method, or a spray method can be applied, but a dipping method or a spin coating method is particularly preferable from the viewpoint of surface accuracy.
Moreover, well-known various resins, such as a polyurethane, can be used for a primer layer from a viewpoint of improving adhesiveness.

  Before depositing the coating liquid on the substrate, the substrate is subjected to chemical treatment with acid, alkali, various organic solvents, physical treatment with plasma, ultraviolet rays, detergent treatment using various detergents, sandblast treatment, By performing primer treatment using various resins, it is possible to improve the adhesion between the substrate and the alignment layer.

By applying the coating liquid onto the substrate and subsequently performing a heat treatment, the coating solution can be deposited on the substrate to form a sol-gel film. The coating method for the coating liquid is not particularly limited, and known methods such as spin coating, dip coating, flow coating, spray coating, and the like can be applied. Among these, spin coating is preferable from the viewpoint of surface accuracy.
The thickness of the sol-gel film is preferably 0.02 to 5 μm, more preferably 0.05 to 0.5 μm. When the thickness is 0.02 μm or more, the entire film can be made to function without being peeled off during polishing, and when it is 5 μm or less, the occurrence of cracks can be reduced.
The conditions for coating and heat treatment are not particularly limited, but for example, the coating conditions are preferably in the range of 0.5 to 3 minutes. The rotation speed of the spin coater in the case of spin coating is preferably in the range of 200 to 2000 rpm. Moreover, it is preferable to perform heat processing at 50-120 degreeC and 0.5 to 3 hours.

It is preferable that the sol-gel film formed in Step II is immersed in an aqueous solution of weak acid or weak alkali after Step II and before the next Step III. By immersing the sol-gel film in a weak acid or alkaline solution, the adhesion between the sol-gel film and the dye layer is increased and is difficult to peel off. Further, the scratch resistance is improved and the generation of haze due to polishing scratches is suppressed. be able to. Herein, the term dissociation constant pK _a from the weak acid points to 3.5 or more acid dissociation exponent pK _b is a weak alkaline refers to a 3.5 or more alkaline.
Examples of the weak acid or weak alkali used for the immersion treatment include weak acids such as acetic acid, oxalic acid, formic acid, and benzoic acid, and weak alkalis such as aqueous ammonia, monoethanolamine, diethanolamine, and triethanolamine. The immersion conditions are not particularly limited, but are preferably 1 to 30 minutes, more preferably 3 to 20 minutes.

In step III, in order to deposit and deposit the dichroic dye on the alignment layer, the sol-gel film formed in step II is uniaxially polished to form an alignment layer having uniaxial polishing marks. (See FIG. 1B). The polishing treatment is preferably performed using an abrasive.
In step III, the alignment layer formed on the substrate is provided for aligning and depositing the dichroic dye. The alignment layer is made of a sol-gel film formed by attaching an alignment film coating solution.
Here, in the case of liquid crystal, it is known that the liquid crystal is arranged in a certain directional relationship with this direction by unidirectional friction processing or polishing processing on the substrate. For example, in manufacturing a liquid crystal display (LCD), it is well known that a so-called rubbing process is performed in which an alignment film (such as polyimide) attached on a substrate is rubbed in one direction in order to align liquid crystals in a cell. . Techniques for coating a dichroic dye solution on a unidirectionally polished substrate, arranging the dye and utilizing the dichroism are disclosed in, for example, US Pat. No. 2,400,087 and US Pat. No. 4,865,668. Is disclosed.
Also in the present invention, the dichroic dyes can be aligned in the uniaxial direction by polishing the sol-gel film formed on the substrate, as in the case of liquid crystals in liquid crystal display (LCD) production.

The abrasive used for the polishing treatment is not particularly limited, and for example, a slurry in which a slurry containing abrasive particles is immersed in a foam material such as urethane foam can be used. Examples of the abrasive particles include Al ₂ O ₃ , ZrO ₂ , TiO ₂ , and CeO ₂ . Among these, Al ₂ O ₃ is preferable from the viewpoints of hardness (easiness of polishing, finishing) for the formed sol-gel film and chemical stability. These may be used alone or in combination of two or more. Moreover, the slurry containing abrasive particles may contain a viscosity modifier, a pH adjuster and the like.

The average particle size of the abrasive particles is preferably less than 2 μm, more preferably 0.5 to 1.5 μm, and even more preferably 0.7 to 1.4 μm.
A conventional thin film made of an inorganic substance such as SiO ₂ vapor deposition is hard and therefore difficult to carry out a fine polishing treatment. For example, depending on the application such as a spectacle lens, there is a problem that a polishing mark becomes rough. In the present invention, since there is no hardness like a thin film made of an inorganic substance, polishing using an abrasive having an average particle size of less than 2 μm is possible. In addition, the use of finer particle abrasive than conventional ones enables finer polishing, resulting in higher haze pressure and haze generation due to polishing scratches even when intensive polishing is performed at one location. It is possible to suppress the generation of defective products, and the polarizing element can be easily manufactured.
The polishing conditions are not particularly limited, and the rotation speed, polishing pressure, polishing time, and the like can be adjusted as appropriate.

In Step IV, a dichroic dye is arranged and deposited on the alignment layer having uniaxial polishing marks formed in Step III to form a polarizing layer (see FIG. 1C).
The polarizing layer in the present invention comprises one or more dichroic dyes. Here, “dichroism” means a property in which the color of transmitted light varies depending on the propagation direction because the medium has selective absorption anisotropy with respect to light, and the dichroic dye is polarized light. On the other hand, the light absorption becomes stronger in a specific direction of the dye molecule, and the light absorption becomes smaller in the direction perpendicular thereto. Among dichroic dyes, those that exhibit a liquid crystal state in a certain concentration and temperature range when water is used as a solvent are known. Such a liquid crystal state is called lyotropic liquid crystal. If the dye molecules can be arranged in one specific direction using the liquid crystal state of the dichroic dye, stronger dichroism can be expressed.
As a dichroic dye used for this invention, it does not specifically limit, What is known as what is normally used for a polarizing element can be used. Examples include azo, anthraquinone, merocyanine, styryl, azomethine, quinone, quinophthalone, perylene, indigo, tetrazine, stilbene, benzidine and the like. Moreover, the thing etc. which are described in US Patent 24000877 specification and Japanese translations of PCT publication No. 2002-527786 are mentioned.

Usually, before forming the polarizing layer, the polished surface of the array layer is completely washed and dried. Next, a polarizing layer is formed by applying an aqueous solution or suspension (preferably an aqueous solution) containing a dichroic dye on an array layer having polishing marks, and further performing a water-insoluble treatment of the dichroic dye. can do.
A polarizing element having a desired hue can be produced by blending a dye other than the above with an aqueous solution or suspension containing a dichroic dye as long as the effects of the present invention are not impaired. Furthermore, additives such as a rheology modifier, an adhesion promoter, a plasticizer, and a leveling agent may be blended as necessary from the viewpoint of improving applicability and the like.
The application method is not particularly limited, and examples thereof include known methods such as spin coating, dip coating, flow coating, and spray coating.
As the water insolubilization treatment, a method of immersing the dichroic dye applied on the alignment layer in an aqueous metal salt solution is preferable. The metal salt that can be used is not particularly limited, and examples thereof include AlCl ₃ , BaCl ₂ , CdCl ₂ , ZnCl ₂ , FeCl _2, and SnCl ₃ . Among these, AlCl ₃ and ZnCl ₂ are preferable from the viewpoint of safety. After the water-insoluble treatment, the surface of the dichroic dye may be further dried.
Although the thickness of a polarizing layer is not specifically limited, It is preferable in it being the range of 0.05-0.5 micrometer.

Step V is a step of forming a protective layer for fixing the dye on the polarizing layer formed in Step IV (see FIG. 1D).
As a material used for the protective layer, an organic silicon compound can be used, for example, glycidoxy group such as γ-glycidoxypropyltrimethoxysilane (γ-GPS), γ-glycidoxypropylmethyldiethoxysilane, and the like. Containing trialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3 4-epoxycyclohexyl) butyltrimethoxy Silane, epoxyalkylalkoxysilanes such as δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ -Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ -Amino group-containing alkoxysilanes such as aminopropylmethyldiethoxysilane are preferred, but not particularly limited thereto. These compounds may be used alone or in combination of two or more.
The dye protective layer can be formed by applying a liquid containing the organosilicon compound on the polarizing layer by a known means such as a dipping method, a spin coating method, or a spray method, and then forming a film by heat curing. At this time, the organosilicon compound penetrates into the polarizing layer to form a layer in which the dye protective layer and the polarizing layer are substantially integrated. The thickness of the layer in which the dye protective layer and the polarizing layer are integrated is not particularly limited, but is preferably in the range of 0.05 to 1 μm.

  For the obtained polarizing element, functional films such as a hard coat film, an antireflection film, a water repellent film, a UV absorbing film, an infrared absorbing film, a photochromic film, and an antistatic film that improve the scratch resistance are known. (See FIG. 1E).

  According to said method, a high quality polarizing element can be manufactured according to a simple process. The polarizing element of the present invention is widely used for optical applications such as spectacle lenses, sunglasses, display devices, optical transmission devices, automobiles and building window glass, and is particularly preferably used as a plastic lens for spectacles. In the case of a plastic lens for spectacles, the refractive index is usually 1.50 to 1.80, and the Abbe number is usually 30 or more.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In addition, the physical property evaluation of the obtained polarizing element was performed as follows.
(1) Polarization degree The polarization degree (P _eff ) was evaluated by calculating the parallel transmittance (T _// ) and the vertical transmittance (T⊥) according to ISO 8980-3 and calculating by the following formula. Parallel transmittance and vertical transmittance were measured using a visible spectrophotometer and a polarizer.
P _eff (%) = [(T _{// −} T⊥) / (T _// + T⊥)] × 100

(2) Transparency (haze value)
The haze value of the produced polarizing element was measured with a haze meter MH-150 manufactured by Murakami Color Research Laboratory, and the presence or absence of cloudiness was determined.
(Evaluation criteria)
A: Haze value <0.4%
○: 0.4% ≦ haze value <1.0%
Δ: 1.0% ≦ haze value <2.0%
×: Haze value ≧ 2.0%

(3) Releasability of polarizing layer When forming the dye protective layer, peeling is observed when the peeling of the polarizing layer (dye layer) is visually observed in the plane of the polarizing element (x), and peeling is not observed when it is not recognized ( ○).

Example 1
(Manufacture of array film coating solution)
Ethanol 40 g was added to 85 g of tetraethoxysilane (TEOS) (molecular weight 208.3, trade name “KBE-04”, manufactured by Shin-Etsu Chemical Co., Ltd.) and stirred. Next, 14.75 g of 0.01 mol / L hydrochloric acid (containing 2 times the molar amount of water of TEOS) was added with stirring. The mixture was stirred for 5 minutes until it became clear.
Next, the above-mentioned mixed solution was filled in a round bottom flask equipped with a cooling pipe, the flask was heated with a mantle heater, and water at room temperature was passed through the cooling pipe to heat and reflux for 1 hour. During this time, the liquid was stirred and the liquid temperature was maintained at 75-80 ° C. Thereafter, this liquid was cooled to room temperature over 1 hour by natural cooling to obtain an array film coating stock solution. 30 g of ethanol was added to 5 g of the obtained alignment film coating stock solution, diluted and stirred to obtain alignment film coating liquid 1 (solid component: 2.5% by mass of the total coating liquid).
Here, the solid component is the stoichiometric amount when all alkoxy groups (OR group, R: alkyl group) in the alkoxysilane material are hydrolyzed to form siloxane bonds (Si—O—Si bonds). “Solid component” amount.

(Array film formation)
As a lens base material, a phoenix lens (manufactured by HOYA Corporation, refractive index 1.53, with hard coat, diameter 70 mm, base curve 4) is used. Spin coating (about 2 ml at 800 rpm) is applied to the concave surface of the lens. Supply, hold for 60 seconds), followed by heat treatment at 85 ° C. for 1 hour to cure to form an array film (sol-gel film) having a thickness of about 100 nm.

(Polishing process)
Abrasive-containing urethane foam (abrasive: “POLIPLA304M”, manufactured by Fujimi Incorporated, average particle size 0.85 μm Al ₂ O ₃ particles, urethane foam: substantially the same shape as the curvature of the concave surface of the spherical lens ) Was applied for 10 seconds under the conditions of a rotational speed of 350 rpm and a polishing pressure of 50 g / cm ² . The lens subjected to the polishing treatment was washed with pure water and dried.

(Formation of polarizing layer)
After the lens is dried, spin coating is performed on the polished surface using 2 to 3 g of an about 5 mass% aqueous solution of a dichroic dye [trade name “Varilight solution 2S”, manufactured by Sterling Optics Inc.]. To form a polarizing layer. Spin coating was performed by supplying an aqueous dye solution at a rotation speed of 300 rpm and holding it for 8 seconds, then supplying it at a rotation speed of 400 rpm and holding it for 45 seconds, and further supplying it at 1000 rpm and holding it for 12 seconds.
Next, an aqueous solution of pH 3.5 having an iron chloride concentration of 0.15 M and a calcium hydroxide concentration of 0.2 M was prepared, and the lens obtained above was immersed in this aqueous solution for about 30 seconds, and then pulled up to obtain pure water. Wash thoroughly. By this step, the water-soluble dye is converted into hardly soluble.

(Formation of dye protective film)
Thereafter, the lens was immersed in a 10% by mass aqueous solution of γ-aminopropyltriethoxysilane for 15 minutes, then washed three times with pure water, and thermally cured at 85 ° C. for 30 minutes. Further, after cooling, the lens was immersed in a 2% by mass aqueous solution of γ-glycidoxypropyltrimethoxysilane for 30 minutes in the air, and then cured in a furnace at 100 ° C. for 30 minutes and cooled after curing to form a dye protective film. Formed.
The polarization degree of the obtained polarizing lens, transparency, and peelability of the polarizing layer were evaluated. The obtained polarizing lens showed a high degree of polarization of 99.7%, a haze value of 1.2%, and no haze was observed. Moreover, peeling was not observed. The results are shown in Table 1.

Example 2
(Manufacture of array film coating solution)
In a round bottom flask covered with a heat insulating material other than the tubular portion, tetraethoxysilane (TEOS) (molecular weight 208.3, trade name “KBE-04”, manufactured by Shin-Etsu Chemical Co., Ltd.) 85 g, ethanol 40 g, and 0.01 mol / L Hydrochloric acid 14.75 g (including 2 times the molar amount of TEOS water) was added and mixed with stirring. At this time, the mixed solution generated heat due to water in hydrochloric acid, and the temperature was raised to 50 ° C. to proceed the hydrolysis reaction. Further, stirring was continued even after the temperature was raised, and this temperature was maintained for about 2.5 hours by the heat insulating material. After the completion of the reaction, the temperature of the mixed solution began to drop, but it was allowed to cool naturally with the heat insulating material covered around the flask and allowed to cool to room temperature to obtain an array membrane coating stock solution. 30 g of ethanol was added to 5 g of the array film coating stock solution prepared as described above, diluted and stirred to obtain array film coating liquid 2 (solid component: 2.5 mass% of the total amount of the coating liquid).
Next, a polarizing lens was produced in the same manner as in Example 1 except that the alignment film coating liquid 2 was used as the alignment film coating liquid.
The polarization degree of the obtained polarizing lens, transparency, and peelability of the polarizing layer were evaluated. The degree of polarization was as high as 99.5%, the haze value was 1.5%, and no severe haze was observed. Moreover, peeling was not observed. The results are shown in Table 1.

Example 3
(Preparation of array film coating solution)
In the same manner as in Example 1, 1.4 g of aluminum acetylacetonate (1% by mass with respect to the array film coating stock solution) was added and mixed well with the solution obtained by heat reflux treatment. This solution was stirred for 4 hours while being kept at 50 ° C., and then cooled to room temperature to obtain an array film coating stock solution. 30 g of ethanol was added to 5 g of the obtained alignment film coating stock solution, diluted and stirred to obtain alignment film liquid coating liquid 3 (solid component: 2.5 mass% of the total amount of the coating liquid).
Next, a polarizing lens was produced in the same manner as in Example 1 except that the alignment film coating solution 3 was used as the alignment film coating solution.
The obtained polarizing lens showed a high degree of polarization of 99.5%, a haze value of 0.65%, and no strong haze was observed. Moreover, peeling was not observed.

Example 4
After forming the alignment film on the base material in the same manner as in Example 1, before the subsequent polishing step, the base material on which the alignment film was formed was immersed in a 10% by mass acetic acid aqueous solution for 15 minutes, and then taken out and purified water. A polarizing lens was produced in the same manner as in Example 1 except that the treatment washed with and dried was added, and then the polishing step was carried out in the same manner as in Example 1.
The obtained polarizing lens showed a high degree of polarization of 99.4%, a haze value of 0.62%, and no strong haze was observed. Moreover, peeling was not observed. The results are shown in Table 1.

Example 5
In Example 4, a polarizing lens was produced in the same manner as in Example 4 except that the array film coating solution 3 prepared in Example 3 was used in place of the array film coating solution 1.
The obtained polarizing lens showed a high degree of polarization of 99.7%, a haze value of 0.35%, and no haze was observed. Moreover, peeling was not observed. The results are shown in Table 1.

Example 6
A polarizing lens was produced in the same manner as in Example 5 except that 28% by mass of ammonia water was used in place of the acetic acid aqueous solution for the immersion treatment of the base material on which the alignment film of Example 5 was formed. The obtained polarizing lens showed a high degree of polarization of 99.7%, a haze value of 0.35%, and no haze was observed. Moreover, peeling was not observed. The results are shown in Table 1.

Examples 7-9
In the manufacturing process of the alignment film coating liquid of Example 2, instead of tetraethoxysilane, tetramethoxysilane (Example 7: KBM-04, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 62.1 g, methyltrimethoxysilane ( Example 8: KBM-13, trade name of Shin-Etsu Chemical Co., Ltd. 55.6 g, methyltriethoxysilane (Example 9: KBE-13, trade name of Shin-Etsu Chemical Co., Ltd.) 72.7 g, respectively. Polarizing lenses were produced in the same manner as in Example 2 except that the alignment film coating solutions 4 to 6 were prepared and used. In all cases, a high degree of polarization was obtained, and no severe haze was observed. Moreover, peeling was not observed. The results are shown in Table 1.

Comparative Example 1
In the production of the alignment film coating solution of Example 2, the raw materials were added and mixed in a round bottom flask not covered with a heat insulating material. The solution generated heat by water contained in 0.01 mol / L hydrochloric acid added as a raw material, and the temperature was raised to about 50 ° C., but then the temperature started to drop to 35 ° C. after 10 minutes and further to room temperature over 1 hour. The solution was allowed to cool to obtain an array film coating stock solution. 30 g of ethanol was added to 5 g of the obtained array membrane coating stock solution, diluted and stirred to obtain an array membrane solution coating solution 7 (solid component: 10% by mass of the total coating solution).
Next, a polarizing lens was produced in the same manner as in Example 2 except that the alignment film coating liquid 7 was used as the alignment film coating liquid.
The obtained polarizing lens showed a low degree of polarization of 65%, a haze value of 5.5%, and intense clouding occurred. Many peelings were observed. The results are shown in Table 1.

According to the present invention, it is possible to provide a method for manufacturing a polarizing element such as a polarizing lens that can be manufactured by a simple process and does not cause peeling of the polarizing layer in the manufacturing process and has excellent performance.
The obtained polarizing element can be widely applied to optical applications such as spectacle lenses, sunglasses, display equipment, light transmission equipment, automobile and building window glass, and can be suitably used especially as plastic lenses for spectacles.

It is a cross-sectional schematic diagram which shows an example of the manufacturing process of the polarizing element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; Base material 2; Hard-coat layer 3; Adhesion layer 4; Sol-gel film 5; Arrangement layer 6; Polarizing layer (arranged dye layer)
7; Dye protective film (protective layer)
8; Functional film (water repellent film, etc.)

Claims (7)

The manufacturing method of the polarizing element which has the following process I-process V.
Step I: 40 mixture containing alkoxysilane represented by the following general formula (1) and / or hexaalkoxydisiloxane (A), water (B) and alcohols (C) represented by the following general formula (2) Step of preparing an alignment film coating solution by performing a heat treatment at ~ 120 ° C for 0.5 to 24 hours Si (OR ¹ ) _a (R ² ) _4-a (1)
_{^{(R 3 O) 3 Si-}} O-Si (OR 4) 3 (2)
(Wherein R ¹ , R ³ and R ⁴ are each independently an alkyl group having 1 to 5 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, and a is 3 or 4. .)
Step II: A process of depositing the alignment film coating solution prepared in Step I on the base material to form a sol-gel film Step III: A uniaxial polishing treatment is applied to the sol-gel film formed in Step II Step VI: forming a polarizing layer by depositing dichroic dyes on the alignment layer formed in Step III and forming a polarizing layer Step V: forming in Step VI Forming a protective layer for fixing the dye on the polarizing layer   The mixture containing the components (A) to (C) in Step I is 0.5 to 3 molar equivalents of water (B) and alcohols (C) 20 to the component (A) and the component (A). The manufacturing method of the polarizing element of Claim 1 which is a mixture containing 500 mass%.   The manufacturing method of the polarizing element of Claim 1 or 2 which heat-refluxs the mixture containing (A)-(C) component in the heat processing of the process I.   Step I adds 0.3 to 5% by mass of aluminum chelate (D) to component (A) to the mixture obtained by heat-treating the mixture containing components (A) to (C). And the manufacturing method of the polarizing element in any one of Claims 1-3 which is a process of performing heat processing and preparing an arrangement | sequence film coating liquid.   Aluminum chelate (D) is aluminum acetylacetonate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris The manufacturing method of the polarizing element of Claim 4 which is 1 or more types chosen from the group which consists of (acetylacetonate) and aluminum monoisopropoxy monooroxyethyl acetoacetate.   6. The method according to claim 1, further comprising a step of immersing the sol-gel film formed in Step II in any one of an organic acid aqueous solution, an ammonia aqueous solution, and an amine aqueous solution between Step II and Step III. The manufacturing method of the polarizing element in any one.   The component (A) is selected from the group consisting of tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetraisopropoxysilane, methyltriisopropoxysilane, hexaethoxydisiloxane, and hexamethoxydisiloxane. The manufacturing method of the polarizing element in any one of Claims 1-6 which is 1 or more types.