JP2010224504A - Dyeing method of base material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dyeing method capable of easily changing a dyeing density without damaging the quality of a base material or a hard coat layer. <P>SOLUTION: The dyeing method includes an ultraviolet irradiation step of executing ultraviolet irradiation to the surface of the base material and a dyeing step of dyeing the base material thereafter, and the dyeing density of the base material in the dyeing step is controlled by the ultraviolet irradiation. When the surface of the base material is the hard coat layer, the dyeing density of the hard coat layer is easily controlled. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for dyeing a substrate.

Plastic lenses as optical articles, particularly plastic lenses for spectacles, are often used in a colored manner for imparting fashionability and protecting eyes. As a coloring method, the method of dying by immersing a plastic lens in a dyeing liquid in which a dye is dispersed in a solvent is simple, wide choice of colors, half and gradation dyeing, etc. Widely used in.
On the other hand, in recent years, high refractive index materials such as thiourethane-based resins and episulfide-based resins have been developed in order to meet further demands for reducing the thickness and weight of spectacle lenses.
However, since such a high refractive index material is inferior in dyeability, it is difficult to dye a lens substrate made of the material itself.
Therefore, a method for dyeing a hard coat layer provided on the surface of a plastic lens substrate has been proposed (see, for example, Patent Documents 1 and 2). According to the method disclosed in Patent Document 1, the hard coat layer contains a compound having a long molecular chain and a small number of reactive groups, such as a polyfunctional epoxy compound, thereby widening the gap between molecules and adding a dye. Dyeability can be improved by facilitating penetration. Further, according to the method disclosed in Patent Document 2, since the hard coat layer is formed from a coating composition containing biaryl sulfide, a high dyeing effect can be obtained without impairing the hardness and durability of the hard coat layer. Can demonstrate.

JP 2008-096886 A JP 2008-233676 A

However, although the methods disclosed in Patent Documents 1 and 2 both improve the dyeability of the hard coat layer, it is difficult to control the degree of dyeing. For example, when trying to change the dyeing density at the time of dyeing the hard coat layer, various types of dyeing liquids with different dyeing agent concentrations are prepared, or the coating composition is changed in various ways. It is necessary to form a hard coat layer having the above dyeing property. Such preparatory work is complicated and not only increases the dyeing cost, but also may reduce the scratch resistance and durability of the hard coat layer.
Then, this invention is made | formed in view of such a situation, and it aims at providing the dyeing | staining method which can change a dyeing density easily, without impairing the property of a base material or a hard-coat layer. .

  As a result of intensive studies on the above problems, the present inventors have found that the dyeability can be controlled by subjecting the substrate surface to high energy treatment such as ultraviolet irradiation or plasma treatment or ozone treatment. The present invention has been completed.

That is, the present invention is a substrate dyeing method, comprising a high energy treatment step of applying a high energy treatment to the surface of the substrate, and then a dyeing step of dyeing the substrate. The dyeing density of the base material in the dyeing process is controlled by energy treatment.
Here, the high-energy treatment on the substrate means irradiation with high-energy electromagnetic waves such as ultraviolet rays, irradiation with high-energy particle beams such as electron beams, or plasma treatment.
According to the base material dyeing method of the present invention, since the surface of the base material is provided with a high energy processing step for performing high energy processing, the dyeing density in the subsequent step can be changed depending on the processing conditions. Become. Specifically, the staining density can be reduced by high energy treatment. Therefore, it is possible to control the staining density in the subsequent process only by a simple operation of controlling the energy level and the processing time in the high energy processing process.
In the present invention, when a hard coat layer is formed on the substrate surface, the hard coat layer and the hard coat layer may be referred to as a substrate.

In this invention, it is preferable that the said dyeing process changes the dyeing density of the said base material by changing the energy of the said high energy process.
According to the present invention, in the dyeing process, the dyeing density of the base material is changed by changing the energy in the high energy treatment process, which is the preceding process, so that the dyeing density is easily controlled.

In the present invention, the high energy treatment is preferably at least one of ultraviolet irradiation and plasma treatment.
According to this invention, since the high energy treatment is at least one of ultraviolet irradiation and plasma treatment, the treatment conditions can be easily controlled, and the dyeing concentration in the dyeing process can be more easily controlled. Become.
Here, as a lamp used for ultraviolet irradiation, a low-pressure mercury lamp or an excimer lamp is suitable.

In the present invention, it is preferable to perform ultraviolet irradiation through a mask material having ultraviolet absorbing ability. Such a mask material can be manufactured by a method similar to a photomask used in the semiconductor field. For example, a light shielding film made of chromium (Cr) or titanium (Ti) may be formed on the surface of a mask base material (quartz glass or the like) with a different thickness.
According to the present invention, since ultraviolet irradiation is performed through a mask material having ultraviolet absorption ability, the mask material functions as a so-called photomask for the substrate irradiated with ultraviolet light. That is, it is possible to freely control the amount of ultraviolet rays irradiated to each position of the base material by the mask pattern drawn on the mask material. Therefore, it is possible to easily control the staining concentration in the staining process.

In this invention, it is preferable that the said mask material is manufactured by forming the composition formed by mix | blending an ultraviolet absorber on a mask base material with a droplet discharge method. For example, a substrate dyeing method includes a mask material manufacturing process in which a composition formed by blending the ultraviolet absorber is formed on the mask substrate by a droplet discharge method, and ultraviolet rays that are irradiated with ultraviolet rays through the mask material. And an irradiation step.
According to this invention, since the mask material is manufactured by the droplet discharge method (inkjet method), the dyeability of the substrate surface can be freely controlled by changing the mask pattern. In particular, the inkjet method is preferable because the mask pattern of the mask material can be formed very easily.

Further, the present invention is a method for dyeing a base material, comprising an ozone treatment step for performing ozone treatment on the surface of the base material, and then a dyeing step for dyeing the base material. The dyeing concentration of the base material in the dyeing process is controlled.
According to the base material dyeing method of the present invention, since the surface of the base material is provided with an ozone treatment step for performing ozone treatment, the dyeing density in the subsequent step can be changed depending on the treatment conditions. Specifically, it is possible to reduce the staining density by ozone treatment. Therefore, it is possible to control the dyeing concentration in the subsequent process only by a simple operation of controlling the ozone species and the concentration thereof or the processing time in the ozone treatment process.

According to the present invention, in the dyeing step, it is preferable to change the dyeing density of the base material by changing the energy of the ozone treatment.
According to the present invention, in the dyeing process, the dyeing density of the base material is changed by changing the energy in the ozone treatment process, which is the preceding process, so that the dyeing density is easily controlled.

In the present invention, it is preferable that the surface of the base material is a hard coat layer, and in the dyeing step, the hard coat layer is dyed.
According to this invention, since the surface of the base material to be dyed is a hard coat layer, the dyeing density can be controlled regardless of the material of the base body. In particular, when the hard coat layer is formed of a treatment agent based on a silane coupling agent, it is preferable because the dyeing density can be controlled more easily.

In the present invention, it is preferable to use a disperse dye or an oil-soluble dye for the dyeing in the dyeing step.
According to this invention, since the disperse dye or the oil-soluble dye is used for dyeing, the dyeing density on the substrate can be controlled more easily. Moreover, as a dyeing | staining method, the immersion method with which it is simple and it is easy to control immersion conditions is suitable. Furthermore, a so-called annealing transfer method is also preferable in which a mixture of a dye and a resin is used for dyeing and an annealing treatment is performed after immersion and drying to transfer the dye to the base material layer.

In the present invention, it is preferable that the material of the base material is either plastic or inorganic glass.
According to this invention, since the material of the base material is either plastic or inorganic glass, plastic or inorganic glass having a predetermined dyeing concentration can be provided by a simple method.

In the present invention, the substrate is preferably a spectacle lens.
According to the present invention, a spectacle lens having a predetermined staining density can be provided by a simple method.

The figure which shows the ultraviolet irradiation which concerns on this embodiment. The figure which shows the photomask for ultraviolet irradiation in this embodiment. The figure which shows the ultraviolet irradiation to the lens base material at the time of letting a photomask pass in this embodiment. Schematic which shows an inkjet dyeing apparatus in this embodiment. Schematic which shows the manufacturing process of the photomask by an inkjet dyeing apparatus in this embodiment. The figure which shows the relationship between the ultraviolet irradiation time and the light absorbency in each wavelength in a present Example. The figure which shows the relationship between an ultraviolet irradiation time and the light absorbency in 600 nm in a present Example. The figure which shows the difference in the dyeing density by a mask material in a present Example. The figure which shows the effect of ultraviolet irradiation and ozone treatment in a present Example.

  In this embodiment, a plastic for eyeglass lenses is used as the base material. In the base material dyeing method of the present embodiment, a primer layer and a hard coat layer are formed on the surface of the plastic lens base material, subjected to ultraviolet treatment thereon, and then subjected to predetermined dyeing. Hereinafter, embodiments of the dyeing method for a substrate of the present invention will be described in detail.

[1. (Plastic lens substrate)
The material of the plastic lens substrate (hereinafter also referred to as “lens substrate”) is not particularly limited as long as it is a transparent plastic, but from the viewpoint of thinning the lens, a plastic having a refractive index of 1.6 or more is used. preferable. As a plastic having a refractive index of 1.6 or more, a thiourethane plastic produced by reacting a compound having an isocyanate group or an isothiocyanate group with a compound having a mercapto group, or a compound having an episulfide group is included. Examples thereof include episulfide plastics produced by polymerizing and curing raw material monomers.

  A known compound can be used as the compound having an isocyanate group or an isothiocyanate group as a main component of the thiourethane plastic. Specific examples of the compound having an isocyanate group include ethylene diisocyanate, trimethylene diisocyanate, 2,4,4-trimethylhexane diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate and the like. It is done.

  Moreover, a well-known compound can be used as a compound which has a mercapto group. For example, 1,2-ethanedithiol, 1,6-hexanedithiol, aliphatic polythiol such as 1,1-cyclohexanedithiol, 1,2-dimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, etc. Aromatic polythiols are mentioned.

  Further, in order to increase the refractive index of the plastic lens, a polythiol containing a sulfur atom can be more preferably used in addition to the mercapto group. Specific examples include 1,2-bis (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2-bis ((2-mercaptoethyl) thio) -3-mercaptopropane, and the like. Is mentioned.

  As a specific example of a compound having an episulfide group used as a raw material monomer for an episulfide plastic, a known compound having an episulfide group can be used without any limitation. For example, an episulfide compound obtained by replacing part or all of oxygen of an epoxy group of an existing epoxy compound with sulfur can be mentioned.

  In addition to the episulfide group, a compound containing a sulfur atom can be more preferably used for increasing the refractive index of the plastic lens. Specific examples include 1,2-bis (β-epithiopropylthio) ethane, bis- (β-epithiopropyl) sulfide, 1,4-bis (β-epithiopropylthiomethyl) benzene, 2,5 -Bis (β-epithiopropylthiomethyl) -1,4-dithiane, bis- (β-epithiopropyl) disulfide and the like.

The polymerization method for the lens substrate in the present invention is not particularly limited, and a polymerization method generally used for producing a lens substrate can be used.
For example, when a vinyl monomer is used as a material, a lens base material can be manufactured by performing thermosetting using a thermal polymerization initiator such as an organic peroxide. In addition, a monomer can be cured by irradiating with ultraviolet rays using a photopolymerization initiator such as benzophenone to produce a lens substrate.

  In addition, when using a thiourethane plastic produced by reacting a compound having an isocyanate group or an isothiocyanate group with a compound having a mercapto group, the compound having an isocyanate group or an isothiocyanate group Then, after mixing a compound having a mercapto group, a curing catalyst for urethane resin is added and mixed, followed by polymerization and curing by heating. Specific examples of the curing catalyst include amine compounds such as ethylamine, ethylenediamine, triethylamine, and tributylamine, dibutyltin dichloride, dimethyltin dichloride, and the like.

  Furthermore, when using an episulfide-based plastic obtained by polymerizing and curing a raw material monomer containing a compound having an episulfide group as a lens material, the compound having an episulfide group alone or other copolymerizable with the episulfide group is used. After mixing with the monomer, it can be produced by adding and mixing a curing catalyst for epoxy resin, and performing polymerization and curing by heating.

The curing catalyst for epoxy resin can be used without particular limitation. Specific examples include dimethylbenzylamine, dimethylcyclohexylamine, diethylethanolamine, dibutylethanolamine, tertiary amines such as tridimethylaminomethylphenol, imidazoles such as ethylmethylimidazole, and the like.
Examples of other monomers copolymerizable with a compound having an episulfide group include a compound having a hydroxyl group, a compound having a mercapto group, a primary or secondary amine, and a compound having a carboxyl group.

  Specific examples of the compound having a hydroxyl group include alcohols such as isopropyl alcohol and n-hexyl alcohol, and polyhydric alcohols such as ethylene glycol, 1,6-hexanediol, pentaerythritol dimethacrylate, and pentaerythritol diacrylate. . Specific examples of the compound having a mercapto group include thiophenol, ethylthioglycolate, bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, and the like.

[2. (Primer layer)
The primer layer is formed on the lens substrate surface. The primer layer is present at the interface between both the plastic lens substrate and the hard coat layer described later, and plays a role of improving the durability of the surface treatment film formed on the lens substrate. In addition, it also has properties as an external shock absorbing layer, and has the property of improving impact resistance. The primer layer is formed using a coating composition containing a resin as a binder component and metal oxide fine particles as a filler component. The resin as the binder component exhibits adhesion to both the lens substrate and the hard coat layer. The metal oxide fine particles as the filler component exhibit the refractive index of the primer and act to improve the crosslinking density of the primer layer, thereby improving water resistance, weather resistance, and light resistance.

  As the resin, polyester resin, polyurethane resin, epoxy resin, melamine resin, polyolefin resin, urethane acrylate resin, epoxy acrylate resin, or the like can be used. Of these resins, a polyester resin can be preferably used from the viewpoints of durability, impact resistance, liquid pot life, moisture absorption stability, dyeing stability, low temperature curability, and the like. The polyester resin has many functional groups that affect the adhesion in the resin, and excellent adhesion is obtained with respect to the lens substrate and the hard coat layer, so that the durability is improved.

  Examples of the polyester resin include polyester-based thermoplastic elastomers described in “Japanese Patent Laid-Open No. 2000-144048”. The polyester-based thermoplastic elastomer is a multi-block copolymer using polyester as a hard segment (H) component and polyether or polyester as a soft segment (S) component. The weight ratio [H / S] between the hard segment and the soft segment is in the range of [30/70] to [90/10], preferably in the range of [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 dicarboxylic acids 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. Of these, terephthalic acid and 2,6-naphthalenedicarboxylic acid can be preferably used.

  Examples of the low molecular weight glycol include aliphatic glycols such as ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,6-cyclohexanedimethanol And the like, and ester-forming derivatives thereof. Of these, ethylene glycol and 1,4-butanediol can be preferably used.

On the other hand, polyester as a soft segment constituent component consists of dicarboxylic acids and long-chain glycol.
Examples of the dicarboxylic acids include those similar to the polyester as the hard segment constituent component. 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 can be preferably used.

  The polyether of the soft segment constituent component includes poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol and the like. (Alkylene oxide) glycols may be mentioned. Of these, poly (tetramethylene oxide) glycol can be preferably used.

  As a method for producing a polyester-based thermoplastic elastomer, for example, a lower alkyl ester of a dicarboxylic acid, an aliphatic long-chain glycol and excess low-molecular glycol are heated at a temperature of 150 to 200 ° C. in the presence of a catalyst such as tetrabutyl titanate. Thus, a transesterification reaction is performed to form a low polymer. The formed low polymer is polycondensed by heating and stirring at a temperature of 220 to 280 ° C. under a high vacuum 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.

  Further, the polyester-based thermoplastic elastomer can be used by mixing with other polymers. For example, normal ester resins (PBT, PET, etc.), amide resins, amide thermoplastic elastomers, and the like can be given. When these polymers are used in combination, the proportion of the total polymer is less than 50%, desirably less than 30%.

  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. .

  On the other hand, as the metal oxide fine particles as the filler component, metal oxides such as Si, Al, Ti, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, and In can be used. Among these, it is preferable to use metal oxide fine particles mainly composed of titanium oxide from the viewpoint of refractive index, transparency, light resistance, stability, and the like. Further, it may be a composite particle of titanium oxide and another inorganic oxide, and an oxide of a metal such as Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, and In A composite of titanium oxide can be used. The composite oxide fine particles preferably have an average particle size of 1 to 200 nm, more preferably 5 to 30 nm.

Further, it is preferable to use metal oxide fine particles dispersed in a dispersion medium such as water, alcohol, or other organic solvent. In this case, in order to improve the dispersion stability of the metal oxide fine particles, the surface of the inorganic oxide particles may be treated with an organosilicon compound or an amine compound.
Examples of the organosilicon compound used in this treatment include monofunctional silane, bifunctional silane, trifunctional silane, and tetrafunctional silane.

  Examples of amine compounds include alkylamines such as ammonium, ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, alkanolamines such as monoethanolamine and triethanolamine. Can be illustrated. In addition, it is preferable that the addition amount of these organosilicon compounds and an amine compound is the range of about 1 to 15 weight% with respect to the weight of an inorganic oxide particle. Among these, it is preferable to treat with an organosilicon compound having an epoxy group. By using metal oxide fine particles treated with an organosilicon compound having an epoxy group, the number of bonding points with the polyester resin can be increased, the crosslinking density of the primer film can be further improved, and the durability is improved.

  When metal oxide fine particles containing titanium oxide are used as the metal oxide fine particles, it is preferable to include composite oxide core particles containing titanium oxide having a rutile crystal structure. However, when using metal oxide fine particles containing titanium oxide having a rutile-type crystal structure in the hard coat layer described later, the hard coat layer has an ultraviolet absorption performance, so that the primer layer is more rutile than the rutile type. It is also possible to use composite oxide fine particles containing titanium oxide having an anatase type crystal structure having a high photoactive effect.

  Furthermore, it is also possible to use tin oxide as inorganic oxide fine particles other than titanium oxide. For example, tin oxide or tin oxide particles and zirconium oxide particles, or composite fine particles such as tin oxide particles, zirconium oxide particles, and silicon oxide particles as a core, and the surface is made of silicon oxide, zirconium oxide, antimony pentoxide, aluminum oxide, etc. It is also possible to use inorganic oxide fine particles coated with one or more composite colloidal particles. Tin oxide has a lower refractive index than titanium oxide, and although it is necessary to increase the amount of use in order to obtain a primer layer with a high refractive index, it is considered that the photoactive action like titanium oxide is small, and the primer layer This is a preferable combination when durability of the hard coat layer itself is required.

  However, in terms of light resistance and refractive index, it is more preferable to use composite oxide fine particles containing titanium oxide having a rutile crystal structure for the primer layer. Composite oxide particles containing titanium oxide having a rutile-type crystal structure are excellent in light resistance and have a higher refractive index than that of anatase type, so the amount used in the primer film can be reduced. The resin component contributing to adhesion can be increased.

The primer layer-forming coating composition thus obtained can be diluted with a solvent and used as necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers and aromatics are used.
In addition, the coating composition may contain a small amount of metal chelate compound, surfactant, antistatic agent, ultraviolet absorber, antioxidant, disperse dye, oil-soluble dye, pigment, photochromic compound, hindered amine, hindered as required. Addition of a light-resistant and heat-resistant stabilizer such as a phenol type can also improve the coating properties of the coating liquid, the curing speed, and the coating performance after curing.

  Furthermore, when applying the coating composition (coating liquid), it is preferable to pre-treat the surface of the lens substrate in advance for the purpose of improving the adhesion between the lens substrate and the primer layer. As the pretreatment, alkali treatment, acid treatment, surfactant treatment, peeling / polishing treatment with inorganic or organic fine particles, plasma treatment, or the like can be used.

  In addition, as a method for applying / curing the coating composition, after coating the coating composition using a dipping method, a spin coating method, a spray coating method, a roll coating method, a flow coating method, or the like, 40 to 200 is applied. The primer layer can be formed by heating / drying at a temperature of 0 ° C. for several hours. The thickness of the primer layer is preferably from 0.01 to 30 μm, particularly preferably from 0.05 to 30 μm. If the primer layer is too thin, durability and impact resistance performance cannot be achieved. Conversely, if the primer layer is too thick, surface smoothness may be impaired, and appearance defects such as optical distortion, white turbidity, and cloudiness may occur. .

[3. Hard coat layer)
The hard coat layer is formed on the surface of the lens substrate. The hard coat layer is required to have a high refractive index comparable to that of a plastic lens substrate having a high refractive index for the purpose of suppressing interference fringes. In order to cope with the increase in the refractive index of the hard coat layer, a method using inorganic oxide fine particles having a high refractive index is generally used. Specifically, Al, Sn, Sb, Ta, Ce, La, Fe, A colorless and transparent inorganic material comprising oxides of one or more metals selected from Zn, W, Zr, In, Ti (including mixtures thereof) and / or composite oxides containing two or more metals Oxide fine particles are used. Of these, inorganic oxide fine particles containing titanium oxide are generally used from the viewpoints of refractive index, transparency, dispersion stability, and the like.

  However, when inorganic oxide fine particles containing titanium oxide are used as a metal oxide for a hard coat layer, there are the following problems. Titanium oxide is active when it receives light (ultraviolet light) energy, and has the property of decomposing organic matter by a strong oxidative degradation power (hereinafter referred to as photoactivity). As a result, when titanium oxide is contained as a constituent component of the hard coat film, organic substances such as a silane coupling agent, which is another main constituent component, are decomposed by photoactivity, and cracks and film peeling of the hard coat film occur. The durability quality tends to decrease.

  In order to cope with such a problem, it is preferable to use a metal oxide containing titanium oxide having a rutile crystal structure. That is, by using metal oxide fine particles containing titanium oxide having a rutile-type crystal structure, various problems caused by the photoactivity of titanium oxide can be improved. It is possible to improve the weather resistance and light resistance by replacing the crystal structure of the metal oxide containing titanium oxide with the rutile type instead of the anatase type, and the refractive index of the rutile type crystal is higher than that of the anatase type crystal. This is because inorganic oxide fine particles having a relatively high refractive index can be obtained.

Titanium oxide having a rutile-type crystal structure is active when anatase-type titanium oxide receives light (ultraviolet light) energy, and has the property of decomposing organic matter by strong oxidative degradation power. Such photoactivity is low. This is because, when irradiated with light (ultraviolet rays), electrons in the valence band of titanium oxide are excited to form OH free radicals and HO ₂ free radicals, which decompose organic substances by this strong oxidizing power. This is because rutile type titanium oxide is more stable in terms of thermal energy, and the amount of free radicals produced is extremely small. Therefore, since the hard coat layer containing titanium oxide having a rutile crystal structure is excellent in weather resistance and light resistance, there is no possibility that the anti-reflection layer composed of the organic thin film is altered by the hard coat layer, and the weather resistance. A plastic lens with excellent properties and light resistance can be obtained.

The hard coat layer in the plastic lens of the present embodiment is preferably formed from a coating composition containing the following “A component”, “B component”, and “C component”.
“Component A”; metal oxide fine particles. “B component”: an organic silicon compound represented by the general formula, “R ¹ SiX ₁ ³ ” (wherein R ¹ is a C 2 or more organic group having a polymerizable reactive group, and X ₁ is a hydrolysis) Represents a sex group). “Component C”: a compound having a biphenyl sulfide structure represented by the following general formula (1) (wherein R and R ′ are hydrocarbon groups or hydroxyl groups, and n is 0 to 5).

先ず、「Ａ成分」としての金属酸化物微粒子について説明する。
「Ａ成分」は、酸化チタンおよび酸化スズ、または酸化チタン、酸化スズおよび酸化ケイ素からなるルチル型の結晶構造を有する複合酸化物の核粒子の表面を、酸化ケイ素と酸化ジルコニウムおよび／または酸化アルミニウムからなる複合酸化物の被覆層で被覆したものを含む平均粒径１〜２００ｎｍの金属酸化物微粒子を用いることが好ましい。

First, the metal oxide fine particles as the “component A” will be described.
“Component A” refers to the surface of the core particle of a composite oxide having a rutile-type crystal structure composed of titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide, and silicon oxide and zirconium oxide and / or aluminum oxide. It is preferable to use metal oxide fine particles having an average particle diameter of 1 to 200 nm including those coated with a composite oxide coating layer made of

As mentioned earlier, when titanium oxide is irradiated with light (ultraviolet rays), electrons in the valence band of titanium oxide are excited to produce OH free radicals and HO ₂ free radicals, which decompose organic substances by this strong oxidizing power. However, since the rutile type titanium oxide is more stable in terms of thermal energy than the anatase type titanium oxide, the amount of free radicals generated is extremely small. However, since free radicals are also generated in this rutile type titanium oxide, the surface of the core particle made of a composite oxide is coated with a composite oxide coating layer made of silicon oxide and zirconium oxide and / or aluminum oxide. Is preferably used. This is because free radicals generated in the core particles have the same strong oxidizing power but are unstable, and thus disappear due to the catalytic action of the coating layer while passing through the coating layer.

Although several methods for obtaining titanium oxide having a rutile-type crystal structure are conceivable, it is preferable to use a composite oxide with tin oxide and a composite oxide with addition of silicon oxide. When a composite oxide with tin oxide is added, the amount of titanium oxide and tin oxide contained in the inorganic oxide fine particles is [TiO ₂ when titanium oxide is converted to TiO ₂ and tin oxide is converted to SnO _{2. 2} / SnO ₂ ] has a mass ratio in the range of [1/3] to [20/1], preferably [1.5 / 1] to [13/1].

When the amount of SnO ₂ is made smaller than the above mass ratio range, the crystal structure shifts from the rutile type to the anatase type, resulting in a mixed crystal containing the rutile type crystal and the anatase type crystal, or anatase. It becomes a type crystal. Further, when the amount of SnO ₂ is made larger than the range of the above mass ratio, a rutile type crystal structure intermediate between the rutile type crystal of titanium oxide and the rutile type crystal of tin oxide is obtained, so-called rutile type of titanium oxide. A crystal structure different from that of the crystal is exhibited, and the refractive index of the obtained inorganic oxide fine particles is also lowered.

Also, if you make a composite oxide of tin oxide, a further composite oxide added with silicon oxide, titanium oxide contained in the inorganic oxide particles, tin oxide, and the amount of silicon oxide, titanium oxide TiO ₂ When the tin oxide is converted to SnO ₂ and the silicon oxide is converted to SiO ₂ , the mass ratio of [TiO ₂ / SnO ₂ ] is [1/3] to [20/1], preferably [1 .5 / 1] to [13/1] and the mass ratio of [(TiO ₂ + SnO ₂ ) / SiO ₂ ] is [50/45] to [99/1], preferably [70/30 ] To [98/2].

The content of SnO ₂ is the same as that when a composite oxide with tin oxide is added. By adding silicon oxide to this, the stability and dispersibility of the resulting inorganic oxide fine particles are improved. be able to. Here, when the amount of SiO ₂ is made smaller than the range of the mass ratio, stability and dispersibility are lowered. Further, when the amount of SiO ₂ is increased from the above mass ratio range, the stability and dispersibility are further improved, but the refractive index of the resulting inorganic oxide fine particles is lowered, which is not preferable. However, free radicals are also generated in this rutile titanium oxide. The same applies to the case where inorganic oxide fine particles containing two or more composite oxides containing titanium oxide are used as the inorganic oxide fine particles containing titanium oxide.

  Then, the surfaces of the core particles made of a composite oxide having a rutile crystal structure are covered with a composite oxide coating layer made of silicon oxide and zirconium oxide and / or aluminum oxide. The content of silicon oxide and zirconium oxide and / or aluminum oxide contained in the coating layer is preferably selected from the following three items (a) to (c) depending on the combination of the composite oxides used.

(A) When the coating layer is formed of a composite oxide of silicon oxide and zirconium oxide The amount of silicon oxide and zirconium oxide contained in the coating layer is calculated by converting silicon oxide to SiO ₂ and converting zirconium oxide to ZrO ₂ . The mass ratio of [SiO ₂ / ZrO ₂ ] is in the range of [50/50] to [99/1], preferably [65/35] to [90/10].

When the amount of ZrO ₂ exceeds the range of the mass ratio of [SiO ₂ / ZrO ₂ ], the number of Zr atoms capable of scavenging free radicals increases, but the coating layer is distorted to form a dense coating layer. Not. Therefore, there is a possibility that free radicals generated in the core particles migrate to the surface of the inorganic oxide fine particles and cause oxidation of organic substances. If the amount of ZrO ₂ is less than the range of the mass ratio of the [SiO 2 / _{ZrO 2],} dense coating layer is easily possible, since Zr atoms to trap free radicals is small, with the core particles The generated free radicals may migrate to the surface of the inorganic oxide fine particles, leading to oxidation of organic substances.

(B) When the coating layer is formed of a composite oxide of silicon oxide and aluminum oxide The amount of silicon oxide and aluminum oxide contained in the coating layer is calculated by converting silicon oxide to SiO ₂ and converting aluminum oxide to Al ₂ O _3. When converted to, the mass ratio of [SiO ₂ / Al ₂ O ₃ ] is desirably in the range of [60/40] to [99/1], preferably [68/32] to [95/5]. .

Here, when the amount of Al ₂ O ₃ exceeds the range of the mass ratio of [SiO ₂ / Al ₂ O ₃ ], the number of Al atoms that can trap free radicals increases, but a dense coating layer cannot be formed. For this reason, free radicals generated in the core particles come out on the surface of the inorganic oxide fine particles, leading to oxidation of the organic matter. If the amount of _Al 2 _{O 3} is less than the range of the mass ratio of the _{[SiO 2 / Al 2 O 3} ], dense coating layer is easily possible, because Al atoms to trap free radicals is less The free radicals generated in the core particles come out on the surface of the inorganic oxide fine particles and cause oxidation of the organic matter.

(C) When the coating layer is formed of a composite oxide of silicon oxide, zirconium oxide and aluminum oxide The amount of silicon oxide, zirconium oxide and aluminum oxide contained in the coating layer is calculated by converting silicon oxide to SiO ₂ and oxidizing. When zirconium is converted to ZrO ₂ and aluminum oxide is converted to Al ₂ O ₃ , the mass ratio of [SiO ₂ / (ZrO ₂ + Al ₂ O ₃ )] is [98/2] to [6/4], preferably Is preferably in the range of [95/5] to [7/3].

If the total amount of ZrO ₂ and Al ₂ O ₃ exceeds the range of the above mass ratio, the total amount of Zr atoms and Al atoms that can trap free radicals increases, but a dense coating layer cannot be formed. Free radicals generated in the particles come out on the surface of the inorganic oxide fine particles and cause oxidation of organic substances. Further, when the total amount of ZrO ₂ and Al ₂ O ₃ is less than the above mass ratio range, a dense coating layer is easily formed, but the total amount of Zr atoms and Al atoms for capturing free radicals is small. The free radicals generated in the core particles migrate to the surface of the inorganic oxide fine particles, leading to oxidation of the organic matter.
The thickness of the coating layer is 0.02 to 2.27 nm, preferably 0, from the viewpoint of preventing free radicals generated in the core particles from moving to the surface of the inorganic oxide fine particles and causing oxidation of the organic matter. Desirably, it is in the range of 16 to 1.14 nm.

  Here, the composite oxide constituting the core particle is a composite solid solution oxide (including a doped composite oxide) and / or a composite oxide cluster composed of titanium oxide and tin oxide, or titanium oxide and tin oxide. And a complex solid solution oxide (including doped complex oxide) and / or a complex oxide cluster composed of silicon oxide. Further, the composite oxide constituting the core particle and / or the coating layer may be a composite hydrous oxide having an OH group at the terminal, or may further include a part of the composite hydrous oxide.

  The average particle size of the inorganic oxide fine particles containing titanium oxide is 1 to 200 nm, preferably 5 to 30 nm. When the average particle size is less than 1 nm, the particles are bridged and do not shrink uniformly in the drying process for forming a hard coat layer on the plastic lens substrate, and the shrinkage rate is also reduced. A hard coat layer having sufficient film hardness cannot be obtained. On the other hand, if the average particle size exceeds 200 nm, the hard coat layer turns white and becomes unsuitable for use as an optical component.

  The inorganic oxide fine particles containing titanium oxide having a rutile-type crystal structure may be used alone or in combination with other inorganic oxide particles. Examples of other inorganic oxide particles include oxides of one or more metals selected from Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, and In (a mixture thereof) And / or inorganic oxide fine particles composed of a composite oxide containing two or more metals.

  Specific examples of the inorganic oxide fine particles include inorganic oxide fine particles containing titanium oxide having a rutile crystal structure with an average particle diameter of 1 to 200 nm in water, alcohol-based or other organic solvents. A dispersion medium dispersed in a colloidal form. Commercially available dispersion media include titanium oxide and tin oxide, or the surface of a composite oxide core particle having a rutile-type crystal structure composed of titanium oxide, tin oxide and silicon oxide, silicon oxide and zirconium oxide and / or Examples thereof include a dispersion sol for coating containing inorganic oxide fine particles having an average particle diameter of 8 to 10 nm coated with a composite oxide coating layer made of aluminum oxide (manufactured by Catalyst Kasei Kogyo Co., Ltd., OPTRAIK).

  Furthermore, in order to enhance the dispersion stability in the coating composition, it is also possible to use those inorganic oxide fine particles whose surface is treated with an organosilicon compound or an amine compound, and further with a carboxylic acid such as tartaric acid or malic acid. Is possible. 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. Further, after the hydrolysis 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 alkylamines such as ammonium or ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, alkanols such as monoethanolamine and triethanolamine. Examples include amines. In addition, it is preferable that the addition amount of these organosilicon compounds, an amine compound, etc. is the range of about 1-15 mass% with respect to the mass of an inorganic oxide particle.

  The kind and blending amount of the inorganic oxide fine particles are determined by the intended hardness, refractive index, and the like, but the blending amount is 5 to 80% by mass, particularly 10 to 50% by solid content in the hard coat composition. It is desirable to be in the range of% by weight. If the amount is too small, the wear resistance of the coating film may be insufficient. On the other hand, when there are too many compounding quantities, a crack will arise in a coating film and dyeing | staining property may become inadequate.

Next, “B component” (general formula: organosilicon compound represented by “R ¹ SiX ₁ ³ ”) will be described. “Component B” serves as a binder for the hard coat layer. In the general formula: “R ¹ SiX ₁ ³ ”, R ¹ is an organic group having a polymerizable reactive group, and has 2 or more carbon atoms. R ¹ has a polymerizable reactive group such as vinyl group, allyl group, acrylic group, methacryl group, 1-methylvinyl group, epoxy group, mercapto group, cyano group, isocyano group, amino group and the like. X ₁ is a hydrolyzable functional group, and examples thereof include an alkoxy group such as a methoxy group, an ethoxy group, and a methoxyethoxy group, a halogen group such as a chloro group and a bromo group, and an acyloxy group.

  Examples of the organosilicon compound of “Component B” include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, and methacryloxypropyltrialkoxysilane. , Γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane and the like. Two or more of these “B component” organosilicon compounds may be used in combination.

And "A component" is mixed with "B component", and the hard-coat liquid for forming a hard-coat layer is manufactured. In the production, it is preferable to mix the sol in which the “A component” is dispersed with the “B component”.
The compounding amount of “Component A” is determined by the hardness and refractive index of the hard coat layer, and is 5 to 80% by mass, particularly 10 to 50% by mass, based on the solid content in the hard coat liquid. It is preferable. If the blending amount is too small, the wear resistance of the hard coat layer becomes insufficient, and if the blending amount is too large, cracks may occur in the hard coat layer. Moreover, when dyeing | hardening a hard-coat layer, dyeability may fall.

  Next, the compound having a biphenyl sulfide structure as “C component” will be described. "C component" can improve durability by acting as an adhesion component between both the primer layer and the hard coat layer. In addition, the biphenyl sulfide structure has the property that a rigid benzene ring is bonded to a sulfur atom, and it is thought that it exhibits flexibility while adhering to both the primer layer and the hard coat layer, improving impact resistance. Can be made. Furthermore, although a compound having a biphenyl sulfide structure is used in the hard coat layer, it is considered to be localized between both the primer layer and the hard coat layer, and thus hardly contributes to the crosslinking reaction of the hard coat layer itself. , Has the effect of not reducing the scratch resistance.

  Examples of the compound having a biphenyl sulfide structure include 4,4′-thiobis (6-tert-butyl-meta-cresol, 2,2′-thiobis (4-methyl-6-tert-butylphenol) and the like. Is preferably 0.01 to 5.0 mass%, more preferably 0.03 to 1.0 mass%, based on the solid mass of the coating composition, where the solid content of the coating composition is The main component contained in the coating film obtained by drying and curing the coating composition, and the solid content mass refers to the metal oxide sol, organosilicon compound, polyfunctional epoxy compound in the coating composition, This is the total mass of the main components such as the catalyst.If the compound having a biphenyl sulfide structure is less than 0.01% by mass, the above effects are insufficient and durability and impact resistance are reduced. Sex is lowered, the reverse too much than 5.0% by weight adversely affects the crosslinking reaction of the hard coat layer itself, abrasion resistance is lowered.

  Furthermore, it is very useful to contain a polyfunctional epoxy compound in the hard coat layer. The polyfunctional epoxy compound can improve durability and impact resistance by the compound having the biphenyl sulfide structure, but when used in combination with this, the water resistance of the hard coat is improved and a primer layer is provided on the base. The adhesion with the primer layer can be further stabilized. In particular, when a hydroxyl group is present in the molecule of the polyfunctional epoxy compound, it is recognized that the adhesion with the primer layer is improved. Therefore, by using a polyfunctional epoxy compound containing one or more hydroxyl groups in one molecule, it is possible to reduce the blending amount of this polyfunctional epoxy compound as a whole, without causing a decrease in scratch resistance, It is possible to improve durability. In addition, when the antireflection layer is formed on the upper surface of the hard coat layer with an organic thin film, the thickness of the antireflection layer is often very thin, especially silica having an internal cavity in the antireflection layer. When the system particles are used, the hard coat layer needs to have water resistance in order to pass moisture. Therefore, a polyfunctional epoxy compound is very useful.

  Examples of the multifunctional epoxy compound include 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, and 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, neopentyl glycol hydroxyhybalic acid ester Diglycidyl ether, trimethylolpropa Diglycidyl ether, trimethylolpropane triglycidyl 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, diglycidyl ether of tris (2-hydroxyethyl) isocyanate, triglycidyl ether of tris (2-hydroxyethyl) isocyanate, etc. Compound, isophoronediol diglycidyl Ether, alicyclic epoxy compounds such as bis-2,2-hydroxycyclohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ether And aromatic epoxy compounds such as phenol novolac polyglycidyl ether and cresol novolac polyglycidyl ether.

  Among these, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, tris (2-hydroxyethyl) isocyanate An aliphatic epoxy compound such as triglycidyl ether can be preferably used.

  Further, a curing catalyst may be added to the hard coat layer. Examples of the curing catalyst include perchloric acids such as perchloric acid, ammonium perchlorate, and magnesium perchlorate, Cu (II), Zn (II), Co (II), Ni (II), and Be (II). Ce (III), Ta (III), Ti (III), Mn (III), La (III), Cr (III), V (III), Co (III), Fe (III), Al (III) Acetylacetonate having a central metal atom such as Ce (IV), Zr (IV), V (IV), amino acids such as amine and glycine, Lewis acid, organic acid metal salts and the like.

  Among these, preferable curing catalysts include acetylacetonate having magnesium perchlorate, Al (III), and Fe (III) as a central metal atom. In particular, it is most preferable to use acetylacetonate having Fe (III) as a central metal atom. The addition amount of the curing catalyst is desirably in the range of 0.01 to 5.0% by mass of the solid content of the hard coat liquid.

  The coating composition for forming a hard coat layer thus obtained can be used after diluting in a solvent, if necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers and aromatics are used. In addition, a coating composition for forming a hard coat layer may contain a small amount of a metal chelate compound, a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye, an oil-soluble dye, a pigment, A light and heat resistant stabilizer such as a photochromic compound, a hindered amine, or a hindered phenol can be added to improve the coating property of the coating liquid, the curing speed, and the coating performance after curing.

  The coating composition can be applied and cured by dipping, spray coating, roll coating, or flow coating, and then at a temperature of 40 to 200 ° C. for several hours. A hard coat film can be formed by heating and drying. In addition, it is preferable that the film thickness of a hard-coat layer is 0.05-30 micrometers. When the film thickness is less than 0.05 μm, basic performance such as scratch resistance cannot be realized. On the other hand, if the film thickness exceeds 30 μm, the surface smoothness may be impaired, or optical distortion may occur.

[4. Dyeing method]
Below, the dyeing | staining method with respect to the lens base material with a hard-coat layer obtained by above described embodiment is demonstrated. First, the ultraviolet irradiation process will be described, and then the dyeing process will be described.

(UV irradiation process)
FIG. 1 is a diagram illustrating ultraviolet irradiation according to the present embodiment. In FIG. 1, a lens substrate 1 with a hard coat layer is fixed to a pedestal (not shown). On the lens substrate 1, a low-pressure mercury lamp 2 is disposed. The low-pressure mercury lamp 2 has a structure that mainly emits ultraviolet rays of 185 nm and 254 nm. Moreover, after irradiating one side of the lens substrate 1 with ultraviolet rays, the lens substrate 1 may be reversed and the other side may be irradiated with ultraviolet rays. The irradiation distance is the shortest distance between the irradiated surface (hard coat surface) of the lens substrate 1 and the low-pressure mercury lamp 2, and is preferably 100 mm or less and more preferably 50 mm or less in consideration of irradiation efficiency.

  Further, the lens substrate 1 may be irradiated with ultraviolet rays through a photomask 4 as shown in FIGS. Here, in the photomask 4, the transmittance of the ultraviolet rays continuously changes from 0% to 100% from the shielding portion 5 that does not transmit any ultraviolet rays to the transmission portion 6 that allows the ultraviolet rays to pass well. When such a photomask is used, the dyeability of the lens substrate 1 can be continuously changed as will be described later.

  Such a photomask can be manufactured by a method similar to a photomask used in the semiconductor field. For example, a light shielding film made of chromium (Cr) or titanium (Ti) may be formed on the surface of a photomask substrate (quartz glass or the like) with a different thickness. Such a light shielding film can be easily formed by a sputtering method, a CVD method, a vacuum deposition method, or the like.

  Furthermore, a droplet discharge method (inkjet method) is also suitable as a method for manufacturing a photomask. The ink jet method is generally a method in which a pressure chamber provided with a fine nozzle opening having a diameter of 10 to 100 μm and a pressure generating element is filled with ink (a composition having an ultraviolet absorbing ability), and the pressure generating element is electronically controlled. In this way, the ink in the pressure chamber is pressurized, and the ink is ejected as fine droplets from the nozzle opening at that pressure.

Here, the composition having ultraviolet absorbing ability can be prepared by blending an ultraviolet absorbent in an appropriate solvent.
The ultraviolet absorber is not particularly limited as long as it is dissolved or dispersed in the solvent used. Examples include benzophenone, benzotriazole, salicylate, cyanoacrylate, and nickel complex salts. Specifically, there is a Chemisorb series manufactured by Chemipro Kasei.
Moreover, when forming the film | membrane for ultraviolet absorption on the photomask base-material surface, it is preferable to mix | blend resin from a film forming viewpoint. The resin may be soluble in the above-described solvent and has a film-forming ability, and examples thereof preferably include polyurethane resin, acrylic resin, polystyrene resin, ABS resin, and polyvinyl chloride resin.

  From the viewpoint of wettability of the composition to the substrate surface, the surface energy (critical surface tension) of the photomask substrate for producing the photomask 4 is equal to or more than the surface tension of the composition. Larger is preferred. Conversely, the surface tension of the composition should be low. However, in order to dissolve the solid content in the composition, a higher surface tension is better. Therefore, it is preferable to select a solvent that provides the composition with a surface tension at 25 ° C. of 20 mN / m or more and 45 mN / m or less. Such a solvent may be a single solvent or a mixed solvent. For example, a solvent mixture obtained by mixing a solvent A having a surface tension at 25 ° C. of 35 mN / m or more and a solvent B having a surface tension at 25 ° C. of 32 mN / m or less is preferably applicable. Examples of the solvent A include γ-butyrolactone, N-methyl-2-pyrrolidone, N, N′-dimethyl-2-imidazolidinone, and propylene carbonate. Examples of the solvent B include propylene glycol monomethyl ether and ethylene glycol monobutyl ether (butyl cellosolve). For example, a solvent in which γ-butyrolactone and butyl cellosolve are mixed at a mass ratio of 1: 1 is preferable from the viewpoints of solubility of solids and wettability to a photomask substrate.

Next, a method for manufacturing the photomask 4 by the ink jet method will be described.
FIG. 4 shows a schematic diagram of an inkjet dyeing apparatus 10 (hereinafter also simply referred to as “dyeing apparatus 10”).
The dyeing apparatus 10 includes an ink tank 11 in which a dye composition that absorbs ultraviolet rays is enclosed, a tube 12 that transports the dye composition, a discharge head 13 that discharges droplets, and a holder that holds the discharge head 13. The member 14 includes an arm 15 that rotatably holds the photomask base material 4 ′ for dyeing.
The discharge head 13 is connected to the holding member 14 and can move up and down, left and right, and can also rotate. Further, the ejection head 13 and the arm 15 that holds the photomask substrate 4 ′ are controlled by the control PC.

As a specific coating method, as shown in FIG. 5A, scanning is performed while controlling the discharge head 13 filled with the dye composition so as to keep the surface of the photomask substrate 4 ′ at substantially equal intervals. Let Then, by controlling the ejection from the nozzles of the ejection head 13, the dye composition is uniformly applied to the necessary portions of the photomask substrate 4 ′ to form the coating film L ′. In this case, only the ejection head 13 may be moved, or the ejection head 13 may be moved in a specific direction, and the photomask substrate 4 ′ may be moved in a direction orthogonal to the above direction at a timing.
The coating film L ′ is dried to become the ultraviolet absorption film L. In addition, when there exists a possibility that sufficient thickness of the ultraviolet-absorbing film | membrane L may not be obtained by one application | coating by the inkjet method, it coats several times.

The lens substrate 1 may be irradiated with ultraviolet rays through the photomask 4 obtained as described above, or the entire surface of the lens substrate 1 may be irradiated with ultraviolet rays as shown in FIG. .
Further, the ultraviolet irradiation conditions may be appropriately determined by experiments in consideration of the dyeing density described later. Specifically, if the amount of light is increased or the irradiation time is lengthened, the dyeing density with disperse dyes or oil-soluble dyes can be lowered. However, the light quantity is preferably 1 to 3000 mJ / cm ² from the viewpoint of irradiation efficiency, and more preferably ² to 1500 mJ / cm ² . An excimer lamp may be used for the ultraviolet irradiation.

  When ultraviolet irradiation is performed in the air, ozone is generated at the same time, and this ozone has the same effect as ultraviolet rays. That is, the dyeing density with disperse dyes or oil-soluble dyes is reduced. Therefore, if you want to eliminate the effects of ozone, you can either irradiate ultraviolet light in an inert gas atmosphere such as nitrogen gas, or paste an appropriate material (polymer film, etc.) that transmits ultraviolet light on the substrate surface. Good.

(Dyeing process)
The lens base material that has undergone the ultraviolet irradiation step described above is preferably colored by a normal immersion dyeing method (dipping method) using a disperse dye. Specifically, this is performed as follows.
A dyeing bath having a predetermined temperature is prepared, and a disperse dye is added to the dyeing bath to increase sales. The disperse dye preferably has good dyeability and light resistance, and examples thereof include anthraquinone derivatives, quinophthalone derivatives, nitrodiphenylamine derivatives, and azo disperse dyes. Disperse dyes can be used alone or in combination of two or more, and the amount added to the dyeing bath can be used in the range of 1 g to 30 g / liter so as to achieve a desired dyeing speed. The temperature of the dyeing bath is usually in the range of 40-100 ° C, more preferably 70 ° C-99 ° C. If it is less than 40 ° C., the dyeing speed becomes extremely slow, and the time until the desired dyeing density is reached becomes extremely long, so that it cannot withstand actual use. Moreover, since it is necessary to pressurize when it exceeds 100 degreeC, an apparatus will enlarge and workability | operativity will fall.

  In the dyeing bath, a surfactant for assisting the dispersion of the disperse dye and a dyeing accelerator for increasing the dyeing speed can be added as necessary. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates, alkylsulfosuccinates and lauryl sulfates, and nonionic surfactants such as polyoxyethylene alkyl ethers. The amount of these surfactants to be used can be appropriately determined in the range of 10 to 200% by mass with respect to the added amount of the disperse dye, and is usually about 1 to 10 g / liter in the dyeing bath. The amount added is preferably used. Examples of the dyeing accelerator include alcohols having an aromatic ring such as benzyl alcohol, phenethyl alcohol, dimethylbenzyl carbinol, o-phenylphenol, p-phenylphenol, trichlorobenzene, dichlorobenzene, methylnaphthalene, and the like. These dyeing accelerators may be used alone or in combination of two or more. The addition amount of the dyeing accelerator can be appropriately determined in the range of 20 to 1000% by mass with respect to the addition amount of the disperse dye. Usually, the addition amount is about 1 to 30 g / liter in the dyeing bath. Is preferably used.

The dyeing bath is usually adjusted with water, but may be adjusted with a mixture of water and an organic solvent such as methanol, ethanol or isopropanol as necessary. When an organic solvent is used, an oil-soluble dye can be used in addition to the disperse dye.
The temperature of the dyeing bath and the time for immersing the lens in the dyeing bath vary depending on the desired color tone and density. Usually, the lens is immersed in the dyeing bath at 40 to 100 ° C. for about 10 seconds to 180 minutes. A lens with the desired density and color tone can be obtained.

  Further, dyeing with disperse dyes or oil-soluble dyes may be performed by a so-called annealing transfer method. Specifically, using a dyeing bath in which a resin and a dye are dissolved in an organic solvent, the mixture of the dye and the resin is coated on the surface of the lens substrate by the method described above, and then an annealing treatment is performed to apply the dye to the lens substrate. Transcript. After completion of the annealing transfer, the resin film is removed from the lens substrate surface. Here, as the organic solvent, THF (tetrahydrofuran), toluene, MEK (methyl ethyl ketone), cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether and ethyl acetate, or a mixed solvent thereof Can be used. As the resin, an acrylic resin or a urethane resin can be suitably used. The annealing temperature range is preferably such that damage to the substrate does not occur. Specifically, it is preferably in the range of 50 to 200 ° C., more preferably about 100 to 150 ° C.

According to the above-described embodiment, the following effects can be obtained.
In the lens substrate dyeing method according to the present embodiment, an ultraviolet irradiation step of performing ultraviolet treatment on the hard coat surface of the lens substrate 1, and then a dyeing step of dyeing the lens substrate 1 with a disperse dye or an oil-soluble dye, Since the dyeing density of the lens substrate 1 in the dyeing process described above is controlled by ultraviolet treatment, it is possible to easily obtain spectacle lenses with a hard coat layer having various dyeing densities.

  Further, when the above-described ultraviolet irradiation is performed in the air, ozone is generated, and this ozone lowers the dyeing density by the disperse dye or the oil-soluble dye. That is, the dyeing density can be controlled by ozone treatment. Therefore, the dyeing concentration in the post-process can be controlled only by a simple operation of controlling the ozone species, the concentration thereof, or the processing time simultaneously with the above-described ultraviolet rays or blocking the ultraviolet rays.

  In the present embodiment, since the surface of the lens substrate 1 is a hard coat layer, the staining density can be controlled regardless of the material (type of plastic) of the lens substrate 1 main body. In particular, when the hard coat layer is formed of a treatment agent based on a silane coupling agent, the dyeing density can be controlled more easily.

In the present embodiment, since the disperse dye or the oil-soluble dye is used for dyeing in the dyeing step, the dyeing density on the lens substrate 1 can be controlled more easily. Moreover, since the immersion method (dipping method) is used as a dyeing method, it can dye easily.
In addition, if the surface of the base material is coated with an appropriate substance that blocks UV light, the effect of UV irradiation and ozone treatment can be eliminated only on that part. You can also.

  Further, when the mask material 4 as shown in FIG. 2 is used when the lens substrate 1 is irradiated with ultraviolet rays, the dyeability of the surface of the lens substrate 1 can be freely controlled by changing the mask pattern. In particular, when the inkjet dyeing apparatus 10 is used, the mask pattern of the mask material 4 can be formed very easily.

In addition, this invention is not limited to the above-mentioned embodiment.
In this embodiment, ultraviolet irradiation is adopted as the high energy treatment, but the same effect can be obtained even with the plasma treatment. The dyeing may be performed directly on the substrate instead of the hard coat layer, and the substrate is not limited to plastic but may be inorganic glass. Further, after dyeing the hard coat layer, an organic or inorganic antireflection layer or an antifouling layer may be provided.

  Hereinafter, the present invention will be described in more detail by way of examples. Specifically, the lens substrate on which the hard coat layer was formed was dyed by irradiating ultraviolet rays under various conditions, and the dyeing density was confirmed.

[Test Example 1]
(Preparation of lens substrate for UV irradiation)
(1) Preparation of primer composition In a stainless steel container, 3700 parts by weight of methyl alcohol, 250 parts by weight of water, and 1000 parts by weight of propylene glycol monomethyl ether were added and stirred sufficiently, followed by titanium oxide, zirconium oxide, silicon oxide. 2800 parts by weight of a composite fine particle sol (anatase type crystal structure, methanol dispersion, Catalytic Chemical Industry Co., Ltd., trade name OPTRAIQUE 1120Z U-25 / A8) mainly composed of Next, after adding 2200 parts by weight of a polyester resin and stirring and mixing, 2 parts by weight of a silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name L-7604) was further added and stirring was continued for a whole day and night, followed by a 2 μm filter. Filtration was performed to obtain a primer composition.

(2) Preparation of hard coat composition Take 1000 parts by weight of butyl cellosolve in a stainless steel container, add 1200 parts by weight of γ-glycidoxypropyltrimethoxysilane as “component B” and stir well, then 0.1 mol 300 parts by weight of / liter hydrochloric acid was added and stirring was continued for a whole day and night to obtain a silane hydrolyzate. After adding 30 parts by weight of a silicone-based surfactant (trade name L-7001, manufactured by Nippon Unicar Co., Ltd.) to this silane hydrolyzate and stirring for 1 hour, titanium oxide, tin oxide, and oxidation as “component A” 7300 parts by weight of a composite fine particle sol mainly composed of silicon (rutile crystal structure, methanol dispersion, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name OPTRAIQUE 1120Z 8RU-25 · A17) was added and mixed with stirring for 2 hours. Next, 250 parts by weight of an epoxy resin (manufactured by Nagase Kasei Co., Ltd., trade name Denacol EX-313) was added and stirred for 2 hours, followed by 20 parts by weight of iron (III) acetylacetonate and 4,4 as “C component”. Add 10 parts by weight of '-thiobis (6-tert-butyl-meta-cresol (0.5% by weight based on the solid content of the coating composition), stir for 3 hours, filter through a 2 μm filter, and hard coat A composition was obtained.

(3) Formation of primer layer and hard coat layer A thiourethane plastic lens base material (manufactured by Seiko Epson Corporation, trade name Seiko Super Sovereign Fabric, refractive index 1.67) was prepared. And it is immersed in the primer composition prepared in (1), and the lifting speed is 30 cm / min. And baked at 80 ° C. for 20 minutes to form a primer layer on the lens substrate surface. And the lens base material in which the primer layer was formed was immersed in the hard coat composition prepared in (2), and the lifting speed was 30 cm / min. And baked at 80 ° C. for 30 minutes to form a hard coat layer on the primer layer. Then, it heated for 3 hours in the oven set to 125 degreeC, and obtained the plastic lens in which the primer layer and the hard-coat layer were formed. The formed primer layer had a thickness of 0.5 μm, and the hard coat layer had a thickness of 2.5 μm.
In addition, nine lens base materials (samples) for ultraviolet irradiation were prepared by the method described above.

(UV irradiation process)
<Irradiation device>
Model: Iwasaki Electric's low-pressure mercury lamp "eye UV-ozone cleaning device OC-250615-D + A"
25W x 6 lights Batch type (desktop type) with damper Irradiation distance: Approximately 42mm from the bottom of the lamp to the sample stage
<Irradiation method and conditions>
As shown in FIG. 1 (A), each sample (lens substrate 1) was placed, and the hard coat surface was irradiated with ultraviolet rays while changing the irradiation time as follows.
UV irradiation time: 0, 15, 30, 45, 60, 75, 90, 105 sec
(0 sec means that ultraviolet rays are not irradiated.)

(Dyeing process)
A dye and a resin were dissolved in an organic solvent to prepare a dyeing solution, and each sample described above was dyed. Specifically, it is as follows.
<Dyeing solution>
A solution having the following constitution (mass% is based on the total amount) was prepared and filtered through a 6 μm pore size filter to obtain a staining solution.
Organic solvent: THF (51.2% by mass), toluene (18.2% by mass), MEK (22.0% by mass) and a mixed solvent consisting of cyclohexanone (6.8% by mass) Resin: Acrylic resin (manufactured by Mitsubishi Rayon) BR-108) 1.8% by mass
Dye: Blue disperse dye (Futaba Sangyo BlueTN) 6.0% by mass
<Dyeing method>
After each sample was immersed in the solution obtained above, the hard coat layer was dyed by transfer annealing. Note that the opposite surface of the sample was masked with an adhesive tape so that the staining solution would not touch.
Transfer annealing condition: 130 ° C., 30 minutes After transfer annealing, washing and removal of the mask were performed to obtain a dyed sample.

(Evaluation methods)
About each sample after dyeing | staining, the light absorbency in each wavelength was measured with the spectrophotometer. The result is shown in FIG.
(Result)
As shown in FIG. 6, at 0 sec (no ultraviolet irradiation), it was found that the dye concentration decreased significantly as the ultraviolet irradiation time increased, although it showed very high absorbance (staining concentration). . Here, when the absorbance at a wavelength of 600 nm is plotted, it can be seen that the absorbance decreases almost linearly with the ultraviolet irradiation time as shown in FIG. Therefore, it can be understood that the absorbance, that is, the staining concentration can be easily controlled by the ultraviolet irradiation time.

[Test Example 2]
About one of the samples produced in Test Example 1, alphabet letters were drawn on the hard coat surface with a commercially available oil-based felt pen. Then, ultraviolet rays were irradiated (105 sec) in the same manner as in Test Example 1, and further dyeing was performed. Thereafter, when the letters were removed with a felt pen with acetone, it was found that the portion described with the felt pen was strongly stained as shown in FIG. Thus, it is possible to suppress the influence of ultraviolet rays by covering the lens substrate surface with an appropriate mask material, and various patterns can be easily imparted to the lens substrate.
In addition, you may manufacture such a mask material with the inkjet dyeing apparatus 10 shown in FIG. 4 using a suitable mask base material.

[Test Example 3]
In the test example described above, since ultraviolet rays are irradiated in the atmosphere, it can be assumed that ozone is generated. Therefore, an experiment was conducted to separate and evaluate the effect of ultraviolet irradiation and the effect of ozone treatment. Specifically, 4 samples were prepared using a smooth white plate glass having a thickness of 2 mm and forming a primer layer and a hard coat layer in the same manner as in Test Example 1. And after performing ultraviolet treatment by the following four methods, dyeing was performed in the same manner as in Test Example 1.
(1) No ultraviolet irradiation treatment was performed.
(2) Ultraviolet irradiation was performed by the method shown in FIG. 1 (A) (120 sec).
(3) As shown in FIG. 1B, after the quartz glass 3 having a thickness of 1 mm was brought into close contact with the surface of the sample (base material 1), ultraviolet irradiation was performed (120 sec).

(Evaluation methods)
About each sample after dyeing | staining, the light absorbency in each wavelength was measured with the spectrophotometer. The result is shown in FIG.
(Result)
As shown in FIG. 9, when the quartz glass 3 is brought into close contact with the sample surface and the ultraviolet irradiation is performed (FIG. 1B), the absorbance is lower than that when the ultraviolet irradiation treatment is not performed. That is, it is considered that this decrease corresponds to a decrease in absorbance due to ultraviolet rays alone. Moreover, when the quartz glass 3 is closely attached to the sample surface and ultraviolet irradiation is performed (FIG. 1 (B)), the difference from the absorbance curve corresponding to FIG. 1 (A) corresponds to the effect of ozone. Conceivable. In any case, it can be seen that the absorbance (staining concentration) can be controlled by either ultraviolet rays or ozone.

DESCRIPTION OF SYMBOLS 1 ... (Lens) base material, 2 ... Low pressure mercury lamp, 3 ... Quartz glass, 4 ... Photomask, 4 '... Photomask base material, 10 ... Dyeing device, 11 ... Ink tank, 12 ... Tube, 13 ... Discharge head , 14 ... holding member, 15 ... arm, L ... ultraviolet absorbing film, L '... coating film

Claims (12)

A method for dyeing a substrate,
A high energy treatment step of subjecting the surface of the substrate to a high energy treatment;
Thereafter, a dyeing step of dyeing the base material,
A dyeing method for a substrate, wherein the dyeing concentration of the substrate in the dyeing step is controlled by the high energy treatment. It is the dyeing | staining method of the base material of Claim 1, Comprising:
In the dyeing step, the dyeing concentration of the base material is changed by changing the energy of the high energy treatment. The substrate dyeing method according to claim 1 or 2, wherein the high energy treatment is at least one of ultraviolet irradiation and plasma treatment. In the dyeing method of the substrate according to claim 3,
A method for dyeing a substrate, characterized by performing ultraviolet irradiation through a mask material having ultraviolet absorbing ability. In the dyeing method of the substrate according to claim 4,
The method for dyeing a base material, wherein the mask material is produced by forming a composition containing an ultraviolet absorber on a mask base material by a droplet discharge method. In the dyeing method of the substrate according to claim 4,
A mask material manufacturing step of forming a composition comprising the ultraviolet absorber on the mask base material by a droplet discharge method;
A method of dyeing a substrate, comprising: an ultraviolet irradiation step of performing ultraviolet irradiation through the mask material. A method for dyeing a substrate,
An ozone treatment step of performing ozone treatment on the surface of the substrate;
Thereafter, a dyeing step of dyeing the base material,
A substrate dyeing method, wherein the dyeing concentration of the substrate in the dyeing step is controlled by the ozone treatment. It is a dyeing | staining method of the base material of Claim 7, Comprising:
In the dyeing step, the dyeing concentration of the substrate is changed by changing the energy of the ozone treatment. In the dyeing | staining method of the base material of any one of Claim 1- Claim 8,
The surface of the substrate is a hard coat layer,
In the dyeing step, the substrate is dyed by dyeing the hard coat layer. In the dyeing | staining method of the base material of any one of Claim 1- Claim 9,
Dispersing dye or oil-soluble dye is used for dyeing in the dyeing step. In the dyeing | staining method of the base material of any one of Claim 1- Claim 10,
The method for dyeing a substrate, wherein the material of the substrate is either plastic or inorganic glass. In the dyeing method of the substrate according to claim 11,
The substrate is a spectacle lens. A method for dyeing a substrate.

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