JP4386568B2 - Organic glass coloring method - Google Patents

Description

【０１４３】
【表２】

【０１４４】
【表３】

【０１４５】
【表４】

【０１４６】
なお、上記表１・２からも分かる如く、実施例１８〜２７は、実質的にそれぞれ実施例１〜１０に対応しており、染色浴が異なるのみである。実施例１１〜１７は、上記以外の他の態様である。
【０１４７】
表１・２・３・４から、本発明の有機ガラスの着色方法を用いた実施例は、製品として十分な染色が可能であることが分かる。特に、実施例１〜１７の染色方法で得られた染色品は、実施例１８〜２７で得られた染色品よりも全体的に透過率が低いことが分かる。すなわち、より染色性が良好であって、望ましい態様であることが分かる。
【０１４８】
対して、比較例１〜４は、染料媒体膜の溶解による剥離ができず、染色性に劣るものであった。また、比較例５は、対応する実施例３，４と比較し、ハードコート前と比べてハードコート後の視感度透過率の差が大きく上昇していることから、後工程での色落ちが激しいことが分かる。また、比較例６は、対応する実施例５と比較し、ハードコート前の視感度透過率の値が大きいことから、ほとんど着色されなかったことが分かる。
【０１４９】
なお、上記各実施例と各請求項との対応を明確にするため、以下に参考として実施例−請求項対応表を付す。
【０１５０】
【表５】

【図面の簡単な説明】
【図１】本発明の有機ガラス着色方法を示す概略工程図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for coloring optical organic glass such as glasses and cameras, and an optical element obtained by the coloring method. In the following, description will be made by taking a spectacle lens as an example of the optical organic glass.
[0002]
[Prior art]
In recent years, as an optical lens material, organic glass, which is lighter and more shock-resistant than inorganic glass, is dyeable and can be easily processed, has become widespread. Furthermore, as a trend in recent years, there is a growing need for thinning of the edge of the lens due to the demand for fashionability of the optical lens itself. For this reason, ultra-high refractive organic glass lenses having a higher refractive index (refractive index of about 1.70) have been put on the market.
[0003]
However, the organic glass lens has a problem that it becomes difficult to dye as the refractive index increases. For this reason, in the immersion dyeing method in which dyeing is performed by immersing the base material (lens) in an aqueous dye bath (aqueous solution) using a disperse dye or the like, the following problems are likely to appear remarkably.
[0004]
(1) It is difficult to dye a substrate with uniform and stable color tone. Dyeability (dyeing speed and dyeing equilibrium) is the concentration of each component of the aqueous dye dispersion (dispersion dye, surfactant, dyeing accelerator, etc.), variation in dyeing temperature, type of organic glass substrate, etc. It is because it is easy to be influenced by.
[0005]
(2) When high-density dyeing (coloring) is required, dyeing takes a long time.
[0006]
{Circle around (3)} Dyeing at a low temperature, and since the dyeing power is not sufficient, discoloration in the post-process is large, and it is difficult to achieve the desired color tone in the final finish.
[0007]
[Problems to be solved by the invention]
In order to solve the above-mentioned problem, a means to replace the immersion dyeing method, for example,
(1) A method in which a dye is sublimated in the gas phase to form a dye layer on the surface of the organic glass, and then the dye is heated and transferred (transferred) (Japanese Patent Laid-Open No. 56-159376, etc.)
(2) A method of attaching a dyed transfer film to the surface of an organic glass substrate and transferring it by heating (Japanese Patent Laid-Open No. 2000-9905, etc.)
(3) A method of applying oil-based ink containing a dye on an organic glass substrate and transferring it by heating (JP 2000-17586, etc.),
(4) A method in which a disperse dye is dissolved or suspended in a water-soluble polymer and then kneaded or penetrated into an organic glass substrate (Patent Nos. 3022555, 3074503, etc.)
Has been proposed.
[0008]
However, in the method (1), since the sublimation temperature differs depending on the dye, it is difficult to obtain a desired color tone and coloring density on the substrate. In the method (2), it is difficult to apply the transfer film cleanly to the curved surface, and it is difficult to obtain uniform coloring without uneven coloring on the substrate.
[0009]
In addition, the above (1), (2), (3)
(a) Gradation dyeing process called “half” is difficult.
(b) Since the dye is blended (prepared) in advance and heat transfer is performed, it is difficult to color the desired color in a short time, and it takes time to blend (prepare) the desired color.
There was a problem.
[0010]
Further, the method (4) is insufficient in terms of colorability, and it is difficult to obtain a dyed product having a high density (a density of 70% or more and a luminous transmittance of 30% or less).
[0011]
In view of the above, an object of the present invention is to provide a method for coloring an organic glass that can easily change a desired color tone and density, and can also easily perform gradation dyeing, and an optical element obtained by the coloring method. And
[0012]
[Means for Solving the Problems]
As a result of diligent development and research to solve the above-mentioned problems, the present inventors have conceived an organic glass coloring method and an optical element having the following constitution.
[0013]
  Organic glass of the present inventionofColoring method is organic glassOn substrateDyeing by sublimation transfer through the dye medium filmI color organic glassIn the method
  (1) On the surface of organic glass substrateSP value of 15 or lessDissolvable in organic solventWith thermoplastic resin (excluding water-soluble resin)Medium resin coatingFormedThereafter, a dye medium film forming step of immersing the dye in a dye bath to adsorb the dye on the medium resin coating film to form a dye medium film,
  (2) Dye transfer process that heats and transfers (sublimation transfer) the dye in the dye medium film to an organic glass substrate,
  (3) Dye medium filmOrganic solvent with SP value 8-11Dissolutiondo itDye medium removal process for film removal,
  A colored organic glass is obtained through each of the steps.
[0014]
  As another method,
  (1) Dye is contained on the surface of organic glass substrateA thermoplastic resin (excluding water-soluble resins) that can be dissolved in an organic solvent having an SP value of 15 or less.A dye medium film forming step for forming a dye medium film;
  (2) Dye transfer process that heats and transfers (sublimation transfer) the dye in the dye medium film to the organic glass substrate,
  (3) The dye medium filmOrganic solvent with SP value 8-11Dissolutiondo itA colored organic glass is obtained by sequentially performing each step of the dye medium film removing step for film removal.
[0015]
In each of the dye transfer steps, gradation dyeing can be performed by giving a gradient to the temperature and / or time of the heat treatment and, if necessary, partially cooling.
[0016]
As the dye, it is preferable to use a water-insoluble dye because it is easy to obtain a dye having high dyeing property and high sublimation property for a highly refractive organic glass substrate.
[0017]
  Also formed dye medium filmThermoplasticityresinIsIt is desirable to use a krill-based thermoplastic resin because it has excellent dye medium properties and excellent film removal from an organic glass substrate.
[0018]
On the other hand, the optical element of the present invention is characterized by being colored by each of the above-mentioned coloring methods. If necessary, a hard coat film such as a silicone-based cured coating film may be laminated with or without a primer layer, and an inorganic antireflection film may be further laminated.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail. In FIG. 1, the representative example of the manufacturing process of the colored organic glass of this invention is shown. In the following description, “%” and “part” indicating the composition are in “mass (weight)” units unless otherwise specified.
[0020]
The organic glass coloring method of the present invention is based on the premise that the organic glass substrate or the organic glass substrate provided with the hard coat film is dyed by sublimation transfer through a dye medium film.
[0021]
Examples of the organic glass substrate include polymethyl methacrylate (PMMA), polycarbonate (PC), aliphatic allyl carbonate, aromatic allyl carbonate, polythiourethane, thioepoxy resin and the like. The coloring method of the present invention can be applied to both low refractive index lenses and high refractive index lenses.
[0022]
A hard coat film is usually provided on the organic glass substrate. The hard coat film can be provided with a primer layer in order to improve impact resistance.
[0023]
The hard coat film only needs to be formed in the final product,
(1) A method of forming a dye medium film on an organic glass substrate before dyeing and then forming a dye medium film on the hard coat film and dyeing.
(2) A method of forming a hard coat film after forming a dye medium film on an organic glass substrate and completing dyeing,
Either of these may be selected.
[0024]
It is desirable to use a silicone-based cured coating as the hard coat film. For example, a catalyst and metal oxide fine particles (including composite fine particles) can be added to the hydrolyzate of organoalkoxysilane and applied with a diluting solvent. It is formed by applying a hard coat liquid adjusted so as to have a high viscosity on a glass substrate. Furthermore, a surfactant, an ultraviolet absorber and the like can be appropriately added to the hard coat solution.
[0025]
The hard coat film can be dyed regardless of whether it is a dyeable type or a non-dyeable type.
[0026]
(1) As the organoalkoxysilane, those represented by the following general formula can be used.
[0027]
R¹ _aR² _bSi (OR^Three )_{4- (a + b)}
(However, R¹ Is an alkyl group having 1 to 6 carbon atoms, a vinyl group, an epoxy group, a methacryloxy group, a phenyl group, and R² Is an alkyl group having 1 to 3 carbon atoms, an alkylene group, a cycloalkyl group, a halogenated alkyl group, an aryl group, an arylalkyl group, an alkylaryl group, R^Three Is an alkyl group having 1 to 4 carbon atoms, an alkylene group, a cycloalkyl group, an alkoxyalkyl group, or an arylalkyl group. Also, a = 0 or 1, b = 0, 1, or 2.)
[0028]
Specifically, tetramethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, trimethylchlorosilane, glycidoxymethyltrimethoxysilane, α-glycidoxyethyltrimethoxysilane, β -Glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and the like can be mentioned. These can be used alone or in combination of two or more.
[0029]
(2) Examples of the catalyst include organic carboxylic acids such as trimellitic acid, trimellitic anhydride, itaconic acid, pyromellitic acid and pyromellitic anhydride, nitrogen-containing organic compounds such as methylimidazole and dicyandiamide, and metal alkoxides such as titanium alkoxide and zircoalkoxide. Further, metal complexes such as acetylacetone aluminum and acetylacetone iron, and alkali metal organic carboxylates such as sodium acetate and potassium acetate can be used.
[0030]
(3) The metal oxide fine particles include colloidal silica, colloidal titania, colloidal zirconia, colloidal cerium (IV), colloidal tantalum oxide (V), colloidal tin oxide (IV), colloidal having an average particle diameter of about 5 to 50 μm. Antimony (III) oxide, colloidal alumina, colloidal iron (III) oxide and the like can be used, and these can be used in combination of two or more, or as composite fine particles, in addition to single use.
[0031]
(4) As the diluting solvent, polar solvents such as alcohols, ketones, esters, ethers and cellosolve (trade name of VCC: monoalkyl ethers of ethylene glycol) can be preferably used.
[0032]
(5) The coating method is selected from conventional methods such as dipping and spin coating. The curing conditions are about 80 to 130 ° C. × about 1 to 4 hours.
[0033]
A primer layer can be formed between the organic glass substrate and the hard coat film, but it is particularly desirable to use the following primer excellent in impact resistance.
[0034]
As a specific primer, a TPU primer composition in which metal oxide inorganic fine particles are added to a urethane-based thermoplastic elastomer (TPU), and all or a main part of the film-forming polymer is the same as the ester-based thermoplastic elastomer (TPEE) as described above. The TPEE primer composition to which the metal oxide inorganic fine particles are added is used.
[0035]
TPU is composed of a soft segment composed of a long-chain polyol and a polyisocyanate, and a hard segment composed of a short-chain polyol and a polyisocyanate, and is preferably added in the form of an aqueous emulsion (emulsion). .
[0036]
As the metal oxide fine particles, those used for the hard coat described above can be used.
[0037]
TPEE is a multi-block copolymer using polyester as a hard segment and polyether or polyester as a soft segment. The weight ratio of the hard segment to the soft segment is usually the former / the latter = about 30/70 to 10 / 90.
[0038]
Further, the same metal oxide inorganic fine particles as those of the urethane primer are used for adjusting the refractive index.
[0039]
And when dyeing | staining the said organic glass base material etc., as a 1st method, after providing a medium resin coating film on the surfaces, such as an organic glass base material first, it immerses in a dyeing bath and a dye is a medium resin coating film To make a dye medium film. This corresponds to a process of forming a paste (glue) layer in a so-called thread (printing) (a stamping process).
[0040]
The medium resin for forming the medium resin coating film is not particularly limited as long as it is a resin that is soluble (dispersible) with respect to the following dissolving (dispersing) agent. , Saturated ester resin, vinyl butyral resin, acetal resin, vinyl resin, amide resin, cellulose resin (above, thermoplastic resin); urethane resin, fluorine resin, epoxy resin, melamine resin, silicone resin Examples thereof include resins (above, thermosetting resins) and the like, or mixtures thereof, derivative polymers, copolymers, and the like.
[0041]
Of the above resins, thermosetting resins are cured by heating and are difficult to peel off after heating and sublimation. Therefore, it is preferable to use a thermoplastic resin. Of the above thermoplastic medium resins, acrylic thermoplastic resins are desirable because they have excellent dye medium properties and excellent film removal from organic glass substrates. Here, the dye medium property means a property of adsorbing (receiving) the dye in the dyeing bath and transferring it to an organic glass substrate or the like.
[0042]
The concentration of the medium resin in the medium resin coating for forming the medium resin coating film is about 0.01 to 90%, preferably about 0.1 to 70%, and more preferably about 1 to 50%. If the resin concentration is too low, it is difficult to obtain a coating thickness sufficient to adsorb (accept) and transfer the dye. On the other hand, if it is too high, the dye transfer property is lowered and the surface accuracy (leveling property) of the adhered film is lowered, which causes uneven dyeing. Here, the necessary coating thickness is about 0.1 to 10 μm.
[0043]
The dissolving (dispersing) agent for the medium resin in the medium resin coating is not particularly limited as long as it has an SP value of 20 or less, preferably an SP value of 15 or less, as long as it can dissolve or disperse the medium resin. Good. Specifically, alcohols such as methanol (14.8), ethanol (12.8), isopropyl alcohol (11.15), n-butanol (11.1), methyl acetate (9.6), ethyl acetate (9.0), esters such as butyl acetate (8.5), hydrocarbons such as benzene (9.2), toluene (8.9), p-xylene (8.8), acetone (9. 8), ketones such as methyl isopropyl ketone (9.5), methyl propyl ketone (8.9), and the like, and two or more of the above solvents can be used in combination (the SP value is shown in parentheses). .
[0044]
The method for applying the medium resin coating to the organic glass substrate or the like is not particularly limited as long as it can form a uniform film. Specifically, a dipping method, a spin coating method, a brush coating method, Known techniques such as spraying can be used. In particular, the spin coating method can be effectively used because uniform film formation is easy.
[0045]
Usually, before forming on an organic glass substrate or the like, the substrate lens surface is subjected to pretreatment such as degreasing and ultrasonic cleaning using an acid or alkali cleaning solvent. In order to improve the adhesion to the organic glass substrate, a treatment such as plasma etching or alkali etching may be performed. In addition, it is desirable to perform a heat treatment at about 50 to 100 ° C. for about 10 minutes in order to cure or dry the medium resin coating.
[0046]
Further, in order to improve the leveling property of the dissolved or dispersed medium resin coating, it is desirable to add a silicone surfactant or a fluorine surfactant.
[0047]
After the medium resin coating film is formed on the surface (both sides or one side) of an organic glass substrate or the like, a dye medium film is formed by adsorbing (adsorbing / receiving) a dye on the medium resin coating film. As this dye adsorption method, a known technique can be used, and among these, it is desirable to use a dip dyeing method. Specific examples include a carrier dyeing method in which a dye and a carrier agent are contained in a dyeing bath, and a general dyeing method in which a dye and a dispersant are contained. When a water-insoluble dye is used as the dye, the above dyeing bath has a dye dissolving agent (mixed system of water and organic solvent) consisting of an organic solvent having an SP value (solubility parameter) of about 7 to 13 It is desirable to be in a state of being dissolved or partially dissolved. Here, complete dissolution means that the dye in the dyeing bath has not reached the saturation amount, and all the dye is dissolved. Partial dissolution means that there is more than the saturation amount of dye in the dyeing bath. It means a state in which a part of the dye remains without dissolving. In addition, there are ink jet recording methods and the like that have been widespread in recent years, and a plurality of the above methods can be used in combination.
[0048]
As the dye, a water-insoluble dye is desirable because it has good dyeability (transferability to an organic glass substrate) for an organic glass substrate having a high refractive index and can easily obtain a dye having high sublimation properties. As the water-insoluble dye, a general-purpose disperse dye (Disperse Dyes) or an oil-soluble dye (Solvent Dyes) can be preferably used.
[0049]
Disperse dyes include "Sumikaron" manufactured by Sumitomo Chemical; "Diaoelliton", "Dianix", "Samaron", manufactured by Dystar Japan; "Kayalon Polyester" “Nippon Kayaku Co., Ltd.”; “Miketon Polyester” manufactured by Mitsui BASF Dye Co., Ltd., etc. may be used.
[0050]
Oil-soluble dyes are manufactured and sold under the product names such as “Spilit” manufactured by Sumitomo Chemical; “Orient Oil” manufactured by Orient Chemical; “Mitsui SP” manufactured by Mitsui Chemicals, Inc. Things can be mentioned.
[0051]
To the disperse dyes and oil-soluble dyes which are the above water-insoluble dyes, an ultraviolet absorber and a fluorescent whitening agent (one type of water-insoluble sublimation dyes) exhibiting the same sublimation properties as these dyes are added. can do. The ultraviolet absorber and the fluorescent whitening dye are about 0.1 to 50%, preferably about 1 to 20% of the total amount of the water-insoluble dye to which these are added. Dyeing in a dyeing bath containing these UV absorbers and fluorescent brighteners, and heating and sublimation (transfer) of dyes such as substrate lenses as described later, UV absorption and fluorescent whitening simultaneously with dyeing And the like can be imparted to optical elements (eg, glasses). That is, when using glasses, the eyes can be protected from ultraviolet rays, and the fashion function of the glasses can be enhanced.
[0052]
The ultraviolet absorber is not particularly limited as long as it has sublimability, but benzophenone, benzotriazole, cyanoacrylate, salicylate, and the like can be used. As the optical brightener, diaminostilbene disulfonic acid type, imidazole type, coumarin type, triazole type and the like can be used.
[0053]
The adsorption temperature of the dye on the medium resin coating film is not particularly limited as long as the dye can be adsorbed on the medium resin coating film. Specifically, it is about 0 to 100 ° C., preferably about 5 to 85 ° C. ° C, more preferably about 15 to 75 ° C. If the adsorption temperature is too low, agglomeration of the dye occurs, the adsorptivity decreases, and a cooling device is required, which is uneconomical. Conversely, if the adsorption temperature is too high, the organic glass substrate and the medium resin coating film may be damaged by thermal deformation, dissolution, etc., and the organic solvent may bump.
[0054]
As a second method, a dye medium film is formed by providing a dye medium resin containing a dye on the surface of an organic glass substrate or the like. This is a method in which a dye is contained in a dye medium resin, and then the dye medium resin is applied to the surface of an organic glass lens or the like, which is a known technique as a kneading coloring method.
[0055]
As the medium resin for forming the dye medium film, those exemplified in the first method can be used. Furthermore, the concentration of the dye medium resin in the dye medium resin coating, the required coating thickness, the medium resin solubilizer (dispersant), the method of application to organic glass lenses, and the addition of interfacial lubricants can be used. The dyes can also be used in accordance with those described in the first method.
[0056]
When a water-insoluble dye is used as the dye, the dye medium resin has a dye solubilizing agent comprising an organic solvent having an SP value (solubility parameter) of about 7 to 13, preferably about 9 to 11 ( It is desirable to contain a dye that is completely dissolved or partially dissolved in an organic solvent alone or a combined system of water and an organic solvent. Here, complete dissolution means that the dye in the dyeing bath has not reached the saturation amount, and all the dye is dissolved. Partial dissolution means that there is more than the saturation amount of dye in the dyeing bath. It means a state in which a part of the dye remains without dissolving. If the SP value of the dye dissolving agent deviates from the above value, the mutual solubility of the resin, the dye, and the solvent is deteriorated, and the coloring cannot be achieved up to the target concentration, or appearance defects such as dyeing unevenness are caused.
[0057]
The dye dissolving agent is selected in consideration of not affecting the surfaces of the organic glass substrate and the hard coat layer (no surface roughness). In particular,
Benzene (9.15), toluene (8.90), o-xylene (9.00), m-xylene (8.80), p-xylene (8.75), ethylbenzene (8.80), naphthalene ( 9.90), tetralin (9.50), n-propylbenzene (8.65), i-propylbenzene (8,86), mesitylene (8.80), and other aromatic hydrocarbons,
Cyclohexanol (11.40), ethanol (12.7), n-butanol (11.40), i-butanol (10.70), n-propanol (12.10), diacetone alcohol (10.18) , Hydroxyl compounds such as n-heptanol (10.00),
Acetone (10.00), methyl ethyl ketone (9.30), diethyl ketone (8.80), dibutyl ketone (8.10), methyl-n-propyl ketone (8.70), methyl-n-butyl ketone (8. 60), ketones such as methyl-i-amyl ketone (8.50), methyl hexyl ketone (8.45), cyclohexanone (9.90), acetophenone (9.68),
Methylal (8.52), furan (9.09), β-β-dichloroethyl ether (9.80), dioxane (10.00), tetrahydrofuran (9.90), ethyl cellosolve (9.90), etc. Ethers,
These can be used alone, or two or more can be appropriately selected and used (in parentheses indicate SP values).
[0058]
Further, the dye solubilizer contains at least ethers, hydroxyl compounds and / or ketones, so that the solubility of the dye is excellent and the surface of the organic glass substrate or the like is hardly roughened.
[0059]
Then, by heating the dye medium film, the dye is sublimated, and the dye is transferred (transfer-fixed) to the organic glass substrate or the like. This corresponds to a dye fixing step by steaming in so-called silk thread (printing).
[0060]
The method of heating sublimation is not particularly limited, but specifically, wet processing by hot-air circulating furnace, far-infrared furnace, electric furnace, dryer using a drier, etc., immersion in hot water or hot oil bath Etc. Among the above, the hot air circulating furnace has the advantage that there is no temperature unevenness inside the apparatus and the organic glass substrate can be heated uniformly.
[0061]
On the other hand, a colored organic glass having a color density gradient can be easily obtained by performing the following operation during the heat treatment.
[0062]
Uneven heating is performed on the dye medium film infiltrated with or containing the dye dissolved or partially dissolved by the dye dissolving agent. Alternatively, using a hot water bath or a hot water bath, heat treatment is performed so that at least the dye medium film has a temperature gradient or a difference in heating time. By performing such non-uniform heating, it is possible to have a color density gradient corresponding to the cumulative cumulative heating amount. Therefore, in order to obtain a colored organic glass lens having a colored concentration gradient, heating by a far-infrared furnace, an electric furnace, a drier, or a wet process that is easy to locally heat is desirable.
[0063]
Although it does not specifically limit as a cooling method at the time of obtaining the colored organic glass which has a coloring concentration gradient, It is practically suitable to use 40 degrees C or less air. Air cooling can suppress coloring (transfer) due to heat conduction.
[0064]
As the heating sublimation (transfer) temperature, the glass transition temperature of the organic glass substrate, the heat resistant temperature of the hard coat film (including the primer layer) when dyeing the organic glass substrate provided with the hard coat film, and In consideration of the dye sublimation pressure (sublimation temperature).
[0065]
Usually, the temperature is about 60 to 200 ° C, desirably about 70 to 180 ° C, more desirably about 80 to 150 ° C. If the heating sublimation temperature is too low, it is difficult to obtain sufficient colorability. Conversely, if the heating sublimation temperature is too high, the organic glass substrate may be thermally deformed. In this case, if a reduced pressure atmosphere (usually about 10 to 800 hPa) is used, it can be expected that the heat treatment temperature can be relatively lowered and the heat sublimation time can be shortened. Further, an organic glass substrate that is stable against heat (not deformed) can be heated under pressure. At this time, the dye can be transferred to the organic glass substrate at a relatively low temperature.
[0066]
The heating sublimation time varies depending on the dyeability of the organic glass substrate and the like, but is usually about 10 min to 24 h, preferably about 30 min to 6 h. It is necessary to select the organic glass substrate, primer film, or hard coat film (silicone-based cured coating film) that is the object to be dyed in consideration of the heating sublimation temperature and time.
[0067]
In addition, when performing the above-mentioned heat sublimation, a thermoplastic resin is further coated on the surface of the dye medium film as a protective film for the purpose of preventing external scattering of the dye and preventing scratches on the surface of the dye medium film. Also good. The thermoplastic resin for the protective film is not particularly limited as long as it has good heat resistance and solvent resistance and can be dissolved and peeled after forming the protective film. Specifically, polyvinyl butyral, polyvinyl alcohol, or the like can be preferably used.
[0068]
The dye medium film and the protective film adhering to the organic glass substrate after the heat sublimation are removed by dissolution and peeling by immersion in an organic solvent such as acetone or water (warm water). This process corresponds to a paste removing process in textile printing. In addition, as an organic solvent which can be used, the organic solvent of SP value 8-11 is used similarly to what was used for the above-mentioned interposition for dyes.
[0069]
In general, it is desirable to form an antireflection film on the hard coat film. The antireflection film is usually formed by forming inorganic fine particles such as metal, metal oxide, and metal fluoride by a dry plating method such as vacuum deposition, sputtering, or ion plating.
[0070]
Specific examples of the inorganic material forming the antireflection film include metal oxides such as silica, titania (IV), tantalum oxide (V), antimony (III) oxide, zirconia, and alumina, and metal fluorides such as magnesium fluoride. Can be mentioned.
[0071]
【The invention's effect】
The organic glass coloring method of the present invention is formed on the surface of an organic glass substrate or the like, after forming a medium coating film, and dyeing by providing a dye medium film with a dyeing bath, as supported in the examples described later, The following effects are achieved.
[0072]
The film thickness of the medium resin coating film, the dye adsorption conditions using a dyeing bath, and further the conditions for sublimation transfer can be adjusted independently and combined easily.
[0073]
For this reason, it is possible to efficiently and easily color a desired color tone and density even with respect to an organic glass substrate having an ultrahigh refractive index to a low refractive index, particularly a non-dyed organic glass substrate. Further, gradation coloring processing, which has been difficult with the conventional heat sublimation dyeing method, can be easily performed. Further, since the hard coat film formed on the surface of the organic glass substrate can be easily colored, it is possible to color to a desired color tone and density without considering discoloration in a subsequent process.
[0074]
[Experimental example]
Examples and comparative examples, which are experimental examples conducted to confirm the effects of the present invention, will be described below. The materials used in each experimental example were prepared as follows.
[0075]
Organic glass substrate
(1) Organic glass substrate A (low refractive substrate: refractive index 1.50)
A polymerization initiator: 3 parts of diisopropyl peroxycarbonate was mixed with 100 parts of diethylene glycol bisallyl carbonate, filtered through a 0.8 μ membrane filter, and the filtrate was poured into a glass mold. Next, the temperature was raised at 40 ° C. for 3 h, 40 to 60 ° C. for 12 h, and 65 to 85 ° C. over 6 h, and finally heated at 85 ° C. for 3 h. An organic glass substrate was obtained by annealing for 2 h at ℃.
[0076]
(2) Organic glass base material B (high refractive base material: a product with a refractive index of 1.67) ... thiourethane organic glass.
[0077]
(3) Organic glass base material C (super high refractive base material: refractive index 1.74 marketed product) ... thioepoxy organic glass.
[0078]
Hard coat liquid
(1) Hard coat liquid a (low refractive liquid: refractive index 1.50):
γ-glycidoxypropyltrimethoxysilane 100 parts, MeOH 200 parts, 10^-2After 1100 parts of N HCl was hydrolyzed at reflux for 2 hours, 1200 parts of methanol silicasol, 7 parts of acetylacetone aluminum, and 0.4 parts of “FC-430” (a fluorine surfactant manufactured by Sumitomo 3M) were added to prepare.
[0079]
(2) Hard coating liquid b (high refractive liquid: refractive index 1.60):
A mixture of 320 parts of γ-glycidoxypropyltrimethoxysilane, 50 parts of tetraethoxysilane, and 230 parts of MeOH was stirred and homogenized.^-2After 60 parts of N HCl was slowly added dropwise, hydrolysis was carried out overnight at room temperature. To this hydrolyzate, 360 parts of titania composite particles, 40 parts of itaconic acid, 20 parts of dicyanamide and 1 part of a leveling agent were added and stirred at room temperature for about 24 hours.
[0080]
(3) Hard coat liquid c (ultra-high refractive liquid: refractive index 1.66):
A mixture of 320 parts of γ-glycidoxypropyltrimethoxysilane, 50 parts of tetraethoxysilane, and 230 parts of MeOH was stirred and homogenized.^-2After 60 parts of N HCl was slowly added dropwise, hydrolysis was carried out overnight at room temperature. To this hydrolyzate, 700 parts of titania composite particles, 40 parts of itaconic acid, 20 parts of dicyanamide and 1 part of a leveling agent were added, and the mixture was stirred at room temperature for about 24 hours.
[0081]
Medium resin paint
After 9 parts of a commercially available acrylic resin “Dianal BR-80” was dissolved in 21 parts of diacetone alcohol, 30 parts of methyl ethyl ketone (MEK) and 0.01 part of “SILWET L-7001” as a leveling agent were mixed and uniformly Stir until prepared.
[0082]
Dye (containing) medium resin paint
(1) Dye (containing) medium resin paint α (using colored dye)
After adding 6 parts of “Sumikaron Blue E-RPD”, 4 parts of “Sumikaron Red E-RPD” and 2 parts of “Sumikaron Yellow E-RPD”, 12 parts of methyl ketone and 12 parts of dioxane are added and stirred for about 10 minutes. Filtration was performed with a 3 μ filter to prepare a water-insoluble paint solution. Separately, a resin solution in which 3.2 parts of a commercially available acrylic resin “Dianal BR-80” was dissolved in 12.8 parts of toluene was prepared, and “SILWET L- 7001 "was mixed with 0.01 part and stirred until uniform.
[0083]
(2) Dye (containing) medium resin paint β (using UV absorbing dye)
Add 24.4 parts of methyl ketone and 14.39 parts of dioxane to 2 parts of UV absorber “Ubinal D-50”, stir and dissolve for about 10 minutes, filter through a 3μ filter, and dissolve the water-insoluble paint solution. Prepared. Separately, a resin solution prepared by dissolving 3.84 parts of a commercially available acrylic resin “Dianal BR-80” in 15.36 parts of toluene was prepared, and “SILWET” was used as a solution for the above UV absorber and a leveling agent. L-7001 "0.01 parts was mixed and stirred until uniform.
[0084]
(3) Dye (containing) medium resin paint γ (polymer polymer base: used in comparative examples)
Add 6 parts of polyvinyl alcohol # 2000 (molecular weight of about 2000) to 100 parts of pure water, stir until uniform, then 3 parts of “Sumikaron Blue E-RPD”, “Sumikaron Red E-RPD” 2 1 part of “Sumikaron Yellow E-RPD” was added and stirred until uniform.
[0085]
Protective coating
It was prepared by adding 85 parts of pure water to 15 parts of polyvinyl alcohol (degree of polymerization: about 2,000) and stirring until uniform.
[0086]
Dyeing bath
(1) Dyeing bath I (containing dye dissolving agent, using colored dye)
1000 parts of water, 1 part of “Sumikaron Blue E-RPD”, 0.5 part of “Sumikaron Red E-RPD”, 0.5 part of “Sumikaron Yellow E-RPD”, “Isopropyl Alcohol” 25 as a dye dissolving agent In addition, 3 parts of “Lebenol V-700” as a surfactant and 25 parts of benzyl alcohol as a carrier agent were added and stirred, and then heated to 60 ° C. to prepare.
[0087]
(2) Dyeing bath II (containing dye dissolving agent, using UV absorbing dye)
1000 parts of water, 2 parts of UV absorber “Ubinal D-50”, 3 parts of “Lebenol V-700” as surfactant, 25 parts of “isopropyl alcohol” as dye solubilizer, and 25 parts of benzyl alcohol as carrier agent The mixture was stirred and then heated to 60 ° C. to prepare.
[0088]
(3) Dyeing bath III (no dye dissolving agent, using colored dye)
1000 parts of water, 2 parts of “Sumicaron Blue E-RPD”, 1 part of “Sumikaron Red E-RPD”, 1 part of “Sumicaron Yellow E-RPD”, and “Levenol V-700” 3 as a surfactant After stirring, the mixture was stirred and heated to 90 ° C.
[0089]
(4) Dyeing bath IV (no dye dissolving agent, UV absorbing dye used)
To 1000 parts of water, 2 parts of an ultraviolet absorber “Ubinal D-50” and 3 parts of “Lebenol V-700” as a surfactant were added, stirred and heated to 90 ° C.
[0090]
<Example 1>
The organic glass substrate A (low refractive substrate: lens) is wiped with a cloth soaked in ethyl alcohol, and the concave surface of the lens is spin-coated (step 1: 1000 rpm × 5 sec, step 2: 2000 rpm × 5 s). The medium resin coating was applied and heat treatment was performed at 100 ° C. for 5 minutes in an air oven. Thereafter, the medium resin coating was similarly applied to the convex surface, followed by heat treatment to form a medium resin coating film (coating thickness 0.15 μm) on the glass substrate.
[0091]
Next, it is immersed in dyeing bath I (containing a dye solubilizing agent and using a colored dye) for 10 minutes to adsorb the dye onto the medium resin coating film to form a dye medium film, and when the medium resin coating film is formed on the glass substrate after immersion. A protective film was applied under the same conditions.
[0092]
Then, after heating at 130 ° C. × 100 min in an air oven, it is immersed in warm water (about 60 ° C.) for 2 min and then in acetone for 1 min to remove the dye medium film and the protective film, and the colored organic glass substrate Got.
[0093]
The colored organic glass substrate was immersed in a 40 ° C. sodium hydroxide aqueous solution (concentration: 10%), washed with pure water, and drained.
[0094]
Then, it was immersed in the hard coat liquid a (low refractive liquid) and pulled up at 105 mm / min to obtain a temporary curing at 95 ° C. for 20 min. Thereafter, curing was performed at 100 ° C. for 2 hours to obtain a colored organic glass hard coat processed product.
[0095]
<Example 2>
Using organic glass base material A (low refractive base material), dyeing bath II (containing dye dissolving agent, using UV absorbing dye), and hard coat liquid a (low refractive liquid), colored organic in accordance with the method of Example 1 A glass hard coat processed product was obtained.
[0096]
<Example 3>
Colored organic glass according to the method of Example 1 using organic glass substrate B (highly refractive substrate), dyeing bath I (containing dye dissolving agent, using colored dye), and hard coat liquid b (highly refractive liquid) A hard coat processed product was obtained.
[0097]
<Example 4>
Using organic glass base material B (highly refractive base material), dyeing bath II (containing a dye solubilizer, using an ultraviolet absorbing dye), and hard coat liquid b (highly refractive liquid), a colored organic material is prepared according to the method of Example 1. A glass hard coat processed product was obtained.
[0098]
<Example 5>
Colored in accordance with the method of Example 1 using an organic glass substrate C (ultra-high refraction substrate), a dyeing bath I (containing a dye dissolving agent, using a colored dye), and a hard coat liquid c (ultra-high refraction liquid). An organic glass hard coat processed product was obtained.
[0099]
<Example 6>
An organic glass substrate A (low refractive substrate: lens) is immersed in a 40 ° C. aqueous sodium hydroxide solution (concentration: 10%), washed with pure water, drained, and then hard coat solution a (low refractive) The film was dipped in a liquid), pulled up at 105 mm / min, and pre-cured at 95 ° C. for 20 min. Thereafter, curing was performed at 100 ° C. for 2 hours to obtain a glass hard coat processed product.
[0100]
A medium resin coating film is formed on the processed glass hard coat product in accordance with the method of Example 1, and the medium resin coating film is soaked in dye bath I (containing a dye dissolving agent and using a colored dye) for 10 minutes to adsorb the dye onto the medium resin coating film Thus, a dye medium film was formed, and a protective film was formed on the glass substrate after immersion under the same conditions as those for forming the medium resin coating film.
[0101]
Then, after sublimation transfer was performed by heating at 130 ° C. for 100 minutes in an air oven, the dye medium film and the protective film were removed by immersing in warm water (about 60 ° C.) for 2 minutes and then in acetone for 1 minute. After removal, an organic glass hard coat processed product was obtained.
[0102]
<Example 7>
Using organic glass base material A (low refractive base material), dyeing bath II (containing a dye dissolving agent, using UV absorbing dye), and hard coat liquid a (low refractive liquid), a colored organic material is prepared according to the method of Example 6. A glass hard coat processed product was obtained.
[0103]
<Example 8>
Colored organic glass according to the method of Example 6 using organic glass base material B (highly refractive base material), dyeing bath I (containing dye dissolving agent, using colored dye), and hard coat liquid b (highly refractive liquid) A hard coat processed product was obtained.
[0104]
<Example 9>
Using organic glass base material B (highly refractive base material), dyeing bath II (containing a dye dissolving agent, using an ultraviolet absorbing dye), and hard coat liquid b (highly refractive liquid), a colored organic material is prepared according to the method of Example 6. A glass hard coat processed product was obtained.
[0105]
<Example 10>
Colored in accordance with the method of Example 6 using an organic glass substrate C (ultra-high refraction substrate), a dyeing bath I (containing a dye dissolving agent, using a colored dye), and a hard coat liquid c (ultra-high refraction liquid). An organic glass hard coat processed product was obtained.
[0106]
<Example 11>
The organic glass substrate A (low refractive substrate) is wiped with a cloth soaked in ethyl alcohol, and a dye (by a spin coating method (step 1: 300 rpm × 15 s, step 2: 1000 rpm × 15 s) is applied to the convex surface of the lens. Containing) Medium resin coating α (using colored dye) was applied and air-dried to form a dye medium film.
[0107]
Thereafter, formation of a protective film, heat treatment of the organic glass substrate, removal of the dye medium film and the protective film by immersion in warm water (about 60 ° C.) for 2 minutes and then in acetone for 1 minute, hard coat processing (hard coat liquid a (Using a low refractive liquid)) to obtain a colored organic glass hard coat processed product. Each treatment method and treatment conditions were the same as in Example 1, but in this example, the heat treatment time of the organic glass substrate in the air oven was 30 minutes.
[0108]
<Example 12>
Colored organic glass hard according to the method of Example 11 using organic glass substrate B (high refractive substrate), hard coat liquid b (high refractive liquid), dye (containing) medium resin paint α (using colored dye) A coated product was obtained.
[0109]
<Example 13>
Colored according to the method of Example 11 using organic glass substrate C (ultra-high refraction substrate), hard coat liquid c (ultra-high refraction liquid), dye (containing) medium resin paint α (using colored dye) An organic glass hard coat processed product was obtained. However, in this example, the heat treatment time of the organic glass substrate by the air oven was 60 min.
[0110]
<Example 14>
The organic glass substrate A (low refractive substrate) (lens) was hard coated in the same manner as in Example 6 using the hard coating solution a (low refractive solution).
[0111]
In accordance with the method of Example 11, a dye-containing medium resin paint α (using a colored dye) is formed on the processed glass hard coat product, and a protective film is formed. The glass substrate was heat-treated, and further immersed in warm water (about 60 ° C.) for 2 minutes and then in acetone for 1 minute to remove the dye medium film and the protective film to obtain an organic glass hard coat processed product.
[0112]
<Example 15>
Colored organic glass according to the method of Example 11 using organic glass substrate A (low refractive substrate), hard coat liquid a (low refractive liquid), dye (containing) medium resin coating β (using ultraviolet absorbing dye) A hard coat processed product was obtained.
[0113]
<Example 16>
A dye medium film and a protective film were formed according to the method of Example 11 using an organic glass substrate B (highly refractive substrate) and a dye (containing) medium resin paint α (using a colored dye).
[0114]
Thereafter, the organic glass substrate was fixed, and heated by blowing hot air onto the lens with a heating gun from a distance of about 10 cm above the convex surface. At this time, the heating gun was moved downward while swinging up and down, and the portion not exposed to hot air was cooled by applying air at room temperature (23 ° C.). This operation was repeated for 3 minutes, then immersed in warm water (about 60 ° C.) for 2 minutes and then in acetone for 1 minute to remove the dye medium film and the protective film to obtain a colored organic glass substrate.
[0115]
A hard coat liquid b (high refractive liquid) was applied to the colored organic glass substrate in accordance with the method of Example 1 to obtain a colored organic glass hard coat processed product.
[0116]
<Example 17>
Colored according to the method of Example 16 using organic glass substrate C (ultra-high refraction substrate), hard coat liquid c (ultra-high refraction liquid), dye (containing) medium resin paint α (using colored dye) An organic glass hard coat processed product was obtained. However, in this example, the above heating / cooling treatment was repeated for 5 minutes.
[0117]
<Example 18>
A colored organic glass hard coat processed product was obtained under the same conditions as in Example 1 except that Dyeing Bath III (no dye solubilizer, colored dye used) was used.
[0118]
<Example 19>
Using organic glass substrate A (low refractive substrate), dyeing bath IV (no dye solubilizer, using UV-absorbing dye), hard coat liquid a (low refractive liquid), colored organic color according to the method of Example 18 A glass hard coat processed product was obtained.
[0119]
<Example 20>
Colored organic glass according to the method of Example 18 using organic glass base material B (highly refractive base material), dyeing bath III (no dye dissolving agent, using colored dye), and hard coat liquid b (highly refractive liquid) A hard coat processed product was obtained.
[0120]
<Example 21>
Using organic glass base material B (high refractive index base material), dyeing bath IV (no dye solubilizer, using UV-absorbing dye), and hard coat liquid b (high refractive index liquid), colored organic in accordance with the method of Example 18 A glass hard coat processed product was obtained.
[0121]
<Example 22>
Colored according to the method of Example 18 using organic glass substrate C (ultra-high refraction substrate), dyeing bath III (no dye dissolving agent, using colored dye), and hard coat solution c (ultra-high refraction solution) An organic glass hard coat processed product was obtained. However, the immersion time in the dyeing bath was 30 min.
[0122]
<Example 23>
A colored organic glass hard coat processed product was obtained under the same conditions as in Example 6, except that Dyeing Bath III (no dye solubilizer, colored dye used) was used.
[0123]
<Example 24>
Using organic glass substrate A (low refractive substrate), dyeing bath IV (no dye solubilizer, using UV absorbing dye), and hard coat solution a (low refractive solution), colored organic in accordance with the method of Example 23 A glass hard coat processed product was obtained.
[0124]
<Example 25>
Colored organic glass according to the method of Example 23 using organic glass substrate B (highly refractive substrate), dyeing bath III (no dye dissolving agent, using colored dye), and hard coat solution b (highly refractive solution) A hard coat processed product was obtained.
[0125]
<Example 26>
In accordance with the method of Example 23, a colored organic material was prepared using an organic glass substrate B (highly refractive substrate), a dyeing bath IV (no dye dissolving agent, using an ultraviolet absorbing dye), and a hard coat solution b (highly refractive solution). A glass hard coat processed product was obtained.
[0126]
<Example 27>
Colored in accordance with the method of Example 23 using organic glass substrate C (ultra-high refraction substrate), dyeing bath III (no dye dissolving agent, using colored dye), and hard coat solution c (ultra-high refraction solution) An organic glass hard coat processed product was obtained. However, the immersion time in the dyeing bath was 30 min.
[0127]
<Comparative Example 1>
The organic glass substrate A (low refractive substrate) is wiped off with a cloth soaked in ethyl alcohol, and the concave surface of the lens is spin-coated (step 1: 300 rpm × 15 sec, step 2: 1000 rpm × 15 sec) to obtain a dye ( Contained) Medium resin coating γ (polymer polymer base) was applied, and after heat treatment at 100 ° C. for 5 minutes in an air oven, the convex surface was similarly applied to form a dye medium film.
[0128]
Thereafter, the organic glass substrate was heated in an air oven at 150 ° C. for 30 minutes and then immersed in running water for 15 minutes, but the medium film could not be peeled off. Got. The media film containing most of the dye peeled off and was slightly colored.
[0129]
Then, hard coat processing was performed using the hard coat liquid a (low refractive liquid) according to the method of Example 23, and a colored organic glass hard coat processed product was obtained.
[0130]
<Comparative Example 2>
According to the method of Comparative Example 1, using an organic glass substrate C (ultra-high refraction substrate), a hard coat liquid c (ultra-high refraction liquid), and a dye (containing) medium resin paint γ (polymer polymer base). A colored organic glass hard coat processed product was obtained.
[0131]
<Comparative Example 3>
An organic glass substrate A (low refractive substrate) was used.
[0132]
First, 6 parts of polyvinyl alcohol # 2000 (molecular weight of about 2000) was added to 100 parts of pure water, and the mixture was stirred until it became uniform to prepare a dye medium resin coating material.
[0133]
Separately, add 100 parts of water to 3 parts of “Sumikaron Blue E-RPD”, 2 parts of “Sumikaron Red E-RPD”, and 1 part of “Sumikaron Yellow E-RPD”, and stir until uniform. A dyeing solution for coating was prepared.
[0134]
According to the method of Comparative Example 1, a dye medium film was formed on both surfaces of the glass substrate (however, the heat treatment time in an air oven was 15 min). Furthermore, the coating dye solution prepared above was applied to both surfaces by the same spin coat method (the heat treatment time in the air oven was 5 min). However, most of the staining solution was scattered in Step 2, and the slightly remaining staining solution was applied unevenly on the dye medium film.
[0135]
Then, heat treatment was performed in the same manner as in Comparative Example 1, but the medium film could not be peeled off and was scraped off to obtain a colored organic glass substrate. The medium film containing most of the dyes peeled off, was hardly colored, and was impossible as a product.
[0136]
<Comparative example 4>
A colored organic glass lens was obtained according to the method of Comparative Example 3 using the organic glass substrate C (ultra-high refraction substrate) and the hard coat solution c (ultra-high refraction solution).
[0137]
<Comparative Example 5>
The organic glass substrate B (high refractive substrate) was wiped with a cloth soaked with methyl alcohol and immersed in a dye bath III (no dye dissolving agent, using colored dye) for 10 minutes to obtain a dyed organic glass substrate.
[0138]
And according to the method of Example 1, the hard-coat process was given using the hard-coat liquid b (high refractive liquid), and the colored organic glass hard-coat processed product was obtained.
[0139]
<Comparative Example 6>
According to the method of Comparative Example 5, using an organic glass substrate C (ultra-high refraction substrate), hard coat liquid c (ultra-high refraction liquid), and dyeing bath III (no dye dissolving agent, using colored dye). A colored organic glass hard coat processed product was obtained. However, the immersion time of the organic glass substrate in the dyeing bath was 60 min.
[0140]
The transmittances of the colored organic glass substrates and the like obtained in the above experimental examples were each measured using “Photosensitivity transmittance meter: CORE STS-3” manufactured by Fuji Photoelectric Industry Co., Ltd. The surface of the lens after dyeing was once wiped with alcohol to remove moisture, and the luminous transmittance at the center of the lens was measured.
[0141]
The results are shown in Tables 1, 2, 3, and 4. About each Example, the transmittance | permeability after a medium film | membrane heat | fever peeling and the transmittance | permeability after hard-coat formation were each measured suitably. Similarly, in each comparative example, the transmittance after dyeing (after treatment) and the transmittance after forming the hard coat were measured as appropriate.
[0142]
[Table 1]

[0143]
[Table 2]

[0144]
[Table 3]

[0145]
[Table 4]

[0146]
As can be seen from Tables 1 and 2, Examples 18 to 27 substantially correspond to Examples 1 to 10 respectively, and only the dyeing bath is different. Examples 11-17 are other aspects other than the above.
[0147]
From Tables 1, 2, 3 and 4, it can be seen that Examples using the organic glass coloring method of the present invention can be sufficiently dyed as products. In particular, it can be seen that the dyed products obtained by the dyeing methods of Examples 1 to 17 generally have lower transmittance than the dyed products obtained in Examples 18 to 27. That is, it can be seen that this is a desirable mode with better dyeability.
[0148]
On the other hand, Comparative Examples 1 to 4 were inferior in dyeability because they could not be separated due to dissolution of the dye medium film. Further, in Comparative Example 5, compared with the corresponding Examples 3 and 4, the difference in the luminous transmittance after the hard coating is greatly increased as compared with that before the hard coating. I understand that it is intense. Further, it can be seen that Comparative Example 6 was hardly colored because the value of the luminous transmittance before the hard coat was larger than that of the corresponding Example 5.
[0149]
In addition, in order to clarify the correspondence between each of the above embodiments and each claim, an example-claim correspondence table is attached as a reference below.
[0150]
[Table 5]

[Brief description of the drawings]
FIG. 1 is a schematic process diagram showing an organic glass coloring method of the present invention.

Claims (12)

A method for coloring an organic glass I rows stained by sublimation dye transfer through the dye medium film to the organic glass substrate,
(1) A medium resin coating film is formed on a surface of an organic glass substrate with a thermoplastic resin (excluding a water-soluble resin) that can be dissolved in an organic solvent having an SP value of 15 or less , and then immersed in a dyeing bath. dye medium film forming step of forming the dye medium film is not a dye adsorbed on the medium resin film,
(2) heating the transferred organic glass substrate a dye of the dye medium film (sublimation dye transfer) are to dye migration process,
(3) a dye medium film removing step of dissolving the dye medium film with an organic solvent having an SP value of 8 to 11 to remove the film;
A method for coloring an organic glass, wherein a colored organic glass is obtained through each of the steps. 2. The method for coloring an organic glass according to claim 1 , wherein the dyeing bath is obtained by partially or completely dissolving a dye with a dye dissolving agent comprising water and an organic solvent. A method for coloring an organic glass I rows stained by sublimation dye transfer through the dye medium film to the organic glass substrate,
(1) A dye medium film forming step of forming the dye medium film on a surface of an organic glass substrate with a thermoplastic resin (excluding a water-soluble resin) that is soluble in an organic solvent containing a dye and having an SP value of 15 or less. ,
(2) heating the transferred organic glass substrate a dye of the dye medium film (sublimation dye transfer) are to dye migration process,
(3) a dye medium film removing step of dissolving the dye medium film with an organic solvent having an SP value of 8 to 11 to remove the film;
A method for coloring an organic glass, wherein a colored organic glass is obtained through each of the steps. The thermoplastic resin forming the dye medium film, water and an organic solvent or claim 3, wherein the containing part or completely dissolved dye in a dye dissolving agent consisting only of an organic solvent Organic glass coloring method. 5. The organic glass coloring method according to claim 2, wherein the dye solubilizer contains an organic solvent having an SP value of 7 to 13 as an essential component. 4. The organic glass coloring method according to claim 1, wherein the dye is a water-insoluble dye. The organic glass coloring method according to claim 1 or 3, wherein the thermoplastic resin forming the dye medium film is an acrylic thermoplastic resin. The organic dye according to claim 1 or 3 , wherein in the dye transfer step, gradation dyeing is performed by giving a gradient to the temperature and / or time of the heat treatment and, if necessary, partially cooling. Glass coloring method. An optical element colored by the method of claim 1, 3 or 8 . An optical element comprising a surface of the optical element according to claim 9 further laminated with a hard coat film with or without a primer layer. The optical element according to claim 10, wherein the hard coat film is a silicone-based cured coating film. The optical element according to claim 10 or 11 , wherein an inorganic antireflection film is further laminated on the hard coat film .

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