JP5492587B2 - Method for producing dyed eye lens and dyed eye lens obtained thereby - Google Patents

Description

  The present invention relates to a method for producing a dyed eye lens and a dyed eye lens obtained thereby.

  In the field of ophthalmic lenses, especially contact lenses, in order to identify and manage the standards such as the frequency of contact lenses when manufacturing, distributing, selling, etc., a number representing the standard is printed on a part of the lens. Things have been done. In addition, numbers, characters, figures, and the like are also printed and displayed in a similar manner so that the user can easily distinguish the front and back of the lens. Furthermore, for patients who have lost their iris due to illness or injury, a contact that gives a natural appearance to the contact lens by imitating the color and shape of the iris of a person's eye from the viewpoint of stability. A lens may be used. In addition, from the viewpoint of fashion, contact lenses with different iris colors are also in great demand. Applying marks and dyeing to the ophthalmic lens in this way is an important factor in the production of the lens.

  Such dyeing of the ophthalmic lens is performed by applying a dyeing solution in which a pigment or dye is dispersed or dissolved in a solvent or the like to the lens surface. Of these, pigments generally do not dissolve in a solvent, and therefore, a dyeing liquid is used in which finely divided particles are dispersed in a solvent. However, since such pigment particles are considerably larger than the size of the polymer network constituting the ophthalmic lens base material, they cannot penetrate into the lens base material, and only stick to the lens surface fragilely. A convex part is formed on the surface. Even if such convex portions are minute, contact lenses that are in direct contact with eyes may cause physical or physiological adverse effects or damage to the eyes. The convex part is often easily peeled off by friction or the like, and the peeled particles may cause secondary troubles such as further damage to the eyes.

  On the other hand, in the case of dyes, dyeing is usually performed using a dyeing solution dissolved in a solvent. Unlike the pigment, the dye is present in the solvent with a molecular size, so that it can penetrate into the polymer network of the lens substrate unless it is an extremely large molecule. However, it is difficult to completely infiltrate the dye molecules into the lens substrate. In practice, the dye is often deposited on the lens surface or remains as a residue. In particular, this phenomenon occurs remarkably when a high concentration dyeing solution is used for the purpose of obtaining a sharp and high contrast dyed print. The generation of such dye deposits and residues becomes a convex portion on the surface of the ophthalmic lens as in the case of the pigment, and there is a risk of the peeling.

  As a method for removing the convex portion of the lens surface generated during the dyeing in this way, for example, a method of polishing the lens surface after the lens dyeing (see Japanese Patent Application Laid-Open No. 5-257096) has been developed. However, a new process is required to smooth the convex portions or remove the precipitates and residues of the dyes by washing as described above, resulting in complicated manufacturing methods and increased costs. .

  Accordingly, there is a need for a method that does not generate dye precipitates during dyeing. As a specific plan for achieving this, there is known a method in which an ophthalmic lens base material is swollen in advance with a solvent and then a staining solution is permeated (for example, Japanese Patent Publication No. 64-10045, Japanese Patent Laid-Open No. 63). -264719, JP-A-4-270312, etc.). There is also known a method in which a lens substrate is swollen by spraying a small amount of water in advance or at the same time from a micro nozzle when applying a dyeing solution to a dry hydrous contact lens by an ink jet application device (special feature). (See Kaihei 8-112666). By adopting these methods, the dye solution is applied in a state where the polymer network of the lens substrate is already swollen by the solvent. Molecules tend to penetrate faster. As a result, the penetration of the dye can be completed or advanced to a state close thereto, and the precipitation of the dye on the lens surface can be effectively prevented.

  However, this method has the following disadvantages. That is, (1) since the mechanical strength of the swollen lens base material is reduced, damage and the like increase in various processes such as dyeing, leading to a decrease in productivity. In addition, a very careful operation is required for the countermeasure, and a special handling device or instrument is required, resulting in an increase in manufacturing cost. (2) By pre-swelling, the diffusion of the dye in the lens substrate is excessively promoted, so that the diffusion of the dye is likely to occur in a place other than the desired part. As a result, bleeding is likely to occur in the resulting dyed printed matter, which may make it difficult to print sharp characters and symbols.

  Since the method of swelling the lens substrate in advance has various disadvantages, a method of dyeing an ophthalmic lens in a dry state has been studied. For example, a sublimable dye is used to sublimate the dye. There is known a method of dyeing by dyeing into the lens substrate (see JP 2004-38107 A). However, this method has a problem in that usable dyes are limited to special dyes having sublimation properties, and the sublimated dyes adhere to areas other than the desired sites. Therefore, extra steps and special methods are required, such as masking places other than the desired part or limiting the dyeing part by applying an auxiliary agent such as a water-soluble polymer, which complicates the manufacturing process. Has inconvenience.

  Thus, in the method of dyeing an ophthalmic lens with a staining solution, a method capable of allowing a dye to permeate into the lens base material without generating a dye precipitate or residue on the lens surface of a dry ophthalmic lens Does not exist so far.

Japanese Patent Laid-Open No. 5-257096 Japanese Patent Publication No. 64-10045 JP-A 63-264719 JP-A-4-270312 Japanese Patent Application Laid-Open No. 8-112666 JP 2004-38107 A

  The present invention has been made to solve the above-described disadvantages. That is, the object of the present invention is to allow the dye to penetrate into the lens substrate easily and reliably without generating almost any dye precipitate or residue on the lens surface with respect to the dry ophthalmic lens. A method for producing a dyed ophthalmic lens that does not require a step of swelling an ophthalmic lens in advance before dyeing, a step of washing and removing a lens surface convexity after dyeing, and the like for a dyed eye Is to provide a lens.

  As a result of diligent research, the inventors of the present invention generate almost dye precipitates and residues on the lens surface by applying heat to the ophthalmic lens when the dyeing solution is brought into contact with the dry ophthalmic lens surface. The present invention was completed by discovering that the dye can be permeated without any problems.

The invention made to solve the above problems is
[A] A method for producing a dyed eye lens using a dye solution containing a dye and a [B] medium,
A contact step of bringing the dye solution into contact with the dry ophthalmic lens surface;
It has the heat provision process which provides a heat | fever to the said ophthalmic lens before the said contact process and / or simultaneously with a contact process.

  According to the method for producing a dyed ophthalmic lens, the dye can be penetrated by applying heat to the ophthalmic lens before and / or at the same time as the dyeing solution is brought into contact with the dry ophthalmic lens surface. From the initial stage, the penetration rate of the dye into the lens base material is improved, and since the solubility of the dye in the dyeing solution is ensured, almost no dye deposits or residues are generated on the lens surface. The dye can surely penetrate into the lens substrate. Therefore, according to the method for producing a dyed eye lens, it is possible to obtain a safe and highly reliable dyed eye lens that has almost no convex portions made of dye deposits and residues on the lens surface. In addition, according to the method for manufacturing a dyed eye lens, since the generation of dye precipitates and residues can be suppressed, there is no need for a cleaning step for removing these after dyeing or a step for smoothing the convex portion. It becomes. Therefore, a dyed eye lens can be provided easily and inexpensively. Furthermore, according to the method for producing a dyed eye lens, since a dry ophthalmic lens can be dyed, a step of previously swelling the ophthalmic lens is not required, and the dyed eye lens production process is eliminated. Can be greatly simplified. Further, since the diffusion rate of the dye molecules inside the lens base material is increased from the initial stage of penetration of the dye, a dyed print with sharper and no bleeding can be obtained.

  It should be noted that the precipitation of the dye and the generation of residues are suppressed by applying heat to the ophthalmic lens in the above stage when the staining solution is brought into contact with the lens surface, so that the ophthalmic lens itself and the staining solution adhering to the lens surface can be prevented. It is considered that the temperature is achieved when the temperature becomes a certain value or more from the initial stage of dye penetration. That is, since the temperature of the lens base material itself is a certain value or more from the initial stage of dye penetration, the diffusion coefficient of the dye in the lens base material increases and the penetration speed into the base material is improved. Generation | occurrence | production of the residue of the dye in the surface is suppressed effectively. In addition, the dye in the dyeing liquid that occurs because the temperature of the dyeing liquid adhering to the lens surface exceeds a certain value from the initial stage of its penetration, so that the medium molecules penetrate faster into the lens substrate than the dye molecules. Even when the concentration is increased, the dye solubility is ensured by increasing the saturation solubility of the dye, so that the precipitation of the dye is effectively suppressed. It is considered that the penetration of the dye into the lens base material is surely achieved by synergistic effects of both of these, with almost no dye deposits or residues on the lens surface.

  In the method for manufacturing a dyed eye lens, the heat application step may be further provided after the contact step. A stage in which penetration has progressed from the initial stage of penetration of the dye by having the heat application to the ophthalmic lens before and / or simultaneously with the contact process and further after the contact process. Up to a certain value. As a result, the penetration of the dye into the lens base material is continuously promoted and the solubility of the dye in the staining solution on the lens surface is continuously improved, so that the precipitation of the dye and the generation of residues are further reduced. .

  In the method for producing a dyed eye lens, the temperature of the ophthalmic lens at the end of the contact step is preferably 30 ° C. or higher and 90 ° C. or lower. By setting the temperature of the ophthalmic lens at the end of the contact step within the above range, further promotion of penetration of the dye molecules into the lens base material and securing of the solubility of the dye in the dyeing solution adhering to the lens surface are further achieved. This can be achieved effectively and without affecting the ophthalmic lens, and the precipitation of dye and the generation of residues are further suppressed. In addition, the dye molecules can be penetrated into the ophthalmic lens base material particularly effectively to obtain a dyed printed matter that is very sharp and has little bleeding.

  In the method for producing a dyed ophthalmic lens, it is preferable that the equilibrium swelling degree of the ophthalmic lens with the medium [B] is 40% or more and 600% or less. Since the equilibrium swelling degree of the material constituting the ophthalmic lens by the [B] medium in the dyeing liquid is in the above range, the penetration speed of the dye molecule to the ophthalmic lens in the dry state is improved. Precipitation and generation of residues can be further suppressed.

  In the method for manufacturing a dyed eye lens, the contact step may be performed by an ink jet coating apparatus. By bringing the staining solution into contact with the ophthalmic lens surface using an ink jet coating apparatus, a fine dyed printed matter can be accurately and very simply formed on the ophthalmic lens surface.

In the method for producing the dyed eye lens,
The dyeing solution further includes a [C] radical polymerization initiator,
[A] The dye of the component is a dye having at least one group having a carbon-carbon double bond in the molecule;
The medium of the [B] component has at least one [B1] solvent and / or [B2] radical polymerizable group capable of dissolving at least a part of each of the above [A] component and [C] component in the molecule. One monomer,
In order to polymerize the staining solution that has permeated the ophthalmic lens after the contact step and after the heat application step, it is preferable to further include a fixing step of imparting active energy rays and / or heat to the permeated staining solution.

  The dyeing solution used in the method for producing a dyed eye lens dissolves a dye having at least one group having a carbon-carbon double bond in the molecule, a radical polymerization initiator, and at least a part of each of them. And a monomer having at least one radically polymerizable group in the molecule, and the permeation at the stage where the dyeing solution has penetrated after the contact step and after the heat application step. By applying active energy rays and / or heat to the dyed dyeing solution, it is possible to give extremely excellent dissolution resistance to the ophthalmic lens, forming a dyed print that is semi-permanently stable and almost free from dissolution. can do. The dyed printed matter formed from such a dyeing solution has extremely high durability because the dye does not elute even when swollen with water, boiled, or washed. Such excellent elution resistance is due to the fact that the carbon-carbon double bond of the dye molecule undergoes a radical reaction due to electromagnetic waves or heat and polymerizes in the polymer network structure constituting the ophthalmic lens, or for ophthalmic use. It is considered that this dye molecule is firmly fixed on the ophthalmic lens by graft reaction with the polymer of the lens. This fixing effect is similarly obtained for an ophthalmic lens that does not have a group capable of reacting with a reactive dye. Therefore, according to the method for producing a dyed eye lens, such a dyed eye lens having excellent elution resistance can be obtained with almost no dye deposition or residue on the lens surface. Further, by simply polymerizing and curing the staining solution by electromagnetic waves or heat using the staining solution, a dyed eye lens having excellent elution resistance can be obtained very simply.

  In the dye used in the method for producing a dyed eye lens, the group having a carbon-carbon double bond is selected from the group consisting of α, β-unsaturated carbonyl group, styryl group, vinylbenzyl group and allyl group. It is preferably at least one group. By selecting these groups as groups having a carbon-carbon double bond, it is possible to improve the printing characteristics on the ophthalmic lens and the elution resistance of the resulting stained ophthalmic lens.

  In the dye used in the method for producing a dyed eye lens, when the group having a carbon-carbon double bond is an α, β-unsaturated carbonyl group, this group is a (meth) acrylate group or (meth) acrylamide. It is preferably a group. By selecting these groups as a group having a carbon-carbon double bond, it is possible to further improve the printing characteristics on the ophthalmic lens and the elution resistance of the resulting stained ophthalmic lens.

  The staining solution used in the method for producing a dyed eye lens may further include [D] a surfactant. Since the dyeing solution further contains a surfactant, it is possible to improve the speed and uniformity of penetration of the dyeing solution into the ophthalmic lens substrate. Generation | occurrence | production can be suppressed further and it can obtain a sharp dyed printed matter with few blurs.

  In the method for producing a dyed eye lens, a contact lens can be used as the eye lens. Dye deposits and residues are hardly generated on the surface of a dyed contact lens obtained by the method for producing a dyed eye lens using a contact lens widely used for daily life. As a result, since there is almost no convex part on the lens surface and there is almost no possibility of peeling off, it is possible to provide a dyed contact lens that is safe and has high commercial value and reliability. Moreover, since extra steps such as washing and removing dye deposits and smoothing of the convex portions after the dyeing are not required, the manufacturing process is greatly simplified, and a product can be provided at low cost. Such an effect can be obtained similarly when a hydrous contact lens is used as a contact lens.

  In the method for producing a dyed eye lens, it is preferable to use a hydrous contact lens formed from a copolymer having a silicone compound as a constituent monomer unit. As described above, since the water-containing contact lens is formed of a copolymer having a silicone compound as a constituent monomer unit, high flexibility and oxygen permeability can be imparted to the contact lens.

  In the method for producing a dyed eye lens, an oxygen-permeable hard contact lens can be used as the ophthalmic lens that is a base material. Thus, even when an oxygen-permeable hard contact lens is used as an ophthalmic lens, an oxygen-permeable hard contact lens having high commercial value and reliability can be provided by this manufacturing method as described above. Can do.

  The dyed eye lens obtained by the method for producing a dyed eye lens does not have a convex portion due to the dye on the surface, and has a reduced physical or physiological effect on the eye. It is extremely safe and reliable as a lens. In addition, in the manufacturing process of such a dyed eye lens, an extra step such as a step of swelling the ophthalmic lens in advance before dyeing, a step of washing and smoothing the convex portion after dyeing is required. do not do. Therefore, the stained eye lens can be manufactured very simply and inexpensively.

  As described above, according to the method for producing a dyed ophthalmic lens of the present invention, a dye is added to a lens base material with little dye precipitate or residue on the lens surface of a dry ophthalmic lens. It can easily and reliably penetrate inside, and does not require extra steps such as the step of swelling the ophthalmic lens before dyeing, the step of washing and smoothing the convex parts after dyeing, and the like. An ophthalmic lens can be obtained.

2 is a stereoscopic microscope image of the dyed printed matter formed in Example 1. FIG. 3 is a stereoscopic microscope image of a dyed printed material formed in Example 2. FIG. It is a stereoscopic microscope image of the dyed printed matter formed in Example 3. It is a stereoscopic microscope image of the dyed printed matter formed in Example 4. 10 is a stereoscopic microscope image of a dyed printed material formed in Example 5. FIG. It is a stereoscopic microscope image of the dyed printed matter formed in Example 6. It is a stereoscopic microscope image of the dyed printed matter formed in Example 7. 10 is a stereoscopic microscope image of a dyed print formed in Example 8. FIG. 3 is a stereoscopic microscope image of a dyed printed material formed in Comparative Example 1. It is a stereoscopic microscope image of the dyed printed matter formed in Comparative Example 2. It is a stereoscopic microscope image of the dyed printed matter formed in Comparative Example 3. It is a stereoscopic microscope image of the dyed printed matter formed in the comparative example 4. 10 is a stereoscopic microscope image of a dyed printed material formed in Comparative Example 5.

  Hereinafter, embodiments of the present invention will be described in detail.

The method for producing the dyed eye lens of the present invention comprises:
[A] A method for producing a dyed eye lens using a dye solution containing a dye and a [B] medium,
A contact step of bringing the dye solution into contact with the dry ophthalmic lens surface;
It has the heat provision process which provides a heat | fever to the said ophthalmic lens before the said contact process and / or simultaneously with a contact process. Hereinafter, the ophthalmic lens, the staining solution, each step of the staining method, and the stained ophthalmic lens will be described in this order.

[Eye lens]
The ophthalmic lens used in the method for producing the dyed ophthalmic lens is a lens that enables correction of visual acuity, improved tonicity, etc. by being attached to a human eye, and is not limited to a contact lens, but an intraocular lens, The concept includes an artificial cornea, a corneal onlay, a corneal inlay, and the like. Such an ophthalmic lens is generally made of a polymer material having a crosslinked structure, and has a polymer network structure inside the lens. Examples of the contact lens include a hydrous contact lens that softens with water, a non-hydrous contact lens, a hard oxygen permeable contact lens, or a hybrid contact lens made of a combination thereof. As materials for these ophthalmic lenses, any known materials can be used. For example, polyhydroxyethyl methacrylate or the like can be used as the material of the hydrous contact lens.

  In the method for producing a dyed ophthalmic lens, when a hydrous contact lens is used as the ophthalmic lens, one formed from a copolymer having a silicone compound as a constituent monomer unit is preferably used. A hydrous contact lens formed of a copolymer having a silicone compound as a constituent monomer unit can impart high flexibility and oxygen permeability to the contact lens. Such a copolymer is not particularly limited. For example, a copolymer of a silicone compound monomer (or macromer) and a hydrophilic monomer can be used. Examples of the silicone compound monomer used include a compound having an ethylenically unsaturated group and a polydimethylsiloxane structure via a urethane bond, a silicone compound having a hydrophilic structure portion in the molecule, and a silicone-containing alkyl (meth) acrylate. And silicone-containing styrene derivatives and silicone-containing fumaric acid diesters.

  The ophthalmic lens used in the method for producing the stained ophthalmic lens is in a dry state. In the case of an ophthalmic lens in a swollen state, which has a low mechanical strength and is easily damaged, as in the conventional swelling method, it is necessary to use a special handling device or jig. According to the manufacturing method for an ophthalmic lens, it is possible to directly dye a dry ophthalmic lens, so that the process can be simplified and the productivity can be improved. Here, the dry ophthalmic lens refers to an ophthalmic lens that is not swollen and flexible, and includes those that do not contain a swellable medium or little. In the state usually called xerogel.

[Dyeing solution]
The dyeing solution used in the method for producing the dyed eye lens contains [A] dye and [B] medium. Moreover, as other components, [C] radical polymerization initiator, [D] surfactant, etc. may be included. Hereinafter, each component of the staining liquid will be described in order.

<[A] component: Dye>
The dye of the component [A] is a compound having a chemical structure that develops a specific color by absorbing or reflecting a part of visible light, and can be dissolved in the medium of the component [B] or [ Even if the dispersoid is not dissolved in the medium of component B], the dispersoid can be used without particular limitation as long as the dispersoid is smaller than the size of the polymer network constituting the ophthalmic lens.

  As the dye of component [A], a dye having a functional group capable of reacting with the polymer constituting the ophthalmic lens substrate to form a covalent bond is preferable. By having such a functional group, the dye molecule can be bonded to the polymer of the ophthalmic lens base material, and the dye can be fixed semi-permanently and stably in the lens, so that it has excellent elution resistance. A dyed print can be formed. Moreover, as a dye of [A] component, the dye which has a polymeric group in a molecule | numerator is also preferable. [A] When the dye of the component has a polymerizable group, even when the polymer constituting the ophthalmic lens substrate does not have a functional group capable of reacting with the dye molecule, the dye molecule undergoes addition polymerization or the like. When forming a polymer, an interpenetrating network structure is formed between the polymer network and a higher order structure is formed so that the dye cannot physically elute. It is possible to form a dyed printed matter that is extremely excellent in color. As the dye having such a polymerizable group, a dye having at least one group having a carbon-carbon double bond in the molecule is particularly preferable. By using a dye having such a group, in the presence of a radical polymerization initiator or the like, it is possible to easily perform bond formation by polymerization of the dye molecule or graft reaction to the ophthalmic lens base polymer. It is possible to form a dyed printed matter with extremely high elution properties.

  The group having a carbon-carbon double bond is preferably an α, β-unsaturated carbonyl group, a styryl group, a vinylbenzyl group or an allyl group. By using a dye having such a functional group, it is possible to improve the printing characteristics on the ophthalmic lens and the elution resistance of the resulting dyed ophthalmic lens.

  The α, β-unsaturated carbonyl group is preferably a (meth) acrylate group or a (meth) acrylamide group. When the group having a carbon-carbon double bond is these specific groups, it is possible to further improve the printing characteristics on the ophthalmic lens and further improve the elution resistance of the dyed printed matter obtained. . The styryl group may be a styryl group having no substituent or a styryl group having a substituent such as an α-methyl group. The vinylbenzyl group may be any of o-, m- and p-vinylbenzyl groups.

  The dye having at least one (meth) acrylate group in the molecule is not particularly limited. For example, 1-phenylazo-4-acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3-acryloyloxynaphthalene, 1-naphthylazo 2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- (α-anthrylazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-((4-phenylazo) phenyl) azo-2-hydroxy -3-acryloyloxynaphthalene, 1- (2 ′, 4′-xylylazo) -2- (meth) acryloyloxynaphthalene, 1- (o-tolylazo) -2- (meth) acryloyloxynaphthalene, 2,4-dihydroxy -3- (p- (meth) acryloyloxy Tilphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-3- (p- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-3- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy- 5- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-5- (o- ( (Meth) acryloyloxymethyl Phenylazo) benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-5- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2, 4-dihydroxy-3- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-5- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-3- (P- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (pN, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2 , 4-Dihydroxy-3- (o N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (o- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4- Dihydroxy-3- (p- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (p- (N-ethyl-N- (meth) acryloyloxyethyl) Amino) phenylazo) benzophenone, 2,4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (o- (N- Ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzo And the like can be given Enon.

  As another example of the dye having at least one (meth) acrylate group in the molecule, 1-((4- (phenylazo) phenyl) azo) -3-methacryloyloxy-2 represented by the following formula (1) -Naphthol, 1-phenylazo-3-methacryloyloxy-2-naphthol represented by the following formula (2), 1-phenylazo-4-methacryloyloxy-naphthalene represented by the following formula (3), the following formula (4) 2,4-dihydroxy-5- (4- (2- (N- (2-methacryloyloxy) ethyl) carbamoyloxyethyl) phenylazo) benzophenone represented by the formula:

  Although it does not specifically limit as a dye which has at least one (meth) acrylamide group in a molecule | numerator, For example, tetra- (4-methacrylamide) copper phthalocyanine represented by following formula (5), tetra- (methacrylamide) dodecanoyl Examples include copper phthalocyanine.

  The dye having at least one styryl group in the molecule is not particularly limited. For example, 1- (ethenylphenyl) amino-anthraquinone, 1,4-bis ((ethenylphenyl) represented by the following formula (6): ) Amino) -anthraquinone, 1,8-bis ((ethenylphenyl) amino) -anthraquinone represented by the following formula (7), 1- (ethenylphenyl) amino-4-hydroxyanthraquinone, 1- (ethenyl) And phenyl) amino-4- (4-methylphenyl) amino-anthraquinone.

  The dye having at least one vinylbenzyl group in the molecule is not particularly limited, and examples thereof include 1,4-bis ((vinylbenzyl) amino) -anthraquinone.

  The dye having at least one allyl group in the molecule is not particularly limited. For example, 1- (4-allyloxymethylphenyl) amino-4-hydroxyanthraquinone represented by the following formula (8), and the following formula (9) 1- (4-allyloxyethylphenyl) amino-4-hydroxyanthraquinone represented by the formula, 1,4-bis ((4-allyloxyethylphenyl) amino) -anthraquinone represented by the following formula (10) Can do.

  When using a dye having at least one group having a carbon-carbon double bond in the molecule, an amount of a non-reactive dye (for example, “D & C Green No. 6” or the like which does not inhibit the above effect). “D & C Red No. 17”) may be used in combination.

  The dye of the component [A] is an azo dye, anthraquinone dye, nitro dye, phthalocyanine dye from the viewpoint of the chemical structure of the dye that develops a specific color by absorbing or reflecting a part of visible light. Quinoneimine dyes, quinoline dyes, carbonyl dyes, triarylmethane dyes, methine dyes, and the like.

  The ratio of the [A] component dye used in the staining liquid is not particularly limited, but is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total of the component [B] medium. More preferably, it is 5 parts by mass or more and 5 parts by mass or less. By setting the use ratio of the component [A] to 0.1 part by mass or more, sufficient visibility of the obtained dyed printed matter can be obtained. By making the use ratio of the component [A] 10 parts by mass or less, it is possible to reduce the generation of undissolved parts in the dyeing solution, and to induce unevenness of penetration into the ophthalmic lens due to excess of the dye and to it. Occurrence of stained unevenness (deterioration of appearance when a lens is mounted) can be prevented. [A] Dye of a component may be single type, or may mix and use multiple types.

<[B] component: medium>
The medium for the component [B] is not particularly limited as long as it is a liquid capable of dissolving and / or dispersing the dye of the component [A]. As a medium for the component [B], as long as it is a compound having such properties, a radically polymerizable group in addition to a liquid usually used as a solvent (hereinafter also referred to as “solvent” (component [B1])). A monomer having at least one in the molecule (hereinafter also referred to as “radical polymerizable monomer” (component [B2])) may be used.

([B1] component: solvent)
[B1] As a representative solvent of the component,
water;
Alcohols such as methanol, ethanol, propanol, glycerol, trifluoroethyl alcohol, hexafluoroisopropyl alcohol;
Ketones such as methyl ethyl ketone and acetone;
Aromatic hydrocarbon solvents such as toluene, benzene, xylene;
Chain aliphatic hydrocarbon solvents such as hexane and octane;
Cycloaliphatic hydrocarbon solvents such as cyclohexane and decalin;
Ester solvents such as ethyl acetate and methyl acetate;
Ether solvents such as diethyl ether and tetrahydrofuran;
Halogenated carbon solvents such as chloroform, methylene chloride, carbon tetrachloride, and chlorofluorocarbons;
Amide solvents such as dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, N, N-dimethylacetamide;
Other examples include water containing an electrolyte salt such as dimethyl sulfoxide and sodium chloride.
As the solvent for the component [B1], one type may be used alone, or a plurality of types may be used in combination.

([B2] monomer having at least one radical polymerizable group in the molecule)
[B2] In the monomer having at least one radical polymerizable group in the molecule, the “radical polymerizable group” means an unsaturated group capable of radical polymerization. By using the radically polymerizable monomer of the component [B2] as the medium of the component [B], the radically polymerizable monomer of the component [B2] that has penetrated into the ophthalmic lens substrate together with the dye of the component [A] The polymer produced by the polymerization of the polymer encloses the dye, and an interpenetrating network structure is formed between the polymer of the lens base polymer and the polymer. As a result, it is possible to physically fix the dye molecules inside the lens base material and prevent them from eluting out of the ophthalmic lens. In addition, when the dye of the component [A] has a radically polymerizable group such as a carbon-carbon double bond, the dye molecule and the radically polymerizable monomer can be copolymerized to form each other. Dye molecules are more firmly fixed in the intrusion network structure or fixation by graft reaction with the ophthalmic lens base polymer. Becomes even higher.

As an example of the radically polymerizable monomer of the component [B2],
Unsaturated group-containing carboxylic acids such as methacrylic acid and acrylic acid;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n- Pentyl (meth) acrylate, t-pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) Alkyl (meth) acrylates such as acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate;
Alkoxy group-containing (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and methoxydiethylene glycol (meth) acrylate;
Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dihydroxypropyl (meth) acrylate, dihydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate Hydroxy group-containing (meth) acrylates such as dipropylene glycol mono (meth) acrylate and glycerol (meth) acrylate;
Styrene, pentafluorostyrene, o, m, p-methylstyrene, α-methylstyrene, trimethylstyrene, trifluoromethylstyrene, (pentamethyl-3,3-bis (trimethylsiloxy) trisiloxanyl) styrene, (hexamethyl-3-trimethyl) Styrene derivatives such as siloxytrisiloxanyl) styrene and dimethylaminostyrene;
Carbon-carbon unsaturated group-containing lactams such as N-vinyl-2-pyrrolidone, 1-methyl-3-methylene-2-pyrrolidinone, N-vinylcaprolactam, N- (meth) acryloylpyrrolidone;
(Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (Meth) acrylamides such as N-ethyl-N-aminoethyl (meth) acrylamide;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 4-vinylbenzyl (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Allyl (meth) acrylate, vinyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, methacryloyloxyethyl acrylate, divinylbenzene, diallyl phthalate, diallyl adipate, triallyl isocyanurate, α-methylene-N-vinylpyrrolidone, etc. Multifunctional monomers having two or more unsaturated groups of
Pentamethyldisiloxanylmethyl (meth) acrylate, pentamethyldisiloxanylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate, mono ( Methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris (methylbis (trimethylsiloxy) siloxy) silylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropylglyceryl (meth) acrylate, tris ( Trimethylsiloxy) silylpropylglyceryl (meth) acrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) Rupropylglyceryl (meth) acrylate, trimethylsilylethyltetramethyldisiloxanylpropylglyceryl (meth) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, trimethylsilylpropyl glyceryl (meth) acrylate, pentamethyldisiloxa Nylpropylglyceryl (meth) acrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxanylmethyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxybis Silicon-containing (meth) acrylates such as (trimethylsiloxy) silylpropyl (meth) acrylate Door like;
Trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, pentafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, tetrafluoro-t-pentyl (meth) acrylate, hexafluorobutyl (meth) acrylate , Hexafluoro-t-hexyl (meth) acrylate, octafluoropentyl (meth) acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl (meth) acrylate , Dodecafluoroheptyl (meth) acrylate, 2-hydroxyoctafluoro-6-trifluoromethylheptyl (meth) acrylate, 2-hydroxydodecafluoro-8-trifluoromethylnonyl (meth) acrylate DOO, fluorine-containing (meth) acrylates such as 2-hydroxy-hexadecafluoro-10-trifluoromethyl undecyl (meth) acrylate;
Aminoalkyl (meth) acrylates such as aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate;
Aromatic ring-containing (meth) acrylates such as benzyl (meth) acrylate;
Alkyl esters optionally substituted with alkyl groups, fluorine-containing alkyl groups, siloxanyl alkyl groups, such as itaconic acid, crotonic acid, maleic acid, fumaric acid;
Examples include heterocyclic N-vinyl monomers such as vinylimidazole, N-vinylpiperidone, N-vinylpiperidine, and N-vinylsuccinimide.

Among the radically polymerizable monomers of the component [B2], from the viewpoint of radical polymerization reactivity and availability, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, ethylene glycol di (meth) acrylate, 4- Vinylbenzyl (meth) acrylate, dodecyl (meth) acrylate, 1-methyl-3-methylene-2-pyrrolidinone, methyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate, glycerol (meth) acrylate, methoxy Ethyl (meth) acrylate, styrene, N, N-dimethyl (meth) acrylamide, ethyl (meth) acrylate, butyl (meth) acrylate, and N-vinyl-2-pyrrolidone are preferred.
As the radically polymerizable monomer of the component [B2], one type may be used alone, or a plurality of types may be used in combination.

  In the case where a liquid monomer is used as the radical polymerizable monomer of the component [B2], the dye of the component [A] and the radical polymerization initiator of the component [C] described later are included in the liquid monomer. When it can be dissolved, the dye liquid can be formed using the radically polymerizable monomer of the component [B2] without using the solvent of the component [B1] as the medium of the component [B]. In the dyeing solution, a solvent of the component [B1] and a radical polymerizable monomer of the component [B2] can be used in combination as the medium of the component [B].

  As the medium for the component [B], a medium that can swell the polymer network constituting the ophthalmic lens substrate is suitably used. Such a medium cannot be generally defined because the swelling behavior of the polymer network by the medium depends on the type of the ophthalmic lens base polymer and the form of the polymer aggregate structure. A medium capable of dissolving the linear polymer chain constituting the crosslinked structure of the molecule, a medium having a chemical structure similar to the repeating unit of the base polymer, a medium capable of solvating with the base polymer, a polar group And a medium having a ring structure. When the polymer constituting the ophthalmic lens substrate is formed from a copolymer having a silicone compound as a constituent monomer unit, such a polymer generally has an amorphous structure. In many cases, a medium whose chemical structure is not similar to that of the polymer can be preferably used.

  As a specific example of the medium that can swell such a lens base polymer, for example, when the ophthalmic lens base is polymethyl methacrylate, methyl ethyl ketone or the like having a chemical structure similar to the repeating unit of the base polymer is used. Ketones; esters such as ethyl acetate; cyclic amides such as N-methyl-2-pyrrolidone; cyclic ethers such as tetrahydrofuran.

The equilibrium swelling degree is used to represent such swelling behavior. The lower limit of the degree of equilibrium swelling of the ophthalmic lens with the medium of component [B] is preferably 40%, more preferably 70%, and even more preferably 100%. On the other hand, the upper limit of the equilibrium swelling degree of the ophthalmic lens with the medium of component [B] is preferably 600%, more preferably 500%, and even more preferably 400%. If the equilibrium swelling degree of the ophthalmic lens by the medium of the component [B] is smaller than the lower limit, the penetration rate of the dye solution into the ophthalmic lens is lowered, and there is a possibility that it takes a long time for dyeing. On the contrary, if the equilibrium swelling degree exceeds the above upper limit, the penetration of the medium becomes too fast and bleeding or the like tends to occur, and there is a possibility that a sharp and good dyed printed matter cannot be obtained. Here, the equilibrium swelling degree of the ophthalmic lens with the medium of the component [B] is that the dry ophthalmic lens is immersed in the medium for 24 hours at 25 ° C. to swell, and the ophthalmic lens has a dry mass (W1). ) And the value of the swollen mass (W2), which is a value calculated by the following formula (1).
Equilibrium swelling rate (%) = (W2−W1) × 100 / W1 (1)

  The medium for the component [B] is preferably a medium that does not volatilize easily even if it adheres to the surface of the ophthalmic lens whose temperature has been raised by the heat application step described later. Such a medium depends on the set temperature value in the heat application step, and thus cannot be defined unconditionally. Usually, the boiling point in the standard state is preferably 50 ° C or higher, more preferably 60 ° C or higher, and 70 ° C. The above is more preferable.

  The dyeing solution comprises a dye having at least one group having a radical polymerizable group such as a carbon-carbon double bond in the molecule as the [A] component and / or a radical polymerizable monomer of the [B2] component. (They are also referred to as “radical polymerizable compounds” hereinafter), and when the radical polymerization initiator of the later-described [C] component is further contained, as the medium for the [B] component, the [A] component and the [C] It is preferably a liquid that can dissolve at least a part of each of the components. In that case, the medium of the component [B] is more preferably a liquid that can dissolve substantially all of the component [A] and the component [C].

  In the dyeing solution, the solvent used as the component [B1] and the radical polymerizable monomer used as the component [B2] are not particularly limited in terms of the ratio of use and the ratio of both. For example, the usage ratio when using the [B1] component in the staining solution is 0.1 mass% or more and 99.8 mass% or less, and the usage ratio when using the [B2] component is 1 mass% or more and 99.8 mass%. It can be as follows.

<[C] component: radical polymerization initiator>
When the dyeing liquid contains the radical polymerizable compound, the dyeing liquid is allowed to contain a radical polymerization initiator in order to polymerize and harden the dyeing liquid after contacting and penetrating the lens surface. The radical polymerization initiator of component [C] is a compound that generates radicals (free radicals) by applying active energy rays (light rays (electromagnetic waves) such as ultraviolet light and visible light) or heat, and the dye itself Or the radical polymerization of the above-mentioned dye with a radical polymerizable monomer. The radical polymerization initiator is not particularly limited as long as it has the properties defined as described above.

Specific examples of radical polymerization initiators that are cleaved by active energy rays include:
Phosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TMDPO) and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; methyl orthobenzoylbenzoate, methylbenzoylformate Benzoin photopolymerization initiators such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether; 2-hydroxy-2-methyl-1-phenylpropan-1-one, p-isopropyl-α- Hydroxyisobutylphenone, pt-butyltrichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, N, N-tetraethyl-4,4-diaminobenzophenone, 4,4′-bi Phenone photopolymerization initiators such as dimethylaminobenzophenone; 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1- (4-isopropylphenyl)- Ketone photopolymerization initiators such as 2-hydroxy-2-methylpropan-1-one; thioxanthone photopolymerization initiators such as 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone; benzylmethyl ketal, benzyldimethyl ketal, Ketal photopolymerization initiators such as acetophenone diethyl ketal; other examples include dibenzosperone, benzophenone, and benzyl.

As a specific example of a radical polymerization generator that is cleaved by heat,
2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, t- Examples include butyl peroxyhexanoate and 3,5,5-trimethylhexanoyl peroxide.

  Although the usage-amount of the radical polymerization initiator of the [C] component in the said dyeing | staining liquid is not specifically limited, It is 0.1 to 20 mass parts with respect to 100 mass parts of medium of a [B] component. Preferably, it is 0.5 parts by mass or more and 15 parts by mass or less. By setting the use ratio of the component [C] to 0.1 part by mass or more, the radical polymerization reactivity of the radical polymerizable compound is maintained at a high level, and it is caused by elution of the dye not fixed on the ophthalmic lens. Lightening can be suppressed. By making the use ratio of the component [C] 20 parts by mass or less, the residual amount of the radical polymerization initiator in the ophthalmic lens base material is reduced, the safety is improved, and the radical polymerization initiator for the ophthalmic lens is increased. Can be prevented and uneven dyeing induced thereby. As the radical polymerization initiator of the component [C], one type may be used alone, or a plurality of types of compounds may be used in combination.

<D component: Surfactant>
The surfactant of the component [D] can be used for more smoothly penetrating the dye solution into the ophthalmic lens base material and for preventing bleeding of the dyed print formed from the dye solution. Furthermore, the surfactant has an action of stabilizing micelles in the dyeing liquid described later. Such a surfactant is used in a state of being dissolved or emulsified in a staining solution.

As a specific example of the surfactant of [D] component,
Polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene-polyoxypropylene block copolymer and its derivatives, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene sorbitan monooleate, polyoxyethylene cured Nonionic surfactants such as castor oil (eg, polyoxyethylene hydrogenated castor oil), polyoxyethylene alkyl ether carboxylic acid and salts thereof;
Anionic surfactants such as fatty acid salts, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl acetates, alkylbenzene sulfonates;
Cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts;
Examples include amphoteric surfactants such as sodium alkylamino fatty acid, alkylbetaine, and alkylcarboxybetaine.
Among these surfactants, polyoxyethylene hydrogenated castor oil is most preferable from the viewpoint of the permeability of the dye solution into the ophthalmic lens substrate.

  Although the usage-amount of surfactant of [D] component in the said dyeing | staining liquid is not specifically limited, It is preferable to set it as 0.001 mass% or more and 5 mass% or less. By making the use ratio of the component [D] 0.001% by mass or more, the permeability of the dyeing liquid can be effectively increased and the occurrence of bleeding of the dyed printed matter can be suppressed. The proportion of component [D] used is more preferably 0.01% by mass or more. On the other hand, by setting the usage ratio of the [D] component to 5% by mass or less, it is possible to maintain the uniformity of the dyed printed matter obtained by preventing the precipitation of the [D] component and to overuse the [D] component. The uneconomical due to can be prevented. The proportion of component [D] used is more preferably 2% by mass or less. As the surfactant for component [D], one type may be used alone, or a plurality of types may be used in combination.

  The dyeing solution is prepared by mixing an appropriate amount of the above-described dye of [A], the medium of [B], and, if necessary, other components such as [C] radical polymerization initiator and [D] surfactant. Prepared by The order of mixing these components is not particularly limited.

  The form of the staining solution is preferably a uniform solution. Since the dyeing solution is a uniform solution as described above, the dyeing solution can easily and uniformly penetrate into the ophthalmic lens, so that a better dyed printed matter can be obtained. In addition, clogging in the discharge nozzle can be effectively prevented during printing on an ophthalmic lens using an ink jet coating apparatus described later. The “homogeneous solution” as used herein is preferably a state in which the dye is dispersed and dissolved in a molecular form in the dyeing solution, but in a state where at least a part of the dye forms aggregates such as micelles. Included. However, the agglomerates such as micelles here are of a size that can pass through the polymer network formed in the base of the ophthalmic lens so as to penetrate into the ophthalmic lens. It is preferable. The size of the agglomerates such as micelles depends on the type and size of the polymer network constituting the ophthalmic lens material, and thus cannot be defined unconditionally, but the average upper limit is 500 to 600 nm. Is preferred.

  Next, each process of the manufacturing method of the dyed eye lens of this invention is demonstrated. The method for manufacturing a dyed eye lens includes a heat application step and a contact step.

[Heat application process]
In the heat application step, heat is applied to the ophthalmic lens. Heat may be applied to the entire ophthalmic lens, or heat may be applied only to the vicinity of the portion where the ophthalmic lens is dyed. The stage of the heat application process refers to a period during which heat is applied to the ophthalmic lens by a method such as heating described later.

  The method for applying heat is not particularly limited as long as the method can increase the temperature of the ophthalmic lens. For example, a method of standing an ophthalmic lens in a high-temperature place using a thermostat, a method of heating an ophthalmic lens using a heating element such as a heater or an incandescent bulb, irradiation that generates electromagnetic radiation such as far infrared rays Examples thereof include a method of irradiating an ophthalmic lens using an apparatus and a method of supplying warm air to an ophthalmic lens using a dryer. In any case, it is preferable to set and maintain the temperature of the ophthalmic lens at a desired value, or to change the temperature control by programming as necessary. With this configuration, the dyeing quality can be kept constant, and by controlling the temperature of the ophthalmic lens precisely, the generation of dye deposits and residues on the lens surface can be more effectively suppressed. be able to.

  The temperature of the ophthalmic lens reached by the heat application step is not particularly limited, but the lower limit of the ophthalmic lens temperature at the end of the heat application step is preferably 50 ° C, more preferably 60 ° C, and even more preferably 70 ° C. . On the other hand, the upper limit of the ophthalmic lens temperature at the end of the heat application step is preferably 150 ° C, more preferably 135 ° C, and even more preferably 120 ° C. If the ophthalmic lens temperature at the end of the heat application step is lower than the lower limit, the permeation rate of the dye solution into the ophthalmic lens substrate may be reduced, and the dyeing may take a long time. Conversely, when the temperature of the ophthalmic lens at the end of the heat application step exceeds the above upper limit, the ophthalmic lens substrate may be deformed.

  Moreover, as a minimum of the temperature of the ophthalmic lens at the time of completion | finish of the below-mentioned contact process, 30 degreeC is preferable, 40 degreeC is more preferable, and 50 degreeC is further more preferable. On the other hand, the upper limit of the temperature of the ophthalmic lens at the end of the contacting step is preferably 90 ° C, more preferably 75 ° C, and even more preferably 60 ° C. If the temperature of the ophthalmic lens at the end of the contacting step is lower than the lower limit, the diffusion rate of the dye inside the lens base material is lowered, so that there is a possibility that a dyed printed matter with sharpness and little bleeding cannot be obtained. On the contrary, if the temperature of the ophthalmic lens at the end of the contact process exceeds the upper limit, the penetration of the dye into the lens base material becomes non-uniform, and there is a possibility that a homogeneous dyed printed matter cannot be obtained. In these cases, the temperature of the ophthalmic lens refers to the temperature of the lens surface in the vicinity of the place where the staining solution has adhered.

  The time for applying heat is not particularly limited and can be appropriately set according to the heat application method and the desired temperature reached by the ophthalmic lens, but is preferably 10 minutes or less, more preferably 5 minutes or less, and 3 minutes. More preferred are: When the time for applying heat exceeds 10 minutes, the work time in the process becomes long, which may lead to a decrease in productivity and an increase in cost.

[Contact process]
In the contact step, the dyeing solution is brought into contact with the dried ophthalmic lens surface. The contact process refers to the period from the start to the end of the dye solution contact operation such as coating on the ophthalmic lens to be dyed.

  As a method of bringing the staining solution into contact with the ophthalmic lens surface, various known methods such as a method of applying the staining solution to the ophthalmic lens surface and a method of immersing the ophthalmic lens in the staining solution can be used. As a method for applying the staining liquid to the ophthalmic lens surface, for example, a pad printing method, a screen printing method, a method using an ink jet coating apparatus, or the like can be used. Among these, a method using an ink jet coating apparatus is particularly preferable from the viewpoint of easily printing a desired character, numeral, or figure pattern. The inkjet coating apparatus sprays the dyeing liquid on the lens surface as very fine droplets. The droplets deposited on the surface form one dot, and a desired character, number, A graphic pattern can be formed. In general, letters, numbers, and figures when small dots are gathered at high density give sharp contrast and become excellent visibility marks. When printing and drawing with an ink jet coater, the size of the droplets and the point where the droplets land can be accurately controlled by a computer, etc., and easily by changing the computer program It is possible to change the shape and size of the mark. As described above, the coating method using the ink jet coating apparatus has an excellent advantage that the productivity is very high and the printing of a constant high quality can be performed. Furthermore, according to the ink jet type coating apparatus, the applied droplets are very small, and the amount of droplets is small compared to the interface area when landing on the lens substrate, so that it is easier to penetrate more quickly. Therefore, in addition to the above-described advantages, the ink jet coating apparatus can be said to be a more advantageous method for further penetrating the dye into the lens base material by further reducing the precipitation of the dye on the lens surface and the generation of residues.

  Any known ink jet coating apparatus can be used as the ink jet coating apparatus. A typical ink jet coating apparatus is composed of a dyeing liquid supply system and a discharge device composed of a nozzle equipped with a piezoelectric element such as a piezo element, and the dyeing liquid is generated by vibration generated by applying a voltage to the piezoelectric element. It has a mechanism for discharging from the nozzle as fine droplets. Any ink jet coating apparatus can be suitably used as long as it can eject a desired droplet. There may be a single nozzle or a plurality of nozzles. The discharge device with a plurality of nozzles is capable of simultaneously discharging dyeing liquids containing different dyes, has excellent characteristics such as excellent color gradation, and provides high-quality multicolor printing at high speed. It can be carried out. An ink jet coating apparatus having such a plurality of nozzles can also be suitably used. When performing such multicolor printing, each storage tank is filled with two or more types of dyeing liquids containing dyes of different tones, and various dyeing liquids are ejected to desired positions by a scanning method programmed by a computer or the like. By doing so, a dyed printed matter can be obtained.

  The time required for the contact process varies depending on the method of contacting the dyeing liquid, the area and shape of the dyed printed matter to be formed, the size of the ophthalmic lens, etc., but for example, when using an ink jet coating apparatus, usually several seconds to 10 minutes Degree.

[Relationship between contact process and heat application process]
In the method for producing a dyed eye lens of the present invention, the heat application step is performed before the contact step and / or simultaneously with the contact step. That is, the heat application step is performed 1) before, 2) simultaneously, 3) before and simultaneously with the contact step. Among these, 1) before or 3) before and simultaneously are preferable, and 3) before and simultaneously are more preferable. Although it may be at any stage, by providing a heat application process before the contact process, the temperature of the lens substrate can be set to a certain value or more from the initial stage of dye penetration, and the dyeing solution adhered to the lens surface The temperature can be effectively increased. As a result, the penetration of the dye into the lens base material is promoted from the initial stage of the dye penetration, and the solubility of the dye in the dyeing solution on the lens surface is improved, so that the precipitation of the dye on the lens surface and the generation of residues Is further reduced. At the same time, since the temperature of the lens base material becomes a certain value or more from the initial stage of penetration, the diffusion speed of dye molecules inside the lens base material becomes higher, and a dyed print with sharper and less bleeding can be obtained. .

  In the method for producing a dyed ophthalmic lens, by providing the heat application step at the above stage with respect to the contact step, the dyeing solution is formed inside the lens base material with almost no precipitation or residue of the dye on the ophthalmic lens surface. Can be easily and reliably permeated. The reason can be considered as follows. That is, by applying heat to the ophthalmic lens before the contact step, the temperature of the dye solution adhering to the lens surface as well as the temperature of the ophthalmic lens itself can be increased to a certain value from the initial stage of dye penetration. . As a result, the molecular movement of the polymer network constituting the lens base material becomes active, the diffusion coefficient of the dye molecules in the lens base material increases, and the penetration speed of the dye molecules into the lens base material increases. Residual dye on the lens surface is suppressed, and generation of residue is suppressed. On the other hand, in general, the medium molecule has a faster penetration rate into the lens substrate than the dye molecule, so in the droplet of the dyeing liquid adhering to the lens surface, the dye concentration increases with time. There is a risk of precipitation of the dye. However, when the temperature of the droplet is a certain value or more from the initial stage of its penetration, the saturation concentration at which the dye molecules can be dissolved, aggregated or associated in the medium increases, so that the dissolved state of the dye can be continued. And the precipitation of the dye is suppressed. In this way, by applying heat from the stage before the contact process, the synergistic effect of the diffusion promotion of the dye molecules and the improvement of the solubility of the dye, almost no precipitation or residue of the dye on the lens surface, It is believed that reliable penetration of the dye can be achieved.

  It is preferable to have the said heat provision process further after the said contact process. That is, it is preferable to perform the heat application step either a) before and after, b) simultaneously and after, or c) before, simultaneously and after the contacting step. By applying heat to the ophthalmic lens also in a stage after the contact step, the temperature of the lens base material can be kept above a certain value from the initial stage of penetration of the dye to the stage of penetration. . As a result, the penetration of the dye into the lens base material is continuously promoted, the solubility of the dye in the dyeing solution on the lens surface is continuously improved, and the precipitation of the dye and the generation of residues are further reduced. Among these, a) before and after, or c) before, at the same time and after is preferable, and c) before, at the same time and after is particularly preferable from the viewpoint of obtaining a sharp and dyed printed matter with less bleeding.

[Fixing process]
When the staining solution has the radical polymerizable compound and contains the radical polymerization initiator of the component [C], the staining solution that has penetrated into the ophthalmic lens is polymerized after the contact step and after the heat application step. Therefore, it is preferable to have a fixing step of applying active energy rays and / or heat to the ophthalmic lens. By having such a fixing step, after the dyeing solution has permeated into the ophthalmic lens, it is possible to form a dyed printed matter having very excellent elution resistance by polymerization and curing. The time required for the dyeing solution to permeate depends on a number of factors such as the components and the ratio of the dyeing solution and the temperature in the heat application step, but is, for example, 10 seconds to 20 minutes.

  In the fixing step, radical polymerization and curing are performed by applying energy to the dyeing solution containing the radical polymerizable compound that has permeated the ophthalmic lens, and the cured product is fixed to the ophthalmic lens. Such polymerization and curing are started by generating radicals (free radicals) from the radical polymerization initiator by applying energy. As a form of such an energy addition method, any one of active energy rays (light rays (electromagnetic waves) such as ultraviolet light and visible light) and heat, or a combination of plural kinds thereof can be adopted. As a device for generating an active energy ray, a known device can be used. For example, a generator using a high-pressure mercury lamp, a black light, an LED device, or the like can be applied. For example, in the irradiation of ultraviolet light, a dyed printed matter can be formed by applying ultraviolet rays for 30 to 60 seconds using an ultraviolet irradiation device having a peak wavelength near 365 nm. On the other hand, as a device for generating heat, a well-known device can be used, but a thermostatic bath or the like that can be set to an appropriate temperature can be applied.

  In the state where the dyeing solution has sufficiently penetrated into the ophthalmic lens, radical polymerization is performed to form a polymer network structure of the cured product, and the dye molecules are fixed in the ophthalmic lens. Therefore, in the obtained dyed print, it is considered that the dye molecules are included in the ophthalmic lens as a polymer network structure and form an interpenetrating network structure with the network structure of the polymer material of the lens substrate. By such an interpenetrating network structure, the cured product is firmly fixed inside the ophthalmic lens, and a highly durable and stable dyed print can be obtained. In addition, a dyed print having excellent durability can be formed by simply curing the dyeing liquid using electromagnetic waves or heat.

[Stained Eye Lens]
By using the method for producing a dyed eye lens of the present invention, a dyed eye lens having a dyed print on at least a part of the surface of an eye lens such as a contact lens can be obtained.

  As described above, such a dyed eye lens has almost no convex portion due to the dye on the surface thereof, and has a reduced physical or physiological influence on the eye. In addition, as a process for manufacturing such a dyed ophthalmic lens, an extra process such as a process of swelling an ophthalmic lens in advance before dyeing, a process of washing and smoothing a convex part after dyeing is necessary. And not. Therefore, the stained eye lens can be manufactured very simply and inexpensively. Therefore, this dyed eye lens is very excellent in terms of safety and cost, and can provide a consumer with an eye lens having high commercial value and high reliability.

  For contact lenses that are widely used for daily life, by using the method for producing dyed eye lenses, the contact lens surface has almost no convexes consisting of dye deposits and residues, and is a safe and high-grade product. A dyed contact lens having value and reliability can be provided. Even in this case, after the dyeing, extra steps such as washing and removing dye deposits and smoothing the convex portions are not required, so that the manufacturing process is greatly simplified and the product is provided at low cost. Is possible.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[Example of dye preparation]
Each staining solution used in this example was prepared as follows (see Table 1).

(Dyeing liquid (a))
As a dye of [A] component, 0.25 part by mass of 1,4-bis ((ethenylphenyl) amino) -anthraquinone, as a solvent of [B1] component, 10 parts by mass of N-methyl-2-pyrrolidone, and [B1] C] As a radical polymerization initiator of component, 0.5 parts by mass of 2-hydroxy-2-methyl-1-phenylpropan-1-one was blended, mixed and dissolved uniformly to prepare a dyeing liquid (a). did.

(Dyeing liquid (b))
As a dye of [A] component, 0.25 part by mass of 1-((4- (phenylazo) phenyl) azo) -3-methacryloyloxy-2-naphthol, and as a solvent of [B1] component, N-methyl-2- 10 parts by mass of pyrrolidone and 0.5 parts by mass of benzoin ethyl ether were blended as radical polymerization initiators of the component [C], respectively, and uniformly mixed and dissolved to prepare a dyeing liquid (b).

(Dyeing liquid (c))
As a dye of [A] component, 0.25 part by mass of 1-phenylazo-3-methacryloyloxy-2-naphthol, as a solvent of [B1] component, 10 parts by mass of N-methyl-2-pyrrolidone, and [C] component As a radical polymerization initiator, 0.5 part by mass of benzoin ethyl ether was blended, mixed and dissolved uniformly to prepare a dyeing liquid (c).

(Dyeing liquid (d))
As the dye of the component [A], 0.2 part by mass of 1,4-bis ((ethenylphenyl) amino) -anthraquinone and 0.2 part by mass of 1-phenylazo-3-methacryloyloxy-2-naphthol, [B2] As component radical polymerizable monomer, 10 parts by mass of 1-methyl-3-methylene-2-pyrrolidinone and 0.5 part by mass of benzoin ethyl ether as a radical polymerization initiator of [C] component were blended respectively. The dyeing solution (d) was prepared by mixing and dissolving uniformly.

[Example 1]
As the ophthalmic lens, a hydrous contact lens (“Menicon 2WEEK Premio” manufactured by Menicon Co., Ltd.) formed from a copolymer having a silicone compound as a constituent monomer unit was used. Heat was applied to the contact lens in a dry state for 30 seconds using an incandescent bulb (Ohm Electric Co., Ltd. 100 V, 40 W). The temperature of the contact lens surface at the end of the heat application process was measured with a thermocouple thermometer (635-2, probe K thermocouple manufactured by Testo Co., Ltd.) and found to be 65 ° C. Thereafter, the staining solution (a) was immediately applied in a line using a piezo ink jet coating apparatus, and the staining solution was brought into contact with the lens surface. The temperature in the vicinity of the application part on the contact lens surface at the end of the contact process was measured with a non-contact thermometer (Dual Thermo AR-1500 manufactured by Anritsu Keiki Co., Ltd.) and found to be 35 ° C. In this way, a dyed contact lens according to Example 1 was obtained.

[Examples 2 to 4]
Except having used the dyeing | staining liquid shown in Table 2, it carried out similarly to Example 1, and obtained the dyeing | staining contact lens which concerns on these Examples.

[Example 5]
A dyed contact lens according to Example 5 was obtained in the same manner as in Example 1 except that the time for applying heat was 10 minutes. When the temperature of the contact lens surface at the end of the heat application step was measured by the same method as described above, it was 95 ° C. Further, the temperature in the vicinity of the application part on the contact lens surface at the end of the contact process was measured by the same method as described above, and was 45 ° C.

[Example 6]
Implemented in the same manner as in Example 1 except that the distance between the incandescent bulb and the contact lens was made smaller and then the contact lens surface was heated to 130 ° C. as measured by the same method as described above. A dyed contact lens according to Example 6 was obtained. The time for applying heat was 5 minutes. Further, the temperature in the vicinity of the application part on the contact lens surface at the end of the contact process was measured by the same method as described above, and it was 55 ° C.

[Example 7]
Using an incandescent bulb (Ohm Electric Co., Ltd. 100V, 40W) and applying heat to the contact lens in a dry state, the dyeing solution (d) is applied in an annular shape using the ink jet coating apparatus. Thus, a dyed contact lens according to Example 7 was obtained. The temperature in the vicinity of the coated part on the contact lens surface at the end of the contact process was measured by the same method as described above, and it was 40 ° C.

[Example 8]
Using an incandescent bulb (Ohm Electric Co., Ltd., 100V, 40W) and applying heat to the contact lens in a dry state, the dyeing solution (a) was applied in a line using the inkjet coating device. The dyed contact lens according to Example 8 was obtained by applying heat for 10 seconds after the contact process. The temperature in the vicinity of the coated part on the contact lens surface at the end of the contact process was measured by the same method as described above, and it was 40 ° C.

[Comparative Example 1]
A dyed contact lens according to Comparative Example 1 was obtained by applying the dye solution (a) in a line shape to the contact lens in a dry state at room temperature (22 ° C.) using the inkjet coating apparatus.

[Comparative Examples 2 to 5]
A dyed contact lens according to each comparative example was obtained in the same manner as in Comparative Example 1 except that the dyeing solution and the coating shape were as shown in Table 2.

[Presence or absence of dye deposits and residues]
The dyed printed matter formed on the surface of the dyed contact lens obtained in each Example and Comparative Example was observed by magnifying 10 times using a stereoscopic microscope (OLYMPUS SZX16) and evaluated as follows. .
○: Dye deposits and residues were not observed on the contact lens surface.
X: Dye deposits and residues were observed on the contact lens surface.

  The obtained evaluation results are shown in Table 2 together with the heat application time, the distance from the incandescent light bulb, the type of staining liquid used, the condition of the coating shape, and the measured values of the temperature of the ophthalmic lens. Moreover, the stereoscopic microscope image of each dyeing printed matter is shown in each drawing described in Table 2.

  As apparent from the results of Examples 1 to 8 in Table 2, by applying heat to the ophthalmic lens before or simultaneously with applying the staining solution to the lens surface, both of the dyes were applied to the ophthalmic lens surface. Generation | occurrence | production of the deposit and the residue was not recognized, but it was shown that dye can infiltrate completely. On the other hand, in Comparative Examples 1 to 5, since no heat was applied to the ophthalmic lens during dyeing, dye precipitates and residues were observed on the ophthalmic lens surface. In addition, by comparing Example 1, Example 5 and Example 6, it is possible that a dyed printed matter that is sharper and has no blur is obtained when the application temperature of the ophthalmic lens at the end of the contact process is higher. Indicated.

  As described above, the method for producing a dyed eye lens according to the present invention can produce a safe and highly reliable dyed eye lens easily and inexpensively. Widely used.

Claims (11)

[A] a dye having at least one group having a carbon-carbon double bond in the molecule , [B] a method for producing a dyed ophthalmic lens using a polymerizable staining solution containing a medium and [C] a radical polymerization initiator Because
Having a contact step of bringing the dye solution into contact with the ophthalmic lens surface in a dry state by pattern printing of letters, numbers or figures using an ink jet coating apparatus;
Before the contact step and / or simultaneously with the contact step, it has a heat application step of applying heat to the ophthalmic lens so that the dyeing solution penetrates into the lens substrate.
[B] component medium is [B1] a solvent capable of dissolving at least a part of each of the above [A] component and [C] component and / or [B2] radical polymerizable group in the molecule. One monomer,
A method for producing a dyed eye lens, wherein the temperature of the ophthalmic lens at the end of the contact step is 30 ° C. or higher and 90 ° C. or lower.   The method for producing a dyed eye lens according to claim 1, further comprising the heat application step after the contact step.   The method for producing a dyed eye lens according to claim 1 or 2, wherein the degree of equilibrium swelling of the ophthalmic lens with the medium [B] is 40% or more and 600% or less. After top Symbol contacting step and after the heat application step for polymerizing permeated staining solution ophthalmic lens of claims 1, further comprising a fixing step of applying an active energy ray and / or heat to the infiltrated stain The manufacturing method of the lens for dyeing eyes of any one of Claim 3.   The dyeing according to claim 4, wherein the group having a carbon-carbon double bond is at least one group selected from the group consisting of α, β-unsaturated carbonyl group, styryl group, vinylbenzyl group and allyl group. A method for producing an ophthalmic lens.   The method for producing a dyed eye lens according to claim 5, wherein the α, β-unsaturated carbonyl group is a (meth) acrylate group or a (meth) acrylamide group.   The method for producing a dyed eye lens according to any one of claims 1 to 6, wherein the staining liquid further contains a surfactant [D].   The method for producing a dyed eye lens according to any one of claims 1 to 7, wherein the ophthalmic lens is a contact lens.   The method for producing a lens for a dyed eye according to claim 8, wherein the contact lens is a hydrous contact lens.   The method for producing a dyed eye lens according to claim 9, wherein the hydrous contact lens is formed of a copolymer having a silicone compound as a constituent monomer unit. The method for producing a lens for a dyed eye according to claim 8, wherein the contact lens is an oxygen-permeable hard contact lens.