JP2011106064A - Dye composition for ophthalmic lens, method for producing colored ophthalmic lens using the same, and colored ophthalmic lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye composition for ophthalmic lenses, applicable for the dyeing by an inkjet type applying device, and enabling to perform the stable dyeing simply, economically and also considering the environment. <P>SOLUTION: The dye composition used for dyeing the ophthalmic lenses by the inkjet type applying device, includes: [A] the dye having at least one group having a carbon-carbon double bond selected from an α, β-unsaturated carbonyl group, a styryl group, a vinylbenzyl group and an allyl group in its molecule; [B] a radical polymerization initiator; and [C] solvent capable of dissolving at least a part of the [A] component and [B] component, and/or [D] a monomer having at least one radically polymerizable group in its molecule. The dye composition may be a form of not containing [D] the monomer containing at least one radically polymerizable group in its molecule. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a dye composition for an ophthalmic lens, a staining method for an ophthalmic lens using the same, and a colored ophthalmic lens.

  In the field of ophthalmic lenses, especially contact lenses, in order to identify and manage standards such as the frequency of contact lenses in the manufacture, distribution, and sales, standard numbers may be printed on part of the lenses. Has 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 whose eye iris is lost due to illness or injury, a natural appearance can be obtained by printing on the contact lens simulating the color and shape of the human eye iris from the viewpoint of stability. In this way, a contact lens colored with an iris is sometimes used. In addition, from the viewpoint of fashion, there is a great demand for contact lenses with different iris colors. Applying marks and dyeing to the ophthalmic lens in this way is an important factor in the production of the lens.

  Conventionally, as a method for printing letters, numbers, figures, etc. on an ophthalmic lens, a pad printing method or a screen printing method using a dyeing liquid containing a dye or a pigment is known. In the pad printing method, an ink solution is stored in a concave groove engraved with characters to be marked, and then transferred to a pad, and a pad on which ink is placed is further brought into contact with a substrate to be printed. In the screen printing method, a mesh is applied to holes having shapes such as letters, numbers, figures, etc., and then the mesh is pressure-bonded to a printed material, and a dyeing solution is applied thereon to form a desired shape on a specific part. It is something to print. However, these methods have the following disadvantages. For example, when printing a mark at a desired position of an ophthalmic lens such as a contact lens by the pad printing method, a groove corresponding to the number or character shape to be printed is prepared by etching in advance on a base such as metal. It is necessary to keep. Such etching requires a considerable amount of time, making it difficult to systematically supply the substrate. Further, in the screen printing method, it is necessary to prepare holes having shapes such as numbers and letters to be printed in advance using an emulsion or the like, and this also requires a considerable amount of time. Furthermore, for example, when actually printing on a contact lens by these methods, it is necessary to crimp the contact lens so that the pad or screen does not move, but this work requires a dedicated fixing tool or jig for crimping. is necessary. For example, in the case of the screen printing method, it is necessary to fix the screen while pulling it and crimping it to the contact lens, which requires a large-scale tool. Furthermore, it is necessary to prepare an etching substrate and a dyeing screen for each different character, number, and figure. Further, it is necessary to reassemble the tool again for each contact lens printing process or batch printing process, which involves a very complicated process. Therefore, the pad printing method and screen printing method are limited in the number that can be processed due to the complexity of the preparation and manufacturing process of these tools. It will cause an increase. Furthermore, ink transfer defects may occur due to variations in the amount of ink applied and the pressure bonding properties of the ink, and sometimes the printed matter may bleed or the sharpness of the printed matter may be poor.

  Therefore, a method of marking with an ink jet coating apparatus has been proposed in place of the pad printing method and the screen printing method. The ink jet type coating apparatus applies a dyeing solution as very fine droplets to a surface to be dyed, and the droplets deposited on the surface form one dot, and a desired character, It becomes possible to form numbers and figures. In general, letters, numbers, and figures when small dots are gathered at a high density give sharp contrast and become excellent visibility marks. When printing and drawing using an inkjet coating device, the size of the droplets and the point where the droplets land can be accurately controlled by a computer, etc., and can be easily marked by changing the computer program. It is possible to change the shape and size. In addition, by using a plurality of ink jet nozzles, it is possible to print a plurality of dyes at the same time, so that various colors can be easily formed, and the color tone is excellent. Therefore, in printing by an ink jet coating apparatus, it is not necessary to prepare a mold or a screen imprinted for different characters, numbers, and figures as in the pad printing method and the screen printing method. In addition, printing by an ink jet type coating apparatus is a non-contact type printing method, which eliminates the need for extra steps such as contact or pressure bonding of pads and screens. It has the excellent advantage of being able to print. In view of the advantages of such an ink jet coating apparatus, several marking methods for ophthalmic lenses such as contact lenses have been disclosed.

  Japanese Patent Application Laid-Open No. 8-111266 discloses a method of printing a staining solution on a desired portion of a hydrous contact lens using an ink jet coating apparatus. This document shows that marking with excellent workability is possible by using an ink jet coating apparatus. However, this document describes the use of a reactive dye, a vat dye, or the like as a staining solution. When marking or staining an ophthalmic lens such as a contact lens, these ophthalmic lenses are used in direct contact with the eye. It is necessary to prevent elution. Further, contact lenses, particularly hydrous soft contact lenses, are required to swell when immersed in water during storage or use, or to be boiled or washed as necessary. Even if the contact lens is subjected to treatment such as swelling, boiling, and washing many times with water, the dye is prevented from eluting from the marking portion from the viewpoint of quality durability. There is a need. However, among the dyes used in the above-mentioned prior art documents, the reactive dye must have an active group capable of reacting with the dye in the chemical structure of the ophthalmic lens material. In an ophthalmic lens material that does not have an active group capable of reacting with the dye, the dye does not react, and thus the dye may elute to the outside. Therefore, the reactive dye shown in this prior document has the disadvantage that the types of applicable ophthalmic lens materials are limited. On the other hand, when a vat dye is used, it is usually reduced to an alkaline solution to obtain a dye solution. However, since such a solution is easily oxidized in the air to become an insoluble substance, it is used in the discharge nozzle of the ink jet coating apparatus. It may solidify and cause clogging. In order to prevent this, it is necessary to work in an inert environment. To that end, it is necessary to have equipment and equipment that enable the production, filling, and ink-jet application of ink in an inert environment. Inconveniences in production such as high costs are included. In addition, it is necessary to use an alkaline solution or a fixing solution for vat dyes, but there are also economic and environmental problems such as high costs for processing these solutions (waste) that are no longer needed after work. Inherent.

  Thus, in the method for dyeing an ophthalmic lens using an ink jet coating apparatus, a dye composition that hardly causes elution of a dye even for an ophthalmic lens that does not have a group capable of reacting with a reactive dye, Not developed. Furthermore, there is currently no dyeing method that is economically and environmentally friendly so that a large amount of alkaline solution or fixing solution need not be used.

Japanese Patent Application Laid-Open No. 8-112666

  The present invention has been made to eliminate these disadvantages. That is, an object of the present invention is to provide a dye composition for an ophthalmic lens that is applied for dyeing by an ink jet coating apparatus, which makes it possible to perform stable dyeing simply, economically and in consideration of the environment. Object and dyeing method, and an ophthalmic lens based thereon.

  As a result of intensive studies, the present inventors have solved a dye having at least one group having a specific carbon-carbon double bond in the molecule, a radical polymerization initiator, and at least a part of these components. A stable dyed print with extremely high elution resistance to ophthalmic lenses by containing a solvent capable of producing a monomer and / or a monomer having at least one radical polymerizable group in the molecule (radical polymerizable monomer) It was found that a dye composition for an ophthalmic lens capable of forming an ink was obtained, and such a dye composition was suitably used for a printing method using an ink jet coating apparatus, and completed the present invention. .

The invention made to solve the above problems is
A dye composition used for dyeing ophthalmic lenses with an ink jet coating apparatus,
[A] a dye having in the molecule at least one group having a carbon-carbon double bond selected from the group consisting of α, β-unsaturated carbonyl group, styryl group, vinylbenzyl group and allyl group,
[B] radical polymerization initiator, and
[C] A solvent capable of dissolving at least a part of the above-mentioned [A] component and [B] component and / or [D] a monomer having at least one radical polymerizable group in the molecule. And a dye composition for ophthalmic lenses.

  The ophthalmic lens dye composition can dissolve at least a part of these in addition to a dye having at least one group having a specific carbon-carbon double bond in the molecule and a radical polymerization initiator. Since it contains a solvent and / or a radically polymerizable monomer, it is possible to form a dyed printed matter that is extremely excellent in elution resistance (semi-permanently stable and almost free from elution) with respect to an ophthalmic lens. The dyed printed matter formed from the dye composition for an ophthalmic lens 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 radical reaction of dye molecules by electromagnetic waves and heat, and polymerizes within the polymer network structure of the ophthalmic lens, or graft reaction with the ophthalmic lens polymer. This is considered to be achieved by firmly fixing the dye molecule to the ophthalmic lens. This effect can be similarly obtained for an ophthalmic lens that does not have a group capable of reacting with a reactive dye. In addition, since the dye composition for an ophthalmic lens can be easily dyed by simply curing and fixing the dye composition by electromagnetic waves or heat without using a large amount of an alkaline solution or a fixing solution, an ink jet type Used to print on ophthalmic lenses using a coating device.

  The dye composition for an ophthalmic lens can be used in an embodiment not containing a monomer having at least one [D] radical polymerizable group in the molecule. In this way, even when the ophthalmic lens dye composition does not contain a radical polymerizable monomer, it is possible to form a dyed printed material with extremely excellent elution resistance with respect to the ophthalmic lens. It can be easily dyed by simply curing and fixing the dye composition by electromagnetic waves or heat.

  The dye composition for an ophthalmic lens is preferably in the form of a uniform solution. Thus, by making the dye composition into the form of a uniform solution, it is possible to effectively prevent clogging in the discharge nozzle during printing on an ophthalmic lens using an ink jet type coating apparatus, and good A dyed print can be obtained. In addition, the dye composition in the form of a uniform solution can easily and uniformly penetrate into the ophthalmic lens.

  In the ophthalmic lens dye composition, when the group having a carbon-carbon double bond as the component [A] is an α, β-unsaturated carbonyl group, the group is a (meth) acrylate group or (meth) acrylamide. It is preferably a group. By selecting these groups as the group having a carbon-carbon double bond as the component [A], the elution resistance of the dye composition to the ophthalmic lens and the printing characteristics to the ophthalmic lens are further improved. Can do.

  The ophthalmic lens dye composition preferably further contains [E] a surfactant. When the dye composition for an ophthalmic lens further contains a surfactant, the penetration speed and uniformity can be improved when the dye composition is printed on the ophthalmic lens.

The method for dyeing an ophthalmic lens with the ink jet coating apparatus according to the present invention includes the following steps.
(1) The process of apply | coating the said dye composition for ophthalmic lenses on the surface of an ophthalmic lens using an inkjet type coating device,
(2) a step of allowing at least a part of the applied dye composition for an ophthalmic lens to penetrate into the interior of the ophthalmic lens; and (3) then, in order to polymerize the ophthalmic lens dye composition, the dye The process of providing an active energy ray and / or heat to a composition.

  As described above, in the method for dyeing the ophthalmic lens, an ophthalmic lens dye composition containing the components [A], [B], and [C] and / or [D] is used. For any ophthalmic lens including those that do not have a group capable of reacting with a reactive dye, it is possible to form a dyed printed matter having extremely excellent elution resistance. In addition, according to this dyeing method, since the dye composition for an ophthalmic lens containing each of the above components is used, it is not necessary to use an alkaline solution or a fixing solution. In addition, it is possible to perform dyeing by a method that is economically and environmentally friendly. That is, it can be said that the dyeing method is an excellent method from the viewpoints of workability, simplicity, economy, and environment.

  In order to polymerize the ophthalmic lens dye composition after all of the applied ophthalmic lens dye composition penetrates into the ophthalmic lens in the step (2) of the ophthalmic lens staining method. Furthermore, active energy rays and / or heat can be imparted to the dye composition. In this way, a polymer network structure is formed by fixing electromagnetic waves and heat in a state where all of the applied dye composition has permeated the inside of the ophthalmic lens, and is fixed inside the ophthalmic lens. The polymer network structure of such a dye composition forms an interpenetrating network structure with the polymer network structure of the ophthalmic lens and is firmly fixed to each other. A stable print can be obtained.

  In the step (2) of the ophthalmic lens staining method, part of the applied ophthalmic lens dye composition penetrates into the ophthalmic lens and the remaining part forms an interface with the atmosphere. In this state, in order to polymerize the dye composition for an ophthalmic lens, an active energy ray and / or heat can be applied to the dye composition. Even in this case, a part of the dye composition penetrating into the ophthalmic lens forms an interpenetrating network structure with the polymer network structure of the ophthalmic lens, so that the elution of the dye does not occur. The printed matter is firmly formed and fixed on the surface of the ophthalmic lens.

  In the step (1) of the dyeing method for the ophthalmic lens, the ophthalmic lens dye composition can be applied to the surface of the ophthalmic lens in a dry state using an ink jet coating apparatus. Since the dye composition contains a solvent of [C] component and / or a radically polymerizable monomer of [D] component in addition to the above [A] component and [B] component, it is thus dried. Even when the dye composition is applied to an ophthalmic lens in a finished state, the dye composition can be cured and fixed by simply using electromagnetic waves or heat without using a large amount of alkaline solution or fixing solution. The dyed printed matter can be easily obtained.

  A colored ophthalmic lens can be formed by having a cured product obtained by curing the above dye composition for an ophthalmic lens in at least a part of the surface layer. Such an ophthalmic lens is formed from a dye composition containing each of the components [A], [B], and [C] and / or [D], and thus has excellent elution resistance, Sufficient eye safety can be ensured.

  A contact lens can be used as the ophthalmic lens that is the base material of the colored ophthalmic lens. When using the above-mentioned dye composition for ophthalmic lenses for dyeing contact lenses that are widely used for daily life, the cured product of this dye composition has excellent elution resistance, and thus has high commercial value. It is possible to provide a contact lens having high reliability. Such an effect can be similarly obtained when a hydrous soft contact lens is used as a contact lens.

  As the water-containing soft contact lens in the colored ophthalmic lens, it is preferable to use a lens formed from a monomer copolymer containing a silicone compound. Thus, since the hydrous soft contact lens is formed from the copolymer of the monomer containing a silicone compound, high flexibility and oxygen permeability can be imparted to the contact lens.

  An oxygen-permeable hard contact lens can be used as the ophthalmic lens that is a base material in the colored ophthalmic lens. As described above, even when an oxygen-permeable hard contact lens is used as an ophthalmic lens, the cured product of the dye composition has excellent elution resistance, so that the contact lens has high commercial value and reliability. Can be provided.

  As described above, according to the dye composition for an ophthalmic lens of the present invention, it is possible to form a dyed printed matter that is extremely excellent in elution resistance with respect to an ophthalmic lens, is semi-permanently stable, and has almost no elution. it can. The dyed printed matter has extremely high durability because the dye does not elute even when it is swollen with water, boiled, or washed. Such an effect can be similarly obtained for an ophthalmic lens that does not have a group capable of reacting with a reactive dye. Furthermore, since the dye composition for an ophthalmic lens can be easily dyed by simply curing and fixing the dye composition using electromagnetic waves or heat without using a large amount of alkaline solution or fixing solution, It is used for printing on an ophthalmic lens using an ink jet coating apparatus.

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

  The dye composition for an ophthalmic lens used for dyeing an ophthalmic lens with the ink jet coating apparatus according to the present invention includes [A] α, β-unsaturated carbonyl group, styryl group, vinylbenzyl group, and allyl group. A dye having at least one group having a carbon-carbon double bond selected from the group consisting of: [B] radical polymerization initiator, and [C] the above components [A] and [B] A solvent capable of dissolving at least a part thereof and / or a monomer having at least one [D] radical polymerizable group in the molecule; Hereinafter, each component of the dye composition for an ophthalmic lens will be described in order.

[A] component: a dye having at least one group having a specific carbon-carbon double bond in the molecule The dye of [A] component develops a specific color by absorbing or reflecting a part of visible light And a compound having at least one group in the molecule having a specific carbon-carbon double bond. 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. By using such a dye, it is possible to obtain a dye composition capable of forming a dyed printed matter having excellent elution resistance with respect to an ophthalmic lens. The reason why the dyed printed matter thus formed has extremely high elution resistance is that the dye molecules are polymerized in the polymer network constituting the base of the ophthalmic lens, or to the polymer of the base of the ophthalmic lens. This may be because the dye molecules are immobilized by the graft reaction of

  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 in the component [A] is these specific groups, the elution resistance of the dye composition to the ophthalmic lens can be improved, and printing on the ophthalmic lens can be performed. The characteristics can be further improved. 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.

  From the viewpoint of the chemical structure of a dye that develops a specific color by absorbing or reflecting a part of visible light, an azo dye, anthraquinone dye, nitro dye, phthalocyanine dye, quinoneimine dye, quinoline dye And carbonyl dyes, triarylmethane dyes, methine dyes, and the like.

  The dye having at least one (meth) acrylate group in the molecule is not particularly limited. For example, 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3- (meth) acryloyl Oxynaphthalene, 1-naphthylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- (α-anthrylazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-((4′-phenylazo) Phenyl) azo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- (2 ′, 4′-xylylazo) -2- (meth) acryloyloxynaphthalene, 1- (o-tolylazo) -2- (meth) ) Acrylyloxynaphthalene, 2,4-dihydroxy-3- (p- (Meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-3- (p- (meth) acryloyloxyethylphenyl) Azo) 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- (meta ) Acryloyloxymethylphenylazo) 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, -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) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy- 5- (o- (N-ethyl-N- (meth) acryloyloxyethyla) Roh) phenylazo) benzophenone, and the like can be given.

  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 following, 1,4-bis (4-allyloxyethylphenyl) aminoanthraquinone represented by the following formula (10), and the like.

  The proportion of the [A] component dye used in the dye composition is not particularly limited, but is 0 with respect to a total of 100 parts by mass of the solvent of the [C] component and / or the [D] radical polymerizable monomer described below. It is preferably 1 part by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass or more and 5 parts by mass or less. Thus, sufficient visibility of dyed printed matter can be obtained by making the usage-amount of [A] component 0.1 mass part or more. In addition, by making the use ratio of the component [A] 10 parts by mass or less, it is possible to reduce the occurrence of an insoluble part in the composition, and uneven penetration of the ophthalmic lens due to an excess of the dye. Occurrence of induced staining unevenness (deterioration of appearance when the lens is mounted) can be prevented. In the dye composition, the dye of the component [A] may be used alone or as a mixture of plural kinds. In addition to the [A] component, the dye composition contains an amount of a non-reactive dye (eg, “D & C Green No. 6” or “D & C Red No. 17”) that does not inhibit the above effect. May be added.

[B] Component: Radical Polymerization Initiator The radical polymerization initiator of [B] component generates radicals (free radicals) by applying active energy rays (light rays (electromagnetic waves) such as ultraviolet light and visible light) or heat. A radical polymerization of a dye itself having at least one group having a specific carbon-carbon double bond of the component [A], or a dye of the component [A] and [D] described later. Defined as being capable of initiating radical polymerization with a monomer having at least one radical polymerizable group in the molecule. The radical polymerization initiator of the component [B] is not particularly limited as long as it has the properties defined as described above.

As a specific example of the radical polymerization initiator by active energy rays,
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 the radical polymerization generator 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.

  The use ratio of the radical polymerization initiator of the [B] component in the dye composition is not particularly limited, but a total of 100 masses of the solvent of the [C] component and / or the radical polymerizable monomer of the [D] component described later. It is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 15 parts by mass or less with respect to parts. By making the use ratio of the [B] component 0.1 parts by mass or more, radical polymerization reactivity can be maintained at a high level, and elution and lightening of the dye not fixed on the ophthalmic lens can be suppressed. it can. By making the use ratio of the component [B] 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. A radical polymerization initiator may be used individually by 1 type, and may use multiple types of compound together.

[C] Component: Solvent The solvent of the [C] component is not particularly limited as long as it is a liquid capable of dissolving at least part of the [A] component and the [B] component. The solvent of the component [C] is at least one monomer having at least one radical polymerizable group of the component [D], which is an optional component described later, in addition to the components [A] and [B]. It is preferably a liquid that can dissolve the part. In addition, the solvent of [C] component dissolves substantially all of [A] component and [B] component, or substantially all of [A] component, [B] component and optional [D] component. More preferably, it is a liquid that can be made to flow.

As a typical solvent of the component [C] used in the dye composition,
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 [C], one type may be used alone, or a plurality of types may be used in combination.

[D] component: monomer having one radical polymerizable group in the molecule The “radical polymerizable group” as used herein means an unsaturated group capable of radical polymerization. In the case where a liquid monomer is used as the monomer having one radical polymerizable group in the component [D], the dye of the component [A] and the radical polymerization initiator of the component [B] When it can be dissolved in a liquid monomer, a dye solution can be formed using such a monomer without using the solvent of the component [C]. In the dye composition, a solvent of the [C] component and a monomer of the [D] component can be used in combination. In the dye composition, by using the monomer of the component [D], polymerization of the polymer network in the ophthalmic lens substrate by the dye molecule of the component [A], fixing, or the ophthalmic lens substrate. The immobilization by the graft reaction with the polymer is further strengthened, and it is considered that the peeling resistance and the elution resistance against washing and the like of the dyed printed matter are further enhanced. Further, by using such a monomer of the [D] component, it is permanently stable and hardly eluted even for an ophthalmic lens base material having no functional group capable of reacting with a reactive dye. It is possible to give no dyed prints.

As an example of a monomer having one radical polymerizable group in the component [D] in the molecule,
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 these monomers, 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, methoxyethyl (meth) acrylate, Styrene, N, N-dimethyl (meth) acrylamide, ethyl (meth) acrylate, butyl (meth) acrylate and N-vinylpyrrolidone are preferred.
As the monomer of component [D], one type may be used alone, or a plurality of types may be used in combination.

  As described above, only one of the [C] component and the [D] component in the dye composition may be used, and the usage ratio and the ratio of both are not particularly limited. For example, the usage ratio when using the [C] component in the dye composition is 0.1 mass% or more and 99.8 mass% or less, and the usage ratio when using the [D] component is 1 mass% or more and 99.8 mass%. % Or less.

[E] Component: Surfactant The surfactant of the [E] component is used for more smoothly penetrating the solution of the dye composition into the inside of the ophthalmic lens substrate, and for dyed printed matter formed from the dye composition. It can be used to prevent bleeding. Further, the surfactant has an action of stabilizing micelles in the dye composition described later. Such a surfactant is used in a state dissolved or emulsified in the dye composition solution.

Specific examples of surfactants include
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 penetration of the dye composition solution into the ophthalmic lens substrate.

  The ratio of the [E] component used in the dye composition is not particularly limited, but is preferably 0.001% by mass or more and 5% by mass or less. By making the use ratio of the component [E] 0.001% by mass or more, the permeability of the dye composition can be effectively increased, and the occurrence of bleeding of the dyed printed matter can be suppressed. The use ratio of the component [E] is more preferably 0.01% by mass or more. On the other hand, by making the use ratio of the [E] component 5% by mass or less, it is possible to prevent uneconomics due to excessive use of the surfactant. [E] The proportion of component used is more preferably 2% by mass or less. [E] Surfactant of a component may be used individually by 1 type, and may use multiple types together.

[Dye composition for ophthalmic lens]
The dye composition for an ophthalmic lens of the present invention includes a dye having at least one group having a specific carbon-carbon double bond of the above-mentioned [A] component in the molecule, a radical polymerization initiator of the [B] component, In addition, an appropriate amount of a solvent for the component [C] and / or a monomer having at least one radical polymerizable group in the molecule, and if necessary, other optional components such as a surfactant for the component [E] Prepared by mixing. The order of mixing these components is not particularly limited.

  The form of the dye composition is desirably a uniform solution. When the dye composition is such a uniform solution, it is possible to effectively prevent clogging in the discharge nozzle at the time of printing on an ophthalmic lens using an ink jet type coating apparatus, and good A dyed print can be obtained. Moreover, the dye composition in the form of a uniform solution can easily and uniformly penetrate into the ophthalmic lens. The “uniform solution” here includes not only a state in which the dye is dispersed and dissolved in a molecular form in the dye composition but also a state in which at least a part of the dye forms aggregates such as micelles. 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 that forms the ophthalmic lens material, and thus cannot be specified unconditionally, but the average upper limit is 500 to 600 nm. Is preferred.

[Eye lens]
The ophthalmic lens that is dyed with the dye composition is a lens that enables correction of visual acuity, improvement of tonicity and the like by being attached to the human eye, and is not limited to a contact lens, but also an intraocular lens, an artificial cornea, a cornea The concept includes onlay, 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. When the dye composition is used for dyeing contact lenses that are widely used for daily use, the cured product of the dye composition has excellent elution resistance, and thus has high commercial value and reliability. Can be provided. Examples of the contact lens include a hydrous soft contact lens that softens by containing water, a non-hydrous soft contact lens, a hard oxygen-permeable contact lens, or a hybrid contact lens made of a combination thereof. As described above, the dye composition is excellent in elution resistance, and can form a dyed printed matter that is semi-permanently stable and almost free from elution. Therefore, it is suitable for soft contact lenses, particularly hydrous soft contact lenses. A dyed printed material that is used and has excellent durability can be formed. As materials for these ophthalmic lenses, any known materials can be used. For example, as a material of the hydrous soft contact lens, hydrogel obtained by swelling a polymer compound such as polyhydroxyethyl methacrylate with an aqueous solvent can be used.

  As described above, when a hydrous soft contact lens is used as an ophthalmic lens, one formed from a copolymer of a monomer containing a silicone compound is preferably used. Thus, the water-containing soft contact lens formed from the copolymer of the monomer containing the silicone compound can impart high flexibility and oxygen permeability to the contact lens. Such a copolymer is not particularly limited. For example, a silicone hydrogel obtained by copolymerizing a silicone monomer (or a macromer) and a water-containing monomer can be used. Examples of silicone monomers used include compounds having an ethylenically unsaturated group and a polydimethylsiloxane structure via a urethane bond, silicone compounds having a hydrophilic structure moiety in the molecule, silicone-containing alkyl (meth) acrylates, silicones Styrene derivatives and silicone-containing fumaric acid diesters.

  As an ophthalmic lens to be dyed with the dye composition, an ophthalmic lens having no group capable of reacting with a reactive dye can be suitably used. Even when the ophthalmic lens does not have a group capable of reacting with a conventionally used reactive dye, the dye molecule forms a polymer network in the ophthalmic lens as described above, which is excellent. It is considered that a dyed print having elution resistance can be obtained.

[Dyeing method for ophthalmic lens]
Next, a method for dyeing an ophthalmic lens with an ink jet coating apparatus using the above-described ophthalmic lens dye composition will be described. The method is
(1) The process of apply | coating the dye composition for ophthalmic lenses of this invention to the surface of an ophthalmic lens using an inkjet type coating device,
(2) a step of allowing at least a part of the applied dye composition for an ophthalmic lens to penetrate into the interior of the ophthalmic lens; and (3) then, in order to polymerize the ophthalmic lens dye composition, the dye A step of applying active energy rays and / or heat to the composition is included in this order.

[Application step (1)]
In the step (1), the solution or dispersion of the dye composition of the present invention is applied to the surface of the ophthalmic lens using an ink jet coating apparatus. For the application of the dye composition, a known ink jet coating apparatus can be used. A typical ink jet coating apparatus is composed of a dye solution supply system and an ejection device composed of a nozzle equipped with a piezoelectric element such as a piezo element. 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. In a discharge device provided with a plurality of nozzles, solutions or dispersions containing different dyes can be discharged simultaneously, and high-quality multicolor printing can be performed at high speed. An ink jet coating apparatus having such a plurality of nozzles can also be suitably used. When performing such multi-color printing, two or more types of dye compositions (solutions or dispersions) containing dyes of different color tones are respectively filled in storage tanks, and a desired position is obtained by a scanning method programmed by a computer or the like. A printed matter can be obtained by discharging various dye compositions.

  The dye composition can also be applied to the surface of the ophthalmic lens in a dry state. Since the dye composition contains a solvent of the component [C] and / or a radically polymerizable monomer of the component [D] together with the components [A] and [B], it is used for the eye in a dry state. Even when the dye composition is applied to a lens, at least a part of the composition sufficiently penetrates into the ophthalmic lens, and a dyed printed matter having high solvent resistance and durability can be easily obtained. Conceivable.

[Penetration process of (2)]
In the step (2), the dye composition (solution or dispersion) discharged by the ink jet coating apparatus is deposited on the surface of the ophthalmic lens, and the dye composition is introduced from the surface of the ophthalmic lens to the inside. May be left until completely penetrated. Alternatively, after the dye composition is deposited on the surface of the ophthalmic lens, a part of the dye composition penetrates into the ophthalmic lens and the remaining part forms an interface with the atmosphere. You may leave it until it forms the state to do. When any one of these states is formed, electromagnetic waves or heat can be applied in step (3) described later. The time required for the permeation of the dye composition in each case is not particularly limited, and there are a number of components such as the components of the dye composition and the proportion thereof, the required penetrability of the dye composition, and the ambient temperature at the time of application. Depends on factors. Therefore, the penetration time of the dye composition can be determined by visually observing how the dye composition penetrates into the ophthalmic lens using a microscope. The time required for the dye composition to completely penetrate from the surface of the ophthalmic lens into the interior is not particularly limited, but is, for example, 60 seconds or longer and 20 minutes or shorter. Further, the time required for a part of the dye composition to penetrate from the surface of the ophthalmic lens to the inside and the remaining part to form an interface with the atmosphere is not particularly limited, but for example, 10 seconds or more 3 minutes or less.

[Polymerization step (3)]
In the step (3), radical polymerization and curing are performed by applying energy to the dye composition applied to the ophthalmic lens in the step (2), and the cured product is fixed to the ophthalmic lens. The polymerization of the [A] component dye itself, or the polymerization of the [A] component dye and the [D] component radically polymerizable monomer is performed by applying energy to the [B] component radical polymerization initiator. It is initiated by the generation of radicals (free radicals). As a form of such an energy loading 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 active energy rays, 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 cured product can be formed by applying ultraviolet rays for 30 to 60 seconds using an ultraviolet irradiation device having a maximum 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.

  The step of imparting energy to the dye composition applied to the ophthalmic lens as described above is performed in the state where the dye composition has completely penetrated into the ophthalmic lens by the step (2) or the dye composition. It can be carried out in a state where a part of the object penetrates into the inside of the ophthalmic lens and the remaining part forms an interface with the atmosphere. According to the former method, a polymer network structure of a cured product is formed by radical polymerization in a state where the dye composition has completely penetrated into the ophthalmic lens, and is fixed in the ophthalmic lens. Therefore, it is considered that the obtained dyed print is included in the ophthalmic lens as a polymer network structure and forms 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. On the other hand, according to the latter method, a polymer network structure of a cured product is formed by radical polymerization in a state where a part of the dye composition penetrates into the ophthalmic lens, and is fixed in the ophthalmic lens. At this time, a part of the dyed print may protrude from the surface of the ophthalmic lens, but a part of the dye composition penetrates into the ophthalmic lens and polymerizes and cures. In this manner, an interpenetrating network structure similar to the above is formed. Therefore, even when energy is imparted and radically polymerized in a state where a part of the dye composition penetrates into the ophthalmic lens in this way, the cured product is firmly fixed on the ophthalmic lens and is extremely durable. A high and stable dyed print can be obtained. In dyeing using the dye composition, it is possible to select one of the above dyeing methods or a method using them in combination depending on the type of printed matter and the purpose of dyeing.

  In such an ophthalmic lens dyeing method, the dye composition can be cured and fixed by simply using electromagnetic waves or heat without using a large amount of alkaline solution or fixing solution. It can be performed. Moreover, according to this dyeing | staining method, it can dye | stain correctly with respect to the fine object of an ophthalmic lens by using an inkjet type coating device.

[Colored eye lens]
For example, by using the dyeing method including the above steps (1) to (3), at least part of the surface layer of an ophthalmic lens such as a contact lens is colored with a cured product obtained by curing the dye composition. An ophthalmic lens can be obtained.

  As described above, such a colored ophthalmic lens has a dyed printed material that is extremely excellent in elution resistance, semi-permanently stable, and almost free from elution. This dyed printed matter exhibits the characteristic that the dye does not elute even during swelling, boiling and washing with water, and has extremely high durability. The excellent elution resistance of the colored ophthalmic lens is that the dye molecules undergo a radical reaction due to electromagnetic waves or the like and polymerize in the polymer network structure that constitutes the ophthalmic lens. It is considered that the dye molecule is expressed by firmly fixing to the ophthalmic lens by the graft reaction. Since this colored ophthalmic lens has high elution resistance, it is very excellent in terms of safety, and it is possible to provide an ophthalmic lens with high commercial value and reliability to consumers.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly based on description of this Example.

Preparation of dye composition for ophthalmic lens [Example 1]
0.2 part by mass of 1,4-bis ((ethenylphenyl) amino) -anthraquinone as a dye of [A] component, and 2-hydroxy-2-methyl-1-phenylpropane as a radical polymerization initiator of [B] component 0.5 parts by mass of -1-one, and 10 parts by mass of 1-methyl-3-methylene-2-pyrrolidinone and 1 part by mass of ethylene glycol dimethacrylate as a radical polymerizable monomer of the component [D] A dye composition for an ophthalmic lens was prepared. Next, using a piezo-type ink jet coating apparatus, dots were formed on the outer surface of a hydrous soft contact lens containing a silicone group (having no group capable of reacting with a reactive dye). This dye composition was applied so as to form a line pattern. By leaving still for 3 minutes after application | coating and observing with a microscope, it confirmed that all the dye compositions were osmose | permeating the inside of a lens base material. In this state, an ultraviolet irradiator “UV Spot Cure UIS-250-01” manufactured by USHIO INC. Was used as an irradiation device, and the lens composition was irradiated with ultraviolet rays having a maximum wavelength of 365 nm for 40 seconds to polymerize the dye composition. It was cured to obtain a hydrous soft contact lens having a dyed print on the surface layer.

[Examples 2-44, Comparative Examples 1-4]
Except having changed component composition as it described in Tables 1-3, it carried out similarly to Example 1, and obtained the hydrous soft contact lens which has a dyed printed matter in the surface layer which concerns on these Examples and a comparative example. In the table, the abbreviation “Ex” was used for Examples and “Cp” was used for Comparative Examples.

[Example 45]
A dye composition for an ophthalmic lens was prepared by mixing the same components as in Example 1. Subsequently, this dye composition was applied using a piezo-type ink jet coating apparatus so that a line pattern composed of dots was formed on the outer surface of the water-containing soft contact lens containing a silicone group. Immediately after application, the lens is continuously observed with a microscope. After about 60 seconds, a part of the dye composition penetrates into the lens and the remaining part forms an interface with the atmosphere. Confirmed that the condition. In this state, an ultraviolet ray irradiator “UV Spot Cure UIS-250-01” manufactured by Ushio Electric Co., Ltd. was used as an irradiation device, and the dye composition was polymerized by irradiating the lens with ultraviolet rays having a maximum wavelength of 365 nm for 40 seconds. It was cured to obtain a hydrous soft contact lens having a dyed print on the surface layer.

[Examples 46 to 47]
Except having changed component composition as described in Table 3, it carried out similarly to Example 45, and obtained the hydrous soft contact lens which has a dyed printed matter in the surface layer which concerns on these Examples.

[Example 48]
As a dye of [A] component, 0.1 part by mass of 1,4-bis ((ethenylphenyl) amino) -anthraquinone and 0.1 part by mass of 1-phenylazo-3-methacryloyloxy-2-naphthol, [B] component An ophthalmic lens by mixing 0.5 parts by mass of benzoin methyl ether as a radical polymerization initiator and 10 parts by mass of 1-methyl-3-methylene-2-pyrrolidinone as a radical polymerizable monomer of [D] component A dye composition was prepared. Next, an iris pattern is formed on the outer surface of the water-containing soft contact lens containing silicone (which does not have a group capable of reacting with a reactive dye) using a piezo ink jet coating apparatus. By applying this dye composition to the sample and observing with a microscope, it was confirmed that all of the dye composition penetrated into the lens substrate. In this state, an ultraviolet irradiator “UV Spot Cure UIS-250-01” manufactured by Ushio Electric Co., Ltd. was used as the irradiation device, and the lens composition was irradiated with ultraviolet rays having a maximum wavelength of 365 nm for 5 seconds to polymerize the dye composition. It was cured to obtain a silicone-containing hydrous soft contact lens with an iris pattern having a dyed print on the surface layer.

  The physical property evaluation of the hydrous soft contact lens having the dyed printed material on the surface layer produced as described above was performed by the following methods.

[Autoclave resistance]
After two cycles of high-pressure steam sterilization for 20 minutes at a temperature of 121 ° C. in physiological saline, confirm the visibility of the dyed printed matter (to the extent that the line pattern of the dyed printed matter can be clearly identified) with the naked eye. It was evaluated as follows. The results are shown in Tables 1-3.
○: Visibility was good.
X: Visibility was poor.

[Solvent resistance]
After soaking in ethanol at a temperature of 30 ° C. for 6 hours, the visibility of the dyed printed matter (the degree to which the line pattern of the dyed printed matter can be clearly identified) was confirmed by the naked eye and evaluated as follows. The results are shown in Tables 1-3. In addition, evaluation of the solvent resistance about Comparative Examples 1-4 was not implemented since fading was confirmed by the autoclave resistance evaluation.
○: Visibility was good.
X: Visibility was poor.

  From the results of Tables 1 to 3, the reactive dye of [A] component according to the present invention, the radical polymerization initiator of [B] component, the solvent of [C] component and / or the [D] radical polymerizable monomer The dye composition for an ophthalmic lens containing a body can form a dyed printed material with significantly superior dissolution resistance and durability for an ophthalmic lens compared to a dye composition having no such composition. I understood. The ophthalmic lens dye composition exhibits a desired excellent effect even when it contains only one of the solvent of the component [C] and the radically polymerizable monomer [D]. I understood. Furthermore, even when a part of the dye composition for an ophthalmic lens is penetrated into the lens and cured, the same anti-elution resistance and durability as when all of the dye composition is penetrated and cured. A dyed print having a color was obtained.

  As described above, the dye composition for an ophthalmic lens of the present invention can form a dyed printed matter with extremely excellent elution resistance and durability, and exhibits sufficient safety. Widely used for dyeing ophthalmic lenses.

Claims (14)

A dye composition used for dyeing ophthalmic lenses with an ink jet coating apparatus,
[A] a dye having in the molecule at least one group having a carbon-carbon double bond selected from the group consisting of α, β-unsaturated carbonyl group, styryl group, vinylbenzyl group and allyl group,
[B] radical polymerization initiator, and
[C] A solvent capable of dissolving at least a part of the above-mentioned [A] component and [B] component and / or [D] a monomer having at least one radical polymerizable group in the molecule. A dye composition for ophthalmic lenses.   The dye composition for ophthalmic lenses according to claim 1, which does not contain a monomer having at least one [D] radical polymerizable group in the molecule.   The dye composition for an ophthalmic lens according to claim 1 or 2, which is in the form of a uniform solution.   The dye composition for an ophthalmic lens according to claim 1, wherein the α, β-unsaturated carbonyl group is a (meth) acrylate group or a (meth) acrylamide group.   [E] The dye composition for an ophthalmic lens according to any one of claims 1 to 4, further comprising a surfactant. A method for dyeing an ophthalmic lens with an ink jet coating apparatus,
(1) The process of apply | coating the dye composition for ophthalmic lenses of any one of Claims 1-5 on the surface of an ophthalmic lens using an inkjet type coating device,
(2) a step of allowing at least a part of the applied dye composition for an ophthalmic lens to penetrate into the interior of the ophthalmic lens; and (3) then, in order to polymerize the ophthalmic lens dye composition, the dye A method for dyeing an ophthalmic lens comprising a step of applying an active energy ray and / or heat to a composition.   In order to polymerize the dye composition for an ophthalmic lens after all of the applied dye composition for an ophthalmic lens has penetrated into the eye lens in the step (2), the dye composition for an ophthalmic lens is polymerized. The method for staining an ophthalmic lens according to claim 6, wherein active energy rays and / or heat are applied.   In the step (2), in the state where a part of the applied dye composition for the ophthalmic lens penetrates into the ophthalmic lens and the remaining part forms an interface with the atmosphere, the ophthalmic lens The method for dyeing an ophthalmic lens according to claim 6, wherein an active energy ray and / or heat is applied to the dye composition in order to polymerize the dye composition.   In the said process (1), the said dye composition for ophthalmic lenses is apply | coated to the surface of the ophthalmic lens of the dried state using an inkjet type coating device. Dyeing method for ophthalmic lenses.   The colored ophthalmic lens which has a hardened | cured material obtained by hardening | curing the dye composition for ophthalmic lenses of any one of Claims 1-5 in at least one part of surface layer.   The colored ophthalmic lens according to claim 10, wherein the ophthalmic lens is a contact lens.   The colored ophthalmic lens according to claim 11, wherein the contact lens is a hydrous soft contact lens.   The colored ophthalmic lens according to claim 12, wherein the hydrous soft contact lens is formed from a copolymer of a monomer containing a silicone compound.   The colored ophthalmic lens according to claim 11, wherein the contact lens is an oxygen-permeable hard contact lens.