JP2005023294A - Manufacturing method of resin for optical material, resin for optical material and plastic lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a resin for an optical material using a masterbatch capable of in a good productivity and efficiently manufacturing it, to provide a resin for an optical material and to provide a plastic lens. <P>SOLUTION: The method comprises polymerizing a polymerizable composition obtained by mixing (A) a first polymerizable monomer having a first functional group having two or more active hydrogens in one molecule, (B) a second polymerizable monomer having two or more of a second functional group, that can react with the first functional group, such as a (thio)epoxy group, an iso(thio)cyanate group, etc., and (C) a masterbatch obtained by dispersing or dissolving an additive into a compound having the first functional group or the second functional group as a solvent. As the additive, a bluing dyestuff is used. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a resin for optical materials used for plastic lenses, prisms, lenticular sheets, filters, and the like, a resin for optical materials produced by the production method, and a plastic lens using the resin.

  Plastic materials are widely used in various applications such as plastic lenses and prisms instead of conventional inorganic glass materials as optical material resins because they are lightweight and excellent in strength. Among them, plastic lenses are widely used in vision correction lenses and sunglasses, camera lenses, optical elements, and the like in recent years because they are lighter and harder to break than conventional glass lenses and are easy to dye. In addition to low specific gravity, the performance required for optical materials, particularly spectacle lenses, is high refractive index and high Abbe number as optical performance, and high heat resistance and high strength as physical properties. A high refractive index makes it possible to reduce the thickness of the lens, a high Abbe number reduces the chromatic aberration of the lens, and high heat resistance and high strength are important from the viewpoint of ease of secondary processing and safety. In recent years, various plastic lens materials have been developed to meet these requirements, and many attempts have been made to develop new transparent plastic lenses having a high refractive index.

  Furthermore, it is proposed to provide such a plastic lens with ultraviolet absorbing ability and protect the eyes from damage caused by ultraviolet rays. In order to provide ultraviolet absorbing ability, the plastic lens resin material itself has ultraviolet absorbing ability. A material is used, or an ultraviolet absorber is added to a resin material for a plastic lens. However, in these plastic lenses, the plastic lens often becomes yellow due to the color (yellow) of the resin material for the plastic lens or the ultraviolet absorber itself. In such a case, there is a blueing method for maintaining the transparency of the plastic lens by adding a blue or purple dye that cancels the yellowness to the plastic lens resin material itself. For example, a blueing masterbatch prepared by dispersing or dissolving a dye in the polymerized monomer by adding a blue or purple dye to a part of the polymerized monomer that is the main raw material of the plastic lens and stirring. In general, however, a bluing masterbatch system in which this is added to the raw material of plastic lenses is performed. The method for producing a brewing masterbatch is used when the amount of dye added is very small and weighing is difficult.

For example, Patent Document 1 shown below proposes a manufacturing method using this bluing master batch method when manufacturing a urethane resin lens.
Currently, urethane-based plastic lenses and episulfide-based plastic lenses are widely used as high refractive index plastic spectacle lens materials. In Patent Document 2 shown below, as an optical material excellent in the balance between a high refractive index and a high Abbe number, it has one or more disulfide bonds (SS) in the molecule, and an epoxy group and / or a thioepoxy group. Compounds have been proposed. In Patent Documents 3 and 4 shown below, a plastic lens having a thiourethane structure obtained by a reaction between a polyisocyanate compound and a compound having an active hydrogen group such as a polythiol compound is proposed. Patent Document 5 proposes a compound having two or more mercapto groups in the molecule.
JP-A-9-133801 JP 11-322930 A Japanese Patent Publication No. 4-58489 JP-A-5-148340 JP 2001-342252 A

  However, although the polymerization monomer used in these resin materials has been designed to obtain a high refractive index, the viscosity of the polymerization monomer often increases with it. As a problem, when the viscosity of the polymerization monomer used in preparing the bluing masterbatch increases, it becomes difficult to stir the dye, or the dye becomes difficult to disperse or dissolve in the polymerization monomer. Is mentioned. In particular, with a polymerization monomer having a viscosity of 420 mPa · s / 25 ° C. or higher, the viscosity is too high and stirring is very difficult, and it takes time until the dye is dispersed or dissolved in the polymerization monomer.

This invention is made | formed in view of the said situation, and it aims at providing the manufacturing method of resin for optical materials using the masterbatch which can be manufactured with sufficient productivity and efficiency.
Moreover, an object of this invention is to provide resin for optical materials manufactured by this manufacturing method of resin for optical materials.
Furthermore, an object of the present invention is to provide a plastic lens using the resin for optical materials.

  In order to achieve the above-mentioned object, the present invention firstly provides (A) a first polymerized monomer having two or more reactive first functional groups in one molecule, and (B) the above-mentioned in one molecule. A second polymerizable monomer having two or more second functional groups that react with the first functional group, (C) the additive is dispersed or dissolved in the first functional group or the compound having the second functional group as a solvent. There is provided a method for producing a resin for optical materials, characterized by polymerizing a polymerizable composition obtained by mixing the master batch.

  The method for producing a resin for optical materials according to the present invention uses a compound having the same functional group as one of the polymerization monomers, instead of using one of the polymerization monomers as a solvent for preparing a masterbatch. Yes. This makes it possible to select a compound having a low viscosity instead of a polymer monomer having a high viscosity and use it as a solvent for the master batch, and to easily disperse or dissolve the additive in the solvent. In this case, since the compound having the same functional group as one of the polymerization monomers is used and the blending amount of the masterbatch is very small, there is no influence on the obtained optical material resin.

The present invention secondly provides the method for producing a resin for optical materials, wherein in the first method for producing a resin for optical materials, the first functional group is a functional group having active hydrogen. To do.
The functional group having active hydrogen is, for example, a functional group such as —OH, —SH, —NH ₂ , —NH, or —COOH, and an addition reaction with a functional group such as a (thio) epoxy group or an iso (thio) cyanate group. By doing so, it can be polymerized.

Thirdly, in the first or second method for producing a resin for optical materials according to the present invention, the second functional group is a functional group selected from an epoxy group, a thioepoxy group, an isocyanate group, and an isothiocyanate group. The manufacturing method of resin for optical materials characterized by these is provided.
These functional groups can be polymerized by an addition reaction with a functional group having active hydrogen.

Fourthly, in the method for producing a resin for optical materials according to any one of the first to third aspects, the first polymerization monomer having the first functional group is represented by the general formula R- (SCH ₂ SH) _n.
(In the formula, R represents an organic residue excluding an aromatic ring, and n represents an integer of 1 or more.)
And a compound having two or more mercapto groups in a molecule represented by the formula:

  A compound having two or more mercapto groups in the molecule is excellent in high refractive index, heat resistance and impact resistance, and is suitable as a material for plastic lenses, but has a very high viscosity. Therefore, it is not suitable as a solvent for the master batch, and is suitable for the method of the present invention using a polymerization monomer and another compound as the solvent for the master batch.

  Fifth, in the method for producing a resin for optical materials according to any one of the first to fourth aspects, the viscosity of the first polymerization monomer or the second polymerization monomer is 420 mPa · s / 25 ° C. or more. The viscosity of the compound as the solvent of the masterbatch is 400 mPa · s / 25 ° C. or less, and a method for producing a resin for optical materials is provided.

  A polymerization monomer having a viscosity of 420 mPa · s / 25 ° C. or higher is too high in viscosity and is not suitable as a solvent for a masterbatch. By using a compound having a viscosity of 400 mPa · s / 25 ° C. or lower as the solvent of the master batch, the additive can be easily dispersed or dissolved in the solvent.

Sixthly, in the fifth method for producing a resin for optical materials according to the present invention, the viscosity of the compound as a solvent for the masterbatch is 250 mPa · s / 25 ° C. or less. A manufacturing method is provided.
By using a compound having a viscosity of 250 mPa · s / 25 ° C. or lower as the solvent of the masterbatch, dispersion or dissolution of the additive in the solvent is further facilitated.

  Seventhly, in the method for producing a resin for optical materials according to any one of the first to sixth aspects, the concentration of the additive in the master batch is in the range of 100 to 100,000 ppm. A manufacturing method is provided.

  If the concentration of the additive in the master batch is too low, the compounding amount of the master batch becomes too large, and there is a risk of adverse effects on the physical properties of the polymer obtained by using a solvent different from the polymerization monomer, On the other hand, if the concentration of the additive is too high, it becomes difficult to disperse or dissolve the additive, resulting in poor productivity.

Eighth, the present invention provides the method for producing a resin for optical materials, wherein the additive is a dye for bluing in the method for producing a resin for optical materials according to any one of the first to seventh aspects. To do.
Since the addition amount of the dye for bluing is very small, it is difficult to weigh, and the addition method by the master batch method is suitable.

Ninth, the present invention relates to (A) a first polymerization monomer having two or more reactive first functional groups in one molecule, and (B) a reaction with the first functional group in one molecule. Mixing a second polymerization monomer having two or more second functional groups and (C) a master batch in which an additive is dispersed or dissolved using the first functional group or the compound having the second functional group as a solvent. An optical material resin obtained by polymerizing the polymerizable composition is provided.
This resin for optical materials can be manufactured with good productivity and efficiency since a small amount of additive can be added in a master batch system of a low-viscosity solvent.

In the tenth aspect of the present invention, (A) a first polymerization monomer having two or more reactive first functional groups, (B) two or more reactive groups reacting with the first functional group in one molecule. A polymerizable composition in which a second polymerization monomer having a second functional group and (C) a master batch in which an additive is dispersed or dissolved using the first functional group or the compound having the second functional group as a solvent are mixed. Provided is a plastic lens using a resin for optical materials obtained by polymerizing a product.
Since this plastic lens can be added with a small amount of additive in a master batch system of a low viscosity solvent, it can be manufactured with good productivity and efficiency.

Hereinafter, although the manufacturing method of the resin for optical materials of this invention, resin for optical materials, and embodiment of a plastic lens are demonstrated, this invention is not limited to the following embodiment.
In the method for producing a resin for optical materials of the present invention, the first polymerization monomer having two or more reactive first functional groups in one molecule of the component (A) and the one molecule of the component (B) When a polymerizable composition is prepared by mixing a second polymerizable monomer having two or more second functional groups that react with the first functional group, and this polymerizable composition is subjected to a polymerization reaction, (C As a component, a masterbatch in which an additive is dispersed or dissolved using a compound different from the first polymerization monomer of the component (A) and the second polymerization monomer of the component (B) as a solvent is characterized. is there.

Examples of the first functional group of the first polymerization monomer (A) include a hydroxyl group (—OH), a thiol group (—SH), an amino group (—NH ₂ ), an imino group (═NH), and a carboxyl group. A functional group having active hydrogen such as (—COOH) can be exemplified. The first polymerization monomer of the component (A) needs to have two or more functional groups having these active hydrogens in one molecule.

  Examples of the compound having two or more functional groups having active hydrogen include, for example, a polyol having two or more hydroxyl groups, a polythiol having two or more thiol groups, or one or more hydroxyl groups and thiol groups in one molecule. A typical example is a compound. These polyols, polythiols, compounds having one or more hydroxyl groups and thiol groups in each molecule are generally high in viscosity, and when the viscosity is 420 mPa · s / 25 ° C. or higher, the viscosity is too high and added. Since it becomes difficult to disperse or dissolve the agent, it is preferable to adopt a master batch method using the low viscosity solvent of the present invention.

  Examples of the polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucoside, pentaerythritol, diethylene Pentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dolcitol, iditol, glycol, inositol, hexanetriol, triglycerol, diglycerol, triethylene glycol, polyethylene glycol, tris (2- Hydroxyethyl) isocyanurate, cyclobutanedio , Cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,1,0,2,6] decane-dimethanol, bicyclo [4,3 , 0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,3,1,1] dodecane-diethanol, Aliphatic acids such as hydroxypropyltricyclo [5,3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol, maltitol, lactitol Polio , Dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, tetrabromobisphenol A, etc. Aromatic polyol, di- (2-hydroxyethyl) sulfide, 1,2-bis- (2-hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4-dithian-2,5-diol, Bis (2,3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, bis (4-hydroxyphenyl) sulfone (trade name bisphenol) S), tetrabromobisphenol S, tetramethylbisphenol S, 4,4′-thiobis (6-tert-butyl-3-methylphenol), 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane, etc. Examples include polyols containing sulfur atoms.

ちなみに、上記（２）式で示されるペンタエリスリトールテトラキス（３−メルカプトプロピオネート）の粘度は、４３０ｍＰａ・ｓ／２５℃と高粘度である。 In addition, the polythiol is not particularly limited. For example, 4-mercaptomethyl-3,6-dithio-1,8-octanedithiol represented by the following formula (1), pentaerythritol tetrakis represented by the following formula (2) ( 3-mercaptopropionate) and tetrathiol represented by the following general formula (3) can be exemplified.

Incidentally, the viscosity of pentaerythritol tetrakis (3-mercaptopropionate) represented by the above formula (2) is as high as 430 mPa · s / 25 ° C.

Specific examples of the tetrathiol represented by the general formula (3) include compounds (A) to (G) having the following structural formula.

  Other polythiols include, for example, di (2-mercaptoethyl) ether, 1,2-ethanedithiol, 1,4-butanedithiol, ethylene glycol dithioglycolate, trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (2-mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptoacetate), 1,2-dimercaptobenzene, 4-methyl-1,2-di Mercaptobenzene, 3,6-dichloro-1,2-dimercaptobenzene, 3,4,5,6-tetrachloro-1,2-dimercaptobenzene, O-xylylenedithiol, m-xylylenedithiol, p- Xylylenedithiol, and 1 3,5-tris (3-mercaptopropyl) isocyanurate.

  As the polythiol, a polythiol compound having two or more mercapto groups in the molecule represented by the following general formula (4) can be preferably used. A resin obtained using this polythiol compound is excellent in high refractive index, impact resistance and heat resistance, but generally has a high viscosity.

R- (SCH ₂ SH) _n (4)
In said formula (4), R represents the organic residue except an aromatic ring. The organic residue is selected from linear or branched aliphatic, alicyclic, heterocyclic, or linear or branched aliphatic, alicyclic or heterocyclic having a sulfur atom in the chain. One or more of these may be mentioned. In the formula, n is an integer of 1 or more, and one or more, preferably two or more mercaptomethylthio groups are required in one molecule. Moreover, you may have mercapto groups other than a mercaptomethylthio group.

  Specific examples of the polythiol compound represented by the general formula (4) include 1,2,5-trimercapto-4-thiapentane, 3,3-dimercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-dimercaptomethyl-1,9-dimercapto-2, 5,8-trithianonane, 3,7-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 4,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethyl-1,6-dimercapto-2,5-dithiahexane, 3-mercaptomethylthio-1,5-dimercapto 2-thiapentane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,4,8,11-tetramercapto-2,6,10 -Trithiaundecane, 1,4,9,12-tetramercapto-2,6,7,11-tetrathiadecane, 2,3-dithia-1,4-butanedithiol, 2,3,5,6-tetrathia -1,7-heptanedithiol, 2,3,5,6,8,9-hexathia-1,10-decanedithiol, 4,5-bis (mercaptomethylthio) -1,3-dithiolane, 4,6-bis (Mercaptomethylthio) -1,3-dithiane, 2-bis (mercaptomethylthio) methyl-1,3-dithietane, 2- (2,2-bis (mercaptomethylthio) ethyl 1,3 polythiol compounds include such dithietane, it may be used each alone, or may be used in combination of two or more. Among these, 1,1,2,2-tetrakis (mercaptomethylthio) ethane and 1,1,3,3-tetrakis (mercaptomethylthio) propane can be preferably used. The viscosity of 1,1,3,3-tetrakis (mercaptomethylthio) propane is 1000 mPa · s / 25 ° C., which is very high.

  Examples of the compound having one or more hydroxyl groups and thiol groups in one molecule include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerol di (mercaptoacetate), 1-hydroxy-4- Mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3 -Butanediol, pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate) Pentaerythritol pentakis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercaptodiphenylsulfone, 2 Examples include-(2-mercaptoethylthio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulcylate), hydroxyethylthiomethyltris (mercaptoethylthio) methane, and the like.

  (B) As the second functional group of the second polymerization monomer having two or more second functional groups in one molecule that reacts with the first functional group of the component, epoxy group, thioepoxy group, isocyanate, isothiocyanate Groups can be exemplified. Such a functional group can be polymerized by addition reaction with the active hydrogen of the first polymerization monomer.

  Specific examples of the compound having a thioepoxy group include a thioepoxy compound obtained by replacing part or all of the oxygen of an epoxy group of an existing epoxy compound with sulfur. Further, in order to increase the refractive index of the plastic lens, a compound containing a sulfur atom in addition to the thioepoxy group is more preferable. Specific examples include 1,2-bis (β-epithiopropylthio) ethane, bis (β-epithiopropyl) sulfide, bis (2,3-epithiopropyl) sulfide, 2,5-bis (β- Epithiopropylthiomethyl) -1,4-dithian chain aliphatic thioepoxy compounds, 1,4-bis (β-epithiopropylthiomethyl) benzene, 1,2-bis (2,3-epithiopropyl) Mention may be made of aromatic thioepoxy compounds such as thio) benzene and alicyclic thioepoxy compounds such as 1,3-bis (2,3-epithiopropylthio) cyclohexane.

  Moreover, the compound which has one or more disulfide bond (SS) in a molecule | numerator can be illustrated as a compound for high refractive indexes which has an epoxy group and / or a thioepoxy group. Examples of such compounds include (thio) epoxy compounds having one disulfide bond in the molecule such as bis (2,3-epoxypropyl) disulfide and bis (2,3-epithiopropyl) disulfide, and bis ( 2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ethane, bis (6,7-epithio-3,4-dithiaheptane) sulfide, 1,4-dithian-2,5- Bis (2,3-epithiopropyldithiomethyl), 1,3-bis (2,3-epithiopropyldithiomethyl) benzene, 1,6-bis (2,3-epithiopropyldithiomethyl) -2- (2,3-epithiopropyldithioethylthio) -4-thiahexane, 1,2,3-tris (2,3-epithiopropyldithio) propane Having two or more disulfide bonds (thio) epoxy compounds within.

  Examples of the compound having an iso (thio) cyanate group include aliphatic polyisocyanate compounds such as ethylene diisocyanate, trimethylene diisocyanate, 2,4,4-trimethylhexane diisocyanate and hexamethylene diisocyanate, and alicyclic rings such as isophorone diisocyanate. Aromatic polyisocyanate compounds, aromatic polyisocyanate compounds such as xylylene diisocyanate, sulfur-containing aliphatic polyisocyanate compounds such as bis (isocyanate methyl) sulfide, and aromatic sulfide polyisocyanates such as 2-isocyanate phenyl-4-isocyanate phenyl sulfide Compounds, aromatic disulfide polyisocyanate compounds such as bis (4-isocyanatophenyl) disulfide, 2,5-diisocyanate Sulfur-containing alicyclic polyisocyanate compounds such as tetrahydrothiophene, aromatic polyisothiocyanate compounds such as 1,2-diisothiocyanate benzene, aliphatic polyisothiocyanate compounds such as 1,2-diisothiocyanate ethane, thiobis (3 Examples thereof include sulfur-containing aliphatic polyisothiocyanate compounds such as -isothiocyanate propane).

The master batch of component (C), which is a feature of the method for producing a resin for optical materials of the present invention, is obtained by dispersing or dissolving an additive to be incorporated in a small amount in a resin for optical materials in a solvent. In the present invention, as a solvent of the masterbatch, the above example _-OH, -SH, -NH 2, -NH, first functional group or active hydrogen and the addition reaction to epoxy groups having an active hydrogen -COOH like, thioepoxy A compound having a second functional group selected from a group, an isocyanate group, and an isothiocyanate group is used. In the present invention, the compound used as the solvent of the masterbatch is a compound having the same functional group as the compound constituting the polymerization monomer but different. By using a compound different from the compound constituting the polymerization monomer as the solvent for the masterbatch, it is possible to select a solvent having a low viscosity. Either a compound having a first functional group having active hydrogen or a compound having a second functional group that undergoes addition reaction with active hydrogen can be used as a solvent for the masterbatch. However, the compound having the second functional group is unstable although having a low viscosity, and the pot life of the produced master batch is shortened. Therefore, the compound having the first functional group is preferably used as a solvent for the master batch.

  As a compound having in the molecule a functional group having active hydrogen used as a solvent for the masterbatch, it has at least two functional groups having active hydrogen in one molecule so as not to inhibit the polymerization reaction of the polymerization monomer. It is preferable. The viscosity is preferably 400 mPa · s / 25 ° C. or lower, particularly 250 mPa · s / 25 ° C. or lower.

  Specifically, among the above-described polyol having two or more —OH groups, polythiol having two or more —SH groups, or a compound having one or more hydroxyl groups and one thiol group in one molecule, low The thing of a viscosity can be selected and used. Preferable examples include 4,8or4,7or5,7-dimercaptomethyl-1,11-dimercapto-3 in (A) to (C), which are specific examples of tetrathiol represented by the general formula (3). , 6,9-trithiaundecane (viscosity 210 mPa · s / 25 ° C.), 4-merkatomethyl-3,6-dithia-1,8-octanedithiol (viscosity 47 mPa · s / 25 ° C.) represented by the above formula (1) ) And the like.

  As an additive, the purpose of using a masterbatch is to add a precise amount of an additive that is difficult to accurately weigh in a small amount, so a dye for bluing that is blended in a small amount in a resin for optical materials , Polymerization catalyst, internal mold release agent, light stabilizer, antioxidant and the like.

  The blueing dye is a blue or purple dye that counteracts the yellowness when added to the plastic lens resin material itself and maintains the transparency of the plastic lens. The dye for bluing is not particularly limited, but an oil-soluble dye, particularly an anthraquinone violet oil-soluble dye or an anthraquinone blue oil-soluble dye is preferable. Specific examples of these oil-soluble dyes include C.I. I. Solvent Violet 13, C.I. I. Solvent Violet 14, C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12 etc. are mentioned.

  In addition, the color tone of the plastic lens can be finely adjusted by using the red and orange dyes together with the blue and violet dyes. The red and orange dyes are not particularly limited, but specific examples include C.I. I. Solvent Red 111, C.I. I. Solvent Red 179, C.I. I. Solvent orange 60 etc. are mentioned.

  The concentration of additives such as dyes in the masterbatch used in the present invention is not particularly limited, but a concentration of 100 ppm or more in the solvent is preferable, and a range of 300 to 100,000 ppm is particularly preferable. If the concentration is less than 100 ppm, the concentration of the additive in the masterbatch is low. For example, in order to reduce the yellowness of the plastic lens, a large amount of the blueing masterbatch must be added to the plastic lens raw material. May have an influence on the original physical properties, such as refractive index and heat resistance. If the additive is added in excess of 100,000 ppm, the concentration of the additive in the master batch is too high, and it becomes difficult to uniformly disperse or dissolve the additive such as a dye.

  The preferable addition amount of the dye for bluing with respect to the monomer for plastic lenses is in the range of 0.01 ppm to 10 ppm, more preferably 0.1 ppm to 5 ppm. When the addition amount is less than 0.01 ppm, the effect of reducing the yellowness of the plastic lens is very small, and no significant difference is seen with respect to the plastic lens with no dye added. Moreover, when it adds exceeding 10 ppm, the color tone of a plastic lens will become blue or purple too much, and it will become a color tone like the dyed color lens rather than colorless and transparent.

  In the method for producing a resin for optical materials of the present invention, a polymerizable composition can be prepared by mixing the component (A), the component (B) and the component (C). In preparing this polymerizable composition, an ultraviolet absorber can be blended in addition to the above components.

  As the ultraviolet absorber, any ultraviolet absorber can be used as long as it is excellent in compatibility with the polymerizable monomer of the component (A) and the polymerizable monomer of the component (B). Examples thereof include benzophenone, benzotriazole, phenyl salicylate, triazine, and nickel salt. Among these, a benzotriazole type is preferable because it has a good solubility in raw material monomers, a high ultraviolet-absorbing ability, and a feature that the color of the compound itself is light or white and the lens is difficult to be colored.

  Examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 5-chloro-2- (3,5-di-) tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5- Di-tert-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-te t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2 -(2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 1.6-bis (4-benzoyl-3-hydroxyphenoxy) -hexane, 1,4-bis (4-benzoyl-4-octyl) Phenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole and the like can be exemplified. A reactive ultraviolet absorber having a polymerizable functional group such as a (meth) acryloyloxy group, for example, 2- (2-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole can also be used.

  The compounding quantity of a ultraviolet absorber is 0.1-5 weight part with respect to 100 weight part of raw material monomers, Preferably it is 0.2-3 weight part. By dissolving the ultraviolet absorber in such an amount in the monomer, the hue of the resulting resin for optical materials is slightly yellowish. Therefore, by preparing and using a blueing masterbatch in which a blue or violet bluing dye is dispersed or dissolved, a colorless and transparent optical material resin is produced without impairing the properties of the optical material resin. can do.

  Moreover, it is preferable to mix | blend a polymerization catalyst with a polymeric composition. There are no particular restrictions on the polymerization catalyst for the (thio) epoxy group, but specific examples include tertiary amines such as dimethylbenzylamine, dimethylcyclohexylamine, diethylethanolamine, dibutylethanolamine, tridimethylaminomethylphenol, and ethyl. Examples include imidazoles such as methylimidazole. Specific examples of isocyanate and isothiocyanate polymerization catalysts include amine compounds such as ethylamine, ethylenediamine, triethylamine, and tributylamine, dibutyltin dichloride, dimethyltin dichloride, and the like.

  Moreover, a light stabilizer, antioxidant, etc. can be mixed with a polymeric composition other than a polymerization catalyst as needed. Specific examples of the light stabilizer or the antioxidant include a hindered amine light stabilizer, a hindered phenol antioxidant, a phosphite antioxidant, a thioether antioxidant, and the like. By blending these components, it is possible to improve the weather resistance of the plastic lens. The addition of these components can also employ a master batch method if necessary.

  The polymerization and curing of the polymerizable composition containing the above components is not particularly limited, but cast polymerization is usually used when producing a plastic lens. The side surfaces of two circular glass molds arranged opposite to each other are fixed with an adhesive tape or a gasket, and a mold in which a gap between the glass molds is sealed is assembled. The mold is filled with a polymerizable composition, and heat energy or light A plastic lens can be obtained by polymerizing and curing with energy.

  When the plastic lens according to the present invention is used as a correction lens or a fashion lens, it is preferable to apply an antireflection film in order to increase light transmittance and prevent flicker due to surface reflection. It is particularly preferable to provide a hard coat layer in order to improve the adhesion of the antireflection film or to prevent scratches on the surface.

Preferable examples of the hard coat layer include those obtained by applying and curing a coating composition mainly comprising the following (A) and (B).
(A) One or more silane compounds having at least one reactive group.
(B) Inorganic oxide fine particles such as silicon oxide, antimony oxide, zirconium oxide, titanium oxide, tin oxide, tantalum oxide, tungsten oxide, aluminum oxide, titanium oxide, cerium oxide, zirconia oxide, silicon oxide, iron oxide, tin oxide Composite inorganic oxide fine particles using two or more of tungsten oxide.

  The component (b) is an effective component for adjusting the refractive index of the hard coat and increasing the hardness, and can be used alone or in combination. However, the film forming property is poor only with the component (b), and a transparent and tough film can be obtained by using the component (a) together. The component (a) can be used as it is, but it is preferable to use it after hydrolysis because the water resistance and hardness of the film can be improved.

  The thickness of the hard coat layer is usually preferably about 0.2 μm to 10 μm, more preferably about 1 μm to 3 μm. In the present invention, a hard coat in which a primer layer is provided between the lens fabric and the hard coat layer can also be used. This primer layer has the effect of further improving the adhesion between the lens fabric and the hard coat layer and improving the impact resistance of the lens after the hard coat treatment.

  In use as a correction lens, the optical performance is further improved by applying an antireflection film to the surface of the hard coat layer as described above. The antireflection film is a multilayer film obtained by laminating thin films having different refractive indexes, and can be inorganic or organic as long as the reflectance is reduced. However, in order to place importance on the surface hardness and the prevention of interference fringes, it is most preferable to provide a single-layer or multilayer antireflection film made of an inorganic material. Examples of inorganic substances that can be used include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, hafnium oxide, and magnesium fluoride, and so-called PVD such as ion plating, vacuum deposition, and sputtering. Can be applied by law.

Abbreviations of substances used in Examples and Comparative Examples are as follows.
Abbreviation: Substance name A-1: Pentaerythritol tetrakis (3-mercaptopropionate) (viscosity 430 mPa · s / 25 ° C.)
A-2: polythiol compound (viscosity 1000 mPa · s / 25 ° C.) mainly composed of 1,1,3,3-tetrakis (mercaptomethylthio) propane
B-1: m-xylene diisocyanate C-1: 4-mercatomethyl-3,6-dithia-1,8-octanedithiol (viscosity 47 mPa · s / 25 ° C.)
C-2: 4,8or4,7or5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (viscosity 210 mPa · s / 25 ° C.)
C-3: Polythiol compound comprising a polythiol compound and its oligomer (viscosity 350 mPa · s / 25 ° C.)

(Example 1)
As a dye, a trade name of Diaresin Blue J (Mitsubishi Kasei Kogyo Co., Ltd.) (1.0 g) is dispersed or dissolved in C-1 having a viscosity of 47 mPa · s / 25 ° C. As a result, it was possible to prepare a uniform and stable bluing masterbatch with no color unevenness by stirring for about 30 minutes.
Also, as plastic lens raw material, A-1 is 56.5 parts by weight, B-1 is 43.5 parts by weight, and UV absorber is SEESORB701 (Cipro Kasei Kogyo) 1.2 parts by weight, as an internal mold release agent. 0.1 parts by weight of Zelec UN (manufactured by Stepan) was added and mixed, and then thoroughly stirred, and the prepared bluing masterbatch was added to a completely dispersed or dissolved plastic lens raw material at a concentration of 500 ppm ( Then, 80 ppm of dibutyltin dichloride was added as a catalyst, and the mixture was sufficiently stirred at room temperature to obtain a uniform liquid. Subsequently, this composition was degassed for 30 minutes while reducing the pressure to 5 mmHg and stirring. This raw material was poured into a mold held by an adhesive tape using two glass molds, and the temperature was raised from 30 ° C. to 120 ° C. over 24 hours in an atmospheric polymerization furnace to polymerize and cure. Thereafter, the lens was removed from the mold and heated at 120 ° C. for 1 hour for annealing.
The plastic lens thus produced had a refractive index ne = 1.60, high transparency, no color unevenness, and good quality.

(Example 2)
As a dye, a trade name of Diaresin Blue J (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) (powder) 1.0 g is dispersed or dissolved in C-2 having a viscosity of 210 mPa · s / 25 ° C. As a result, it was possible to prepare a uniform and stable bluing masterbatch with no color unevenness by stirring for about 30 minutes.
Further, the plastic lens raw material used in Example 1 was added with the blueing masterbatch prepared in C-2 at a concentration of 500 ppm (0.5 ppm as a whole) to produce a plastic lens in the same manner as in Example 1. However, the refractive index ne = 1.60, high transparency, no color unevenness, and good quality.

Example 3
As a dye, a trade name of Diaresin Blue J (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) (powder) 1.0 g is dispersed or dissolved in C-3 having a viscosity of 350 mPa · s / 25 ° C. As a result, it was possible to prepare a uniform and stable bluing masterbatch having no color unevenness by stirring for about 1 hour.
In addition, the blueing masterbatch prepared in C-3 was added to the plastic lens raw material used in Example 1 at a concentration of 500 ppm (0.55 ppm as a whole) to produce a plastic lens in the same manner as in Example 1. However, the refractive index ne = 1.60, high transparency, no color unevenness, and good quality.

(Example 4)
As a dye, 1.0 g of a trade name OPLAS VIOLET 732 (Orient Chemical Co., Ltd.) (powder) is dispersed or dissolved in C-1 having a viscosity of 47 mPa · s / 25 ° C. to obtain a 1000 ppm bluing masterbatch of a purple dye. An attempt was made to prepare 1 kg. As a result, stirring was easily performed, and a uniform and stable bluing masterbatch with no color unevenness could be prepared by stirring for about 30 minutes.
As a plastic lens raw material, 55.6 parts by weight of A-2, 44.4 parts by weight of B-1, and 1.2 parts by weight of SEESORB 701 (manufactured by Sipro Kasei Kogyo) as an ultraviolet absorber, internal mold release As an agent, 0.1 part by weight of Zelec UN (manufactured by Stepan) was added and mixed, and then sufficiently stirred to be completely dissolved. To this plastic lens raw material, the prepared bluing masterbatch was added at a concentration of 1000 ppm (1 ppm as a whole), and then 150 ppm of dibutyltin dichloride was added as a catalyst, followed by thorough stirring at room temperature to obtain a uniform solution. Subsequently, this composition was degassed for 30 minutes while reducing the pressure to 5 mmHg and stirring. This raw material was poured into a mold held by an adhesive tape using two glass molds, and the temperature was raised from 25 ° C. to 120 ° C. over 24 hours in an atmospheric polymerization furnace to be polymerized and cured. Thereafter, the lens was removed from the mold and heated at 120 ° C. for 2 hours for annealing.
The plastic lens produced in this way had a refractive index ne = 1.70, high transparency, no color unevenness, and good quality.

(Example 5)
As a dye, a trade name of Diaresin Blue J (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) (powder) 1.0 g is dispersed or dissolved in C-2 having a viscosity of 210 mPa · s / 25 ° C. As a result, it was possible to prepare a uniform and stable bluing masterbatch with no color unevenness by stirring for about 30 minutes.
As a plastic lens raw material, 55.7 parts by weight of A-2, 44.3 parts by weight of B-1, and 1.2 parts by weight of SEESORB 701 (manufactured by Sipro Kasei Kogyo) as an ultraviolet absorber, internal release As an agent, 0.1 part by weight of Zelec UN (manufactured by Stepan) was added and mixed, and then sufficiently stirred to be completely dissolved. To this plastic lens raw material, the prepared bluing masterbatch was added at a concentration of 1000 ppm (1 ppm as a whole), and then 150 ppm of dibutyltin dichloride was added as a catalyst, followed by thorough stirring at room temperature to obtain a uniform solution. Subsequently, this composition was degassed for 30 minutes while reducing the pressure to 5 mmHg and stirring. This raw material was poured into a mold held by an adhesive tape using two glass molds, and the temperature was raised from 25 ° C. to 120 ° C. over 24 hours in an atmospheric polymerization furnace to be polymerized and cured. Thereafter, the lens was removed from the mold and heated at 120 ° C. for 2 hours for annealing.
The plastic lens produced in this way had a refractive index ne = 1.70, high transparency, no color unevenness, and good quality.

(Comparative Example 1)
A part of A-1 having a viscosity of 430 mPa · s / 25 ° C., which is a raw material for plastic lenses used in Example 1, is taken out, and 1.0 g of Diaresin Blue J (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) (powder) is added thereto. When an attempt was made to prepare 1 kg of a 1000 ppm bluing masterbatch of a blue dye by dispersing or dissolving, stirring was very difficult, and stirring was not possible unless it was divided into about 200 g, which was smaller than 1 kg. Furthermore, a uniform and stable bluing masterbatch with no color unevenness could not be produced unless the mixture was stirred for about 3 hours.

(Comparative Example 2)
A part of A-2 having a viscosity of 1000 mPa · s / 25 ° C., which is a plastic lens raw material used in Example 2, was taken out, and OPLAS VIOLET 732 (Orient Chemical Co., Ltd.) (powder) 1.0 g was added thereto. An attempt was made to prepare 1 kg of a 1000 ppm bluing masterbatch of a purple dye by dispersing or dissolving, and stirring was more difficult than in Comparative Example 1, and the normal stirring method could be uniformly dispersed or dissolved without color unevenness. It was not possible to produce a brewing masterbatch. Moreover, the preparation amount of the brewing master batch was reduced to 100 g and adjustment was attempted again. However, stirring was difficult as in the case of 1 kg, and the normal stirring method uniformly disperses or dissolves without color unevenness. It was impossible to make a brewing masterbatch.

The method for producing a resin for optical materials according to the present invention can produce a colorless and transparent resin for optical materials with good productivity without impairing various properties of the resin for optical materials. Can be used.
The resin for optical materials of the present invention can be used as a raw material for plastic lenses and the like.
The plastic lens of the present invention can be used as, for example, a spectacle lens.

Claims (10)

(A) a first polymerization monomer having two or more reactive first functional groups in one molecule;
(B) a second polymerization monomer having two or more second functional groups that react with the first functional group in one molecule;
(C) A master batch in which an additive is dispersed or dissolved using the compound having the first functional group or the second functional group as a solvent,
A method for producing a resin for an optical material, comprising polymerizing a polymerizable composition mixed with a polymer. In the manufacturing method of the resin for optical materials of Claim 1,
The method for producing a resin for optical materials, wherein the first functional group is a functional group having active hydrogen. In the manufacturing method of the resin for optical materials of Claim 1 or 2,
The method for producing a resin for an optical material, wherein the second functional group is a functional group selected from an epoxy group, a thioepoxy group, an isocyanate group, and an isothiocyanate group. In the manufacturing method of resin for optical materials in any one of Claims 1-3,
The first polymerization monomer having the first functional group is represented by the general formula R- (SCH ₂ SH) _n.
(In the formula, R represents an organic residue excluding an aromatic ring, and n represents an integer of 1 or more.)
A method for producing a resin for optical materials, which is a compound having two or more mercapto groups in a molecule represented by In the manufacturing method of resin for optical materials in any one of Claims 1-4,
The viscosity of the first polymerization monomer or the second polymerization monomer is 420 mPa · s / 25 ° C. or more, and the viscosity of the compound as a solvent of the master batch is 400 mPa · s / 25 ° C. or less. A method for producing a resin for optical materials. In the manufacturing method of resin for optical materials according to claim 5,
A method for producing a resin for optical materials, wherein the viscosity of the compound as a solvent of the master batch is 250 mPa · s / 25 ° C. or less. In the manufacturing method of resin for optical materials in any one of Claims 1-6,
The method for producing a resin for an optical material, wherein the concentration of the additive in the master batch is in the range of 100 to 100,000 ppm. In the manufacturing method of resin for optical materials in any one of Claims 1-7,
The method for producing a resin for optical materials, wherein the additive is a dye for bluing. (A) a first polymerization monomer having two or more reactive first functional groups in one molecule;
(B) a second polymerization monomer having two or more second functional groups that react with the first functional group in one molecule;
(C) A master batch in which an additive is dispersed or dissolved using the compound having the first functional group or the second functional group as a solvent,
A resin for optical materials obtained by polymerizing a polymerizable composition in which is mixed. (A) a first polymerization monomer having two or more reactive first functional groups in one molecule;
(B) a second polymerization monomer having two or more second functional groups that react with the first functional group in one molecule;
(C) A master batch in which an additive is dispersed or dissolved using the compound having the first functional group or the second functional group as a solvent,
A plastic lens characterized by using a resin for optical materials obtained by polymerizing a polymerizable composition obtained by mixing the above.