JP2002012676A - Colorant masterbatch for optical molded products and optical recording medium substrate - Google Patents

Abstract

(57) Abstract: A colorant masterbatch suitable for producing a colored optical resin molded product such as a colored DVD substrate or a CD-R substrate is provided. SOLUTION: This is a colorant masterbatch for obtaining a colored optical resin molded product by mixing with an optical resin material made of a thermoplastic resin, and having a viscosity average defined in the text of the optical resin material. A colorant masterbatch for an optical molded product that satisfies a specific conditional expression when the molecular weight is Mv1 and the viscosity average molecular weight defined in the text of the masterbatch is Mv2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorant masterbatch used for producing a colored optical resin molded product. Specifically, the viscosity average molecular weight of the colorant masterbatch is used within a certain range with respect to the viscosity average molecular weight of the optical resin material made of a thermoplastic resin. Accordingly, it is possible to provide an optical resin molded product having a design property and other functions while satisfying high optical characteristics required for the optical resin molded product. For more details, DVD,
The present invention relates to a colorant masterbatch capable of imparting functions such as designability and recording storability to a high-performance optical recording medium substrate such as a CD-R.

[0002]

2. Description of the Related Art Optical resin molded products having various optical functions are usually transparent or nearly colorless. However, a colored molded product may be used depending on the application. In particular, in recent years, colored products have increased in optical recording media typified by CDs (compact disks) and DVDs (digital versatile disks). The purpose of such coloring is to have a design property and a long-term storage property of the recording film.

[0003] Various methods are conceivable for coloring the optical recording medium as in the case of coloring a general resin. Among them, the master batch method can be one of the effective methods for the following reasons.

(1) In the case of a master batch, a dispersion medium is not used. Increasing the component increases the instability factor in many respects and is not fundamentally desirable.
In the case of an optical molded product, extremely minute foreign matter or deterioration is a field in which a problem is caused. On the other hand, particularly in the field of optical recording medium substrates and the like, it is exposed to an extremely high molding temperature, and the components contained in the material are likely to be easily degraded. In the case of a masterbatch, there is no need to consider the problem of thermal deterioration due to the dispersion medium, and therefore, the degree of freedom of coloring increases.

(2) In the case of a master batch, the problem of re-agglomeration does not occur. This point is extremely important in the field of optical molded products in which minute aggregates are a problem. Considerable attention must be paid to re-aggregation in so-called liquid colors and the like, and in some cases, the use of colorants may be restricted.

On the other hand, a method of coloring a resin using a masterbatch of a coloring agent is a method which has been used for a long time. For example, an aromatic polycarbonate resin widely used as an optical resin material is also described below. Proposals such as have already been made.

JP-A-61-236854 describes a resin composition for a coloring master in which carbon black is blended with an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 19,000. Such inventions are:
By focusing on the melt viscosity characteristics of a polycarbonate resin having a specific molecular weight, the inventors have reached the point where carbon black is contained in a high concentration. On the other hand, the invention described in this publication did not sufficiently satisfy the characteristics required for a master batch for obtaining a molded article for optical use.

Japanese Patent Application Laid-Open No. 6-345951 proposes a masterbatch of carbon black using a polycarbonate oligomer in place of the above-mentioned polycarbonate resin having a specific molecular weight. In particular, it is described that better dispersibility and the like can be obtained with respect to carbon black having a specific particle size than the invention of the above publication. However, the invention described in this publication also did not sufficiently satisfy the characteristics required for a master batch for obtaining an optical molded product.

That is, the inventions described in the above two publications do not take into account circumstances specific to optical molded products. 1
One is the extremely high dispersibility of the colorant at a level that is not optically recognized as a foreign substance. Such points have been increasingly improved in recent years. The other is high cycle molding represented by an optical recording medium substrate. Therefore, a very short melt plasticization is required, in which the masterbatch components need to be homogeneously mixed.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a colorant masterbatch suitable for producing a colored optical resin molded article such as a colored DVD substrate or a CD-R substrate. It is assumed that. The present inventors have conducted intensive studies to achieve such an object, and as a result, the viscosity average molecular weight of the colorant masterbatch and the viscosity average molecular weight of the optical resin material mixed with the colorant masterbatch are within a certain range. It has been found that such an object can be achieved by doing so. That is, the present inventors have found that a colored optical resin molded product that sufficiently satisfies the optical characteristics can be obtained even in a very short high cycle molding.

By setting the viscosity average molecular weight of the optical resin material to be mixed with the colorant masterbatch within a specific range, it is possible to make the behavior at the time of melt-kneading substantially equal. Thus, for example, the colorant masterbatch is softened and melted first, thereby preventing plasticization of the optical resin material, and conversely, the dispersion of the colorant due to the delayed melting of the colorant masterbatch does not occur. It is considered something.

[0012]

The present invention provides a colorant masterbatch for obtaining a colored optical resin molded product by mixing with an optical resin material comprising a thermoplastic resin,
When the viscosity average molecular weight defined in the text of the optical resin material is Mv1 and the viscosity average molecular weight defined in the text of the master batch is Mv2, a colorant master for an optical molded product satisfying the following formula (1). It depends on the batch.

[0013]

(Equation 2)

The optical resin molded article of the present invention includes an optical recording medium substrate, a lens, an optical filter, an optical fiber, an optical waveguide, an optical prism, and a microlens. It is suitable as a target of.

Further, as the optical recording medium of the present invention, compact discs (CD, CD-R, CD-RW, etc.), magneto-optical discs (MO, MD, etc.), digital versatile discs (DVD-ROM, DVD-V)
video, DVD-Audio, DVD-R, DVD-
And an optical card represented by a RAM and the like. Particularly, an optical disk is a suitable object.

The optical resin molded article of the present invention is colored by a coloring agent for various purposes. Such purposes include the provision of design properties, protection of parts having high photodegradability (by cutting off light rays having harmful wavelengths), identification of product types, and selection of light of specific wavelengths.

The colorant masterbatch for optical molded articles of the present invention is diluted according to the colorant concentration. That is, generally, the masterbatch is mixed with an uncolored optical resin material as a main raw material, and a colored optical resin molded product is obtained through a process such as melt molding. The optical material as the main raw material is generally not colored, but any colored material can be used.

The dilution ratio (weight ratio) of the colorant of the present invention is generally about 2 to 50 times, but preferably 3 to 30 times, more preferably for more precise optical molded products. The ratio is 3 to 25 times, more preferably 3.5 to 20 times, particularly preferably 4 to 18 times. Here, the dilution ratio is
For example, if the ratio is three times, it means that the uncolored optical resin material is 2 parts by weight with respect to 1 part by weight of the colorant master batch. Within the above range, the problem of contamination caused by the colorant masterbatch can be reduced.
In addition, problems such as uneven dilution due to a decrease in the dilution ratio and problems such as thermal deterioration due to an increase in the concentration of the colorant hardly occur.

As the thermoplastic resin forming the optical resin molded article of the present invention, various resins usable for optical applications can be mentioned. Specifically, examples thereof include an aromatic polycarbonate resin, an amorphous polyolefin resin, an acrylic resin, a hydrogenated polystyrene resin, an amorphous polyester resin, and an amorphous polyarylate resin. Further preferred in the present invention are aromatic polycarbonate resins, amorphous polyolefin resins, and amorphous polyarylate resins which require a high molding temperature. Among them, the aromatic polycarbonate resin is suitable as the thermoplastic resin forming the optical resin molded article of the present invention.

Examples of the amorphous polyolefin resin include APO resin manufactured by Mitsui Chemicals, Inc., Arton manufactured by JSR Corporation, and ZEONEX manufactured by Zeon Corporation. The details of the aromatic polycarbonate resin will be described later.

Next, the method of measuring the viscosity average molecular weight in the present invention will be described. Such a viscosity average molecular weight,
First, an optical resin material (for which Mv1 is required) or a colorant masterbatch (for which Mv2 is required) is dissolved in 20 to 30 times the weight of methylene chloride, and the soluble component is collected by filtration through celite. The solution is removed and dried sufficiently to obtain a solid soluble in methylene chloride. From a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride, the specific viscosity at 20 ° C. calculated by the following equation was calculated as follows:
Determined using an Ostwald viscometer. Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of falling methylene chloride, t is the number of seconds of falling of the sample solution]

Further, the viscosity average molecular weight M is determined by inserting the specific viscosity determined above into the following equation. η _SP /c=[η]+0.45×[η] ² c [η] = 1.23 × 10 ^-4 M ^0.83 c = 0.7

Therefore, Mv1 and Mv2, particularly Mv2, obtained as described above are values calculated from the specific viscosities measured in a state in which components other than resins such as coloring agents dissolved in methylene chloride are included.

In the present invention, Mv1 and Mv2 need to satisfy the following equation (1).

[0025]

(Equation 3)

More preferably, the following expression (2) is satisfied.

[0027]

(Equation 4)

More preferably, the following expression (3) is satisfied.

[0029]

(Equation 5)

By satisfying the above formula (1), the colorant masterbatch of the present invention can have almost the same plasticizing and kneading behavior as the optical resin material as the main raw material. This makes it possible to cope with high cycle molding with an extremely short plasticizing time and to achieve excellent dispersibility required for optical resin molded products.

The colorant used as the component B in the present invention includes perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, and quinoline. Organic dyes such as organic dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes, and carbon black. Transparent organic colorants are preferable among these. More preferred are anthraquinone dyes, perinone dyes, quinoline dyes, perylene dyes, coumarin dyes, and thioindigo dyes.

Specific examples of the component B dye include CI S
solvent Red 52, CISolvent R
ed 149, CI Solvent Red 15
0, CI Solvent Red 191, CI S
solvent Red 151, CI Solvent
Red 135, CI Solvent Red16
8, CI Disperse Red 22, CI S
solvent Blue 94, CI Solvent
Blue 97, CI SolventViolet
13, CI Solvent Violet 14,
CI Disperse Violet 28, CI
Solvent Green 3, CI Solven
Anthraquinone dyes known as t Green 28, CI Vat Orange 9, CI Vat
Pyranthrone anthraquinone dyes, isodibenzanthrone anthraquinone dyes known as Orange 2, CIVat Orange 4, CI V
at Orange 1, CI Vat Yellow
And dibenzopyrene quinones and anthraquinone dyes known as No. 4. As thioindigo dyes, CI Vat Red 1, CI Vat
Red 2, CI Vat Red41, CI Vat
Red 47 and the like. As perylene dyes, CI Vat Red 15, CI V
at Orange 7, CI Solvent Gr
F Orange 240, F Red 300, and Luengen series manufactured by BASF
F Yellow083, F Red339 and the like. Coumarin-based dyes include MACROLEX Fluorescent Yel manufactured by Bayer AG.
low 10GN, Solvent Yellow16
0: 1, MACROLEX Fluorescent
Red G and quinoline dyes include CI Solv
entYellow 33, CI Solvent Y
yellow 157, CI Disperse Yellow
ow 54, CI Disperse Yellow
160 and the like. As perinone dyes, CI Solvent Red 135, CI
Solvent Red 179, CI Solven
t Orange 60, CI Pigment Blue 15: 1 as a phthalocyanine dye, CI
Pigment Green 7, CI Pigmen
t Green 36 and the like. These can be used alone or in combination of two or more, and can be colored according to the purpose.

The colorant preferably has a small particle size in order to achieve sufficiently uniform dispersion, and more preferably 50.
It has a particle size of not more than μm, and such a colorant can be obtained by screening with various filters, followed by purification and crystallization.

As the component A which is a thermoplastic resin forming the colorant masterbatch of the present invention, the above-mentioned thermoplastic resins can be exemplified. As the component A, basically, a thermoplastic resin of the same type as the main resin material for optical use is used. On the other hand, from the viewpoint of the molecular weight distribution, those having almost the same characteristics in the molecular weight distribution are more preferable. For example, as long as the molecular weight distribution of the optical resin material as a main raw material has a single peak, it is more preferable that the component A also has a single peak. On the other hand, if the molecular weight distribution of the optical resin material as the main raw material is composed of two or more types of mixed components having different molecular weight ranges and has two or more peaks, the same peaks of two or more peaks are also observed in the component A. Are more preferred. The measurement of the viscosity average molecular weight is the average of the behavior due to the correlation between the individual molecular chains and the solvent, whereas the behavior in the mixed molten state is the average of the behavior of the correlation between the individual molecular chains, This is because the behavior such as the relaxation of the molecular chain may vary greatly depending on the distribution.

A colorant masterbatch containing all of the colorant contained in the obtained optical resin molded product as a B component is most preferable. This is because problems such as contamination can be avoided as much as possible. However, it is also possible to combine two or more masterbatches.

The colored optical resin molded product of the present invention comprises:
0.005 to 10% by weight, preferably 0.02% by weight of the colorant
To 5% by weight, more preferably 0.02 to 2% by weight. With such a content of the coloring agent, it is generally recognized that the coloring is clearly performed, and the function required for the coloring agent can be sufficiently exhibited.
When the content of the coloring agent exceeds 10% by weight, the properties as an optical resin molded product are affected, which is not preferable.

The form of the colorant masterbatch of the present invention,
Various forms and methods can be used for the manufacturing method. As a form of the colorant masterbatch, any form of a granular material and a pellet can be used, but a pellet form is particularly preferable. In the case of powders and granules, it is necessary to manufacture optical resin molded products in consideration of the problem of oxidative deterioration due to air containing minute components and the problem of heat deterioration components adhering to supply ports of molding machines. There is.

Pellets can be obtained by the most common method of cutting a melt-extruded strand.
Therefore, the shape may be cylindrical or prismatic. It is also possible to use a so-called hot cut method of directly cutting the melt extrudate. In such a case, it is general to take a shape close to a sphere.

As described above, the colorant masterbatch of the present invention can take any form or shape, but preferably has the same form and shape as the main raw material for optical use. This is because in such a case, problems of classification and uneven distribution at the time of mixing hardly occur, and the effects intended by the present invention can be further exhibited. Accordingly, the colorant masterbatch is in the form of a pellet, and most preferably in the form of a column. This is because most of optical materials as main raw materials are columnar pellets. Also, the size is preferably substantially the same as the size of the main raw material for optical use from the viewpoint of classification. Generally, the diameter is 2.
Those having a length of 0 to 3.3 mm and a length of 2.5 to 3.5 mm are suitable.

As a method for producing such a colorant master pellet, the following method can be mentioned. For example, (1) a method in which necessary raw materials (A component, B component and other optional components) are premixed and then melt-kneaded,
(2) a method in which a master agent containing a coloring agent in a high concentration is prepared, premixed with other raw materials, and then melt-kneaded;
And (3) a method of independently supplying and melting and kneading a master agent containing a coloring agent at a high concentration and other raw materials.

As the premixing method of the above (1), specifically, there is a method in which each component is put into a mixer such as a super floater, a Henschel mixer, a Nauter mixer, a tumbler and the like, followed by stirring and mixing. Another example is a method of uniformly dissolving the component B in the solution of the component A and then removing the solvent.

In the method (2), the master agent and other raw materials are premixed and melt-kneaded using the same mixer as in (1).

In the above method (3), the supply to the melt kneader is carried out independently for the master agent and other raw materials. In such cases, besides re-feeding the other raw materials into a melt kneader such as an extruder, in the case of a resin produced by melt polymerization, a method such as charging a master agent at any stage during the polymerization is used. Can also be taken.

Here, the master agent (hereinafter, simply referred to as “master agent”) used for producing the above-mentioned colorant master pellets may be in the form of pellets or granules. The master agent is preferably in the form of a powder. In the case of pellets, it is necessary to melt and mix an extremely high concentration of the coloring agent and the thermoplastic resin, which facilitates the thermal deterioration of the coloring agent. That is, in such a master agent, a method in which an excessive heat load can be avoided as much as possible is more preferable.

In order to prepare a powdery master agent, first, a method of mixing a coloring agent and other raw materials necessary for preparing the master agent with a powder mixer such as a Henschel mixer is used. No. As the mixer, a super floater is particularly preferred. Such a coloring agent may be in a liquid state dissolved or dispersed in another medium, in addition to a usual solid state. In the case of a liquid state, it is preferable to evaporate the medium by setting the heat generated during mixing and the setting of the jacket temperature of the mixer. In the case of a liquid, there is an advantage that such a liquid can be filtered to remove necessary foreign substances and poorly dispersed components at the same time.

As a second method for preparing a granular master agent, a method of simultaneously removing a solvent component from a solution of a higher concentration liquid master agent and other raw materials, or a method of preparing other raw materials is used. A method of dissolving in a solution to remove a solvent component is exemplified. The solution of the master agent and the other raw materials can be mixed or independently supplied into the solvent removing device. For example, a powder of the master agent can be obtained using a spray dryer.

The production of the colorant masterbatch is as follows.
It is preferable that the process is performed in an environment in which the presence of foreign matter that inhibits such optical characteristics is minimized. More specifically, it must be at the same level as when manufacturing optical materials for optical recording media. For example, (i) a raw material having a small amount of foreign substances is used, (ii) a manufacturing apparatus such as an extruder or a pelletizer is installed in an atmosphere of clean air obtained through a filter or the like, and (iii) a cooling bath. As the cooling water, one having a small amount of foreign matter such as metal ions obtained through an ion exchange resin or the like is used, and (iv) a raw material supply hopper, a supply flow path, a storage tank for the obtained pellets, and the like. Means such as filling with cleaner air or the like can be given. It is necessary that the colorant masterbatch of the present invention be manufactured in an environment where the levels of foreign substances and impurities obtained by these formulations are at the same level as when manufacturing optical materials for optical recording media.

As a device used for melt kneading, a screw type melt kneading device is preferable. For example, those generally used such as a single screw extruder and a twin screw extruder can be used. For the production of pellets, a vented twin-screw extruder is particularly preferable, and one capable of evacuating from the vent is preferable.

The details of the aromatic polycarbonate resin suitable as the resin forming the optical resin molded article of the present invention will be described below. The aromatic polycarbonate resin used in the present invention is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or a solid phase transesterification method of a carbonate prepolymer. Or a compound obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl @ methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis} (4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl}
Propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4
-Bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α , Α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m
-Diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,
3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-
Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, and these can be used alone or as a mixture of two or more.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred. Further, bisphenol A homopolymer, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) Phenyl｝ propane and α, α '
A copolymer with one or more monomers selected from -bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferably used, and particularly, a homopolymer of bisphenol A or 1,1-bis (4-hydroxy Phenyl) -3,3,5-trimethylcyclohexane and α,
A copolymer with α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferred.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like.

In producing the polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonate precursor by the interfacial polycondensation method or the melt transesterification method, if necessary, a catalyst, a terminal stopper and an oxidation of the dihydric phenol may be carried out. An inhibitor or the like may be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Examples thereof include ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When a polyfunctional compound producing such a branched polycarbonate resin is contained, such a ratio is preferably from 0.001 to 1 mol%, more preferably from 0.005 to 0.5 mol%, particularly preferably from the total amount of the aromatic polycarbonate. 0.01
~ 0.3 mol%. In addition, particularly in the case of the melt transesterification method, a branched structure may occur as a side reaction, and the amount of such a branched structure is also 0.001 to 1 mol%, preferably 0.005 to 5 mol%, of the total amount of the aromatic polycarbonate.
0.5 mol%, particularly preferably 0.01 to 0.3 mol%
Is preferred. The ratio is ¹ H
-It can be calculated by NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for promoting the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the resulting polycarbonate resins are capped by groups based on monofunctional phenols, so that Excellent heat stability. Such a monofunctional phenol is generally a phenol or a lower alkyl-substituted phenol, and may be a monofunctional phenol represented by the following general formula (1).

[0058]

Embedded image

(Wherein A is a hydrogen atom or a carbon number of 1 to 9)
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. )

Specific examples of the above monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

[0062]

Embedded image

[0063]

Embedded image

(Wherein X is -RO-, -R-CO-O
— Or —RO—CO—, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50. Show. )

As the substituted phenols of the general formula (2), those having n of 10 to 30, especially 10 to 26 are preferable. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol and Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

As the substituted phenols of the general formula (3), a compound in which X is -R-CO-O- and R is a single bond is suitable, and n is 10 to 30, especially 10 to 26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

It is desirable that the terminal terminator is introduced at least at 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained polycarbonate resin. More preferably, the terminal terminator is introduced in an amount of 80 mol% or more with respect to all terminals, that is, the terminal hydroxyl group (OH group) derived from dihydric phenol is more preferably 20 mol% or less, and particularly preferably. This is the case when 90 mol% or more of the terminal terminator is introduced to all the terminals, that is, when the OH group is 10 mol% or less. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol with the carbonate ester while heating in the presence of an inert gas. It is performed by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the late stage of the reaction, the system was set at 1.33 × 10 ³ -1.
The distillation of alcohol or phenol generated by reducing the pressure to about 3.3 Pa is facilitated. Reaction time is usually 1-4
About an hour.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be mentioned, with diphenyl carbonate being preferred.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium and potassium salts of dihydric phenol, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine; alkoxides of alkali metals and alkaline earth metals Manganese, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of the polymerization catalyst used is preferably 1 × 10 ⁻⁸ to 1 ×, based on 1 mol of the dihydric phenol used as the raw material.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

In the polymerization reaction, in order to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
It is preferable to add compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate, and ethoxycarbonylphenylphenyl carbonate. Of these, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred, and 2-methoxycarbonylphenylphenyl carbonate is particularly preferred.

Further, it is preferable to use a deactivator for neutralizing the activity of the catalyst in such a polymerization reaction. Specific examples of this deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonic acid, ethylbenzenebenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, phenylbenzenebenzenesulfonic acid, p-toluenesulfonic acid. Sulfonates such as methyl acrylate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; further, trifluoromethanesulfonic acid, naphthalenesulfonic acid, and sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid-2-
Phenyl-2-butyl, octylsulfonic acid tetrabutylphosphonium salt, decylsulfonic acid tetrabutylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetraethylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfone Acid tetrahexyl phosphonium salt, dodecyl benzene sulfonic acid tetraoctyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl Dimethyl ammonium Chill sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.

Among the deactivators, those of the phosphonium salt or ammonium salt type are preferred. The amount of such a catalyst is preferably 0.5 to 50 mol per 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 to 500 ppm, based on the polycarbonate resin after polymerization. It is used at a rate of 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

The polycarbonate resin has a viscosity average molecular weight (M) of preferably 10,000 to 22,000, more preferably 12,000 to 20,000, and more preferably 1 to 20,000.
3,000 to 18,000 is more preferred, and 13,50
0 to 16,500 is particularly preferred. An aromatic polycarbonate resin having such a viscosity average molecular weight can obtain sufficient strength as a resin molded article for optical use, and can reduce optical distortion and birefringence as much as possible. Further, two or more aromatic polycarbonate resins may be mixed.

In the case of optical resin molded articles, particularly optical recording media, it is often necessary to reduce the sodium component contained in the resin as much as possible. This is because such a component is one of the factors for generating optical foreign matter in a long term. As described above, since a polycarbonate resin uses a sodium compound as a catalyst in the production thereof, it is necessary to sufficiently wash with water in the case of interfacial polycondensation and to pay sufficient attention to the amount of such a catalyst in the case of the melt transesterification method. , The content of sodium element in the polycarbonate resin itself is 0.5 pp
m or less is preferable. More preferably, the content is 0.3 ppm or less, particularly preferably 0.2 ppm
It is preferable to use the following polycarbonate resin as an optical resin material as a main raw material of the present invention or an A component of the colorant master pellet.

The optical resin molded article of the present invention may contain various heat stabilizers, release agents, antistatic agents, light stabilizers, and the like. Further, it is possible to include these components in a high concentration as long as the object of the present invention is not impaired. However, it is more preferable that the master batch and the optical material as the main raw material are contained at substantially the same concentration.

As the release agent, various types of release agents can be used, but fatty acid esters are preferred. Examples of such a fatty acid ester include an ester of an aliphatic saturated monovalent carboxylic acid having 6 to 34 carbon atoms and a monohydric or dihydric or higher polyhydric alcohol. Such aliphatic saturated monovalent carboxylic acids include caproic acid, caprylic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, araxic acid, Behenic acid, montanic acid and the like.

Specifically, examples of esters of a monohydric alcohol and a saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like.

Specifically, as a partial ester or a total ester of a polyhydric alcohol and a saturated fatty acid, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate,
Behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetraperargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, etc. All or partial esters of dipentaerythritol.

Further, a partial ester of an aliphatic saturated monovalent carboxylic acid having preferably 10 to 24 carbon atoms, more preferably 16 to 22 carbon atoms, and a polyhydric alcohol having 2 or more valences can be mentioned. Examples of the dihydric or higher polyhydric alcohol include ethylene glycol, glycerin, and pentaerythritol. Particularly preferred is a partial ester of stearic acid and glycerin.

In the release agent, the fatty acid ester is preferably 90% by weight or more, more preferably 95% by weight or more, and particularly preferably substantially only the fatty acid ester based on 100% by weight of the total amount of the release agent. It consists of.

Further, the acid value of the above fatty acid ester is preferably 3 or less, more preferably 2 or less. In the case of glycerin monostearate, the acid value is 1.5 or less, and the purity is 95% by weight.
The above is preferred. More preferred glycerin monostearate has an acid value of 1.2 or less and a purity of 98% by weight or more. A known method can be used to measure the acid value of the fatty acid ester.

The composition ratio of the release agent is 0.005 to 0.5% by weight based on 100% by weight of the optical resin molded product.
Is more preferable, and more preferably 0.01 to 0.2% by weight.

As the heat stabilizer, a phosphorus stabilizer can be preferably mentioned. As the phosphorus-based stabilizer, any of phosphite-based, phosphonite-based, and phosphate-based stabilizers can be used.

Various phosphite stabilizers can be used in the present invention. Specifically, for example, general formula (4)

[0086]

Embedded image

[Wherein R ¹ is hydrogen or C 1-20
An alkyl group, an aryl group or alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio (the alkyl group has 1 to 3 carbon atoms)
0) or a hydroxy substituent, and the three R ^{1 s} can be selected either identically or differently,
Further, a cyclic structure can be selected by being derived from a dihydric phenol. ] It is a phosphite compound represented by these.

In a more preferred embodiment of the general formula (4), the following general formula (5)

[0089]

Embedded image

[0090] [wherein R ² and R ³ is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group or alkyl aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, R ² And R ³ are not hydrogen at the same time and can be selected either the same or different. And a phosphite compound represented by the following formula:

The general formula (6)

[0092]

Embedded image

[Wherein R ⁴ and R ⁵ are each hydrogen and have 1 carbon atom.
An alkyl group having 20 to 20 carbon atoms, an aryl group or an alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms,
And represents 25 2- (4-oxyphenyl) propyl-substituted aryl groups. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group and those substituted with an alkyl group. And a phosphite compound represented by the following formula:

The general formula (7)

[0095]

Embedded image

Wherein R ⁶ and R ⁷ are alkyl groups having 12 to 15 carbon atoms. Note that R ⁶ and R ⁷ may be the same or different from each other. And a phosphite compound represented by the following formula:

Examples of the phosphonite stabilizer include a phosphonite compound represented by the following general formula (8) and a phosphonite compound represented by the following general formula (9).

[0098]

Embedded image

[0099]

Embedded image

[Wherein, Ar ¹ and Ar ^{2 each} represent an aryl group or an alkylaryl group having 6 to 20 carbon atoms, or
It represents 5 to 25 2- (4-oxyphenyl) propyl-substituted aryl groups, and the four Ar ^{1 s} can be the same or different. Or two Ar ²
Can be the same or different from each other. ]

In the present invention, among the above-mentioned phosphite compounds and phosphonite compounds, more preferred phosphorus-based stabilizers include the phosphite compound represented by the above formula (5) (component E1) and the above-mentioned formula (8). )
(E2 component) and the phosphonite compounds represented by the above general formula (9) (E3 component) can be mentioned, and these can be used alone or in combination of two or more, and more preferably the above general formula (1) At least 5% by weight of 100% by weight of the E component
This is the case.

Preferred specific examples of the phosphite compound corresponding to the above general formula (4) include diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, Examples include diphenyl mono (tridecyl) phosphite, phenyl diisodecyl phosphite, and phenyl di (tridecyl) phosphite. More preferred specific examples corresponding to the above general formula (5) include triphenyl phosphite, tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, Tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite and the like. Dialkyl-substituted phenyl) phosphite is preferred, tris (di-tert-butylphenyl) phosphite is more preferred, and tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred. The above phosphite compounds can be used alone or in combination of two or more.

Preferable specific examples of the phosphite compound corresponding to the above general formula (6) include distearyl pentaerythritol diphosphite, bis (2,4-
Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite And distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-ter
(tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Such phosphite compounds can be used alone or in combination of two or more.

Preferred specific examples of the phosphite compound corresponding to the above general formula (7) include 4,4'-isopropylidenediphenol tetratridecyl phosphite.

Preferred specific examples of the phosphonite compound corresponding to the above general formula (8) include tetrakis (2,4-di-iso-propylphenyl) -4,4 ′
-Biphenylenediphosphonite, tetrakis (2,4-
Di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di- tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,
3'-biphenylenediphosphonite, tetrakis (2,
6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n
-Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl) Phenyl)-
4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3 ′
-Biphenylenediphosphonite; tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred; tetrakis (2,4-di-t
(tert-butylphenyl) -biphenylenediphosphonite is more preferred. This tetrakis (2,4-di-te
(rt-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically, tetrakis (2,4-di-tert-butylphenyl) -4,
4'-biphenylenediphosphonite (E2-1 component),
Tetrakis (2,4-di-tert-butylphenyl)
One kind of -4,3'-biphenylenediphosphonite (E2-2 component) and tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite (E2-3 component) Alternatively, two or more of them can be used in combination, but a mixture of these three is preferred. In the case of three kinds of mixtures, the mixing ratio is E2-1.
Component, E2-2 component and E2-3 component in a weight ratio of 10
The range of 0:37 to 64: 4 to 14 is preferable, and 100:
The range of 40-60: 5-11 is more preferable.

Preferred specific examples of the phosphonite compound corresponding to the above general formula (9) include bis (2,4-di-
iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,4-di-te
rt-butylphenyl) -3-phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3 -Phenyl-
Phenylphosphonite, bis (2,6-di-tert-
Butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)-
3-phenyl-phenylphosphonite and the like, and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferable, and bis (2,4-di-te
(rt-butylphenyl) -phenyl-phenylphosphonite is more preferred. This screw (2,4-di-tert)
-Butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite (E3-1 component). )and,
Bis (2,4-di-tert-butylphenyl) -3-
One or two of phenyl-phenylphosphonite can be used in combination, but a mixture of these two is preferred. In the case of two types of mixtures, the mixing ratio is
The weight ratio is preferably in the range of 5: 1 to 4, more preferably 5: 2 to 3.

On the other hand, examples of the phosphate-based stabilizers include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenylmonoorthoxenyl phosphate, tribubutoxyethyl phosphate, and the like. Examples thereof include dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, and preferred is trimethyl phosphate.

The optical resin molded article of the present invention may contain an antioxidant commonly known for the purpose of preventing oxidation. Examples of such antioxidants include pentaerythritol tetrakis (3-mercaptopropionate),
Pentaerythritol tetra (β-laurylthiopropionate) ester, glycerol-3-stearylthiopropionate, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-
Methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionate], tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane,
n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,
3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5
-Di-tert-butyl-4-hydrocinnamide),
3,5-di-tert-butyl 4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-
Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis {1,1-dimethyl-2-
[Β- (3-tert-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy] ethyl} -2,
4,8,10-tetraoxaspiro (5,5) undecane and the like.

The heat stabilizer is preferably contained in an amount of 0.0001 to 0.1 part by weight, more preferably 0.0005 part by weight, per 100 parts by weight of the optical resin molded article of the present invention.
To 0.05 parts by weight, more preferably 0.001 to 0.0 parts by weight
3 parts by weight. The antioxidant is used in an amount of 0.001 to 0.0 per 100 parts by weight of the optical resin molded product of the present invention.
5 parts by weight are preferred.

As a method for obtaining a resin molded article for optical use using the colorant masterbatch of the present invention, various conventionally known methods can be used. For example, desired methods such as injection molding, extrusion molding and compression molding can be used. It can be formed into a shape.
Particularly preferred is injection molding, and the colorant masterbatch of the invention is fully compatible with such injection molding. That is, the colorant master pellet of the present invention achieves good colorant dispersion even in a molding method with a short plasticization time by high cycle molding of an optical recording medium or the like, and does not lower optical characteristics caused by poor dispersion. Things.

The method for supplying the colorant masterbatch of the present invention and the optical material as a main raw material to a molding machine such as an injection molding machine may be a method of supplying them as a mixture thereof, or a method of independently supplying each of them in a specific amount. Any of the methods of supplying and mixing in an injection molding machine or the like can be performed. The mixture can be prepared by a method of mixing a predetermined ratio in a batch system, a method of continuously supplying the mixture to a mixer with a weighing machine to obtain a mixture, or the like.

[0112]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Further, “parts” in the examples means parts by weight unless otherwise specified. The evaluation items and methods are as follows.

(1) Observation of Optical Disk Appearance An optical disk manufactured as a sample for evaluation was visually observed for external appearance, and classified according to the following criteria. ：: Good appearance △: Slight appearance defects such as color unevenness and color streaks are observed

(2) Measurement of BLER The BLER of each sample was measured for a CD disk sample.
Is a BLER measuring machine (manufactured by SONY, CDplayer c)
otor unit CDS-3000). Note that C ₁ AVE in Table 3 is an average value per second of C1 errors (random errors that can be corrected by the C1 code).

(3) Measurement of viscosity average molecular weight The optical resin material or the colorant masterbatch was dissolved in 25 times the weight of methylene chloride, and the soluble matter was collected by filtration through celite. And dried sufficiently to obtain a solid soluble in methylene chloride. From a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride, the specific viscosity at 20 ° C. was determined using an Ostwald viscometer, and the viscosity average molecular weight was calculated by the conversion formula described in the text.

Reference Examples 1 to 15 (Production of Colorant Master Pellets) Each component shown in Tables 1 and 2 was produced in the following manner, and various evaluations were made.
The coloring agent component shown in Table 1 and the powder component of the A component were uniformly mixed with a super floater to obtain a master agent. This master agent was mixed with the remaining component A so as to have the composition ratios shown in Tables 1 and 2, and then uniformly mixed with a V-shaped blender with comb teeth. The obtained mixture was subjected to a twin-screw extruder with a vent of 30 mm in diameter [KTX-3, Kobe Steel, Ltd.].
0], while evacuating the vent from the vent, cylinder temperature 2
The resulting strand was melt-kneaded at 60 ° C., and the obtained strand was cooled with water for cooling and then pelletized with a pelletizer. The temperature of the pellet immediately after pelletization was about 129 ° C.

Further, a filter of a sintered metal was provided in the die portion of the extruder so that the number of foreign substances having a size of 5 μm or more was 20 or less per gram. All of the above devices were placed under an atmosphere of 1.005 atm in which clean air circulated through a filter, and water for strand cooling was passed through a 1 μm filter, and ion-exchanged water passed through an ion-exchange membrane was used. .

The size of the pellets was measured for 150 pellets with a digital caliper, and the average value was calculated. The average value was an average length of 3.0 mm and an average diameter of 2.7 mm in each of the prepared colorant master pellets.

[0119]

[Table 1]

[0120]

[Table 2]

[Examples 1 to 4 and Comparative Examples 1 and 2] The colorant master pellets obtained above and the pellets of the optical material as the main raw material were weighed from the respective tanks so as to have the proportions shown in Table 3. It was fed into the hopper of the molding machine by automatic conveyance through the machine. In addition, a mixing zone was provided immediately after the colorant master pellet conveying pipe, where uniform mixed pellets were formed and then charged into a hopper of a molding machine. The pellets were dried in a clean oven at 120 ° C. for 5 hours with hot air before being charged into the tank.

On the other hand, an injection molding machine (Sumitomo Heavy Industries, Ltd.)
DISK3 M3) is equipped with a mold for exclusive use of CD, a pitted nickel CD stamper is mounted on the mold, and the molding material is automatically fed into a hopper of a molding machine, and a cylinder temperature of 340 ° C. A mold having a diameter of 120 mm and a thickness of 1.2 mm was formed under the conditions of a mold temperature of 75 ° C., an injection speed of 100 mm / sec, and a holding pressure of 3.9 MPa, and an aluminum film was sputtered on the substrate to obtain a CD disk. Table 3 shows the evaluation results of these CD disks.

[0123]

[Table 3]

[Examples 5 to 7 and Comparative Example 3] In the same manner as in Example 1 except that the mold temperature was set to 125 ° C, the colorant master pellets and the main material pellets were placed in a hopper of an injection molding machine. The substrate was automatically conveyed, a disk substrate was formed, and a dye-based recording layer and a metal reflection film were formed on the disk substrate to produce a CD-R disk. Table 4 shows the evaluation results of the obtained CD-R discs.

[0125]

[Table 4]

Further, the recording surface of the CD-R disc was pasted on a window glass so that the recording medium was exposed to sunlight through the substrate, and a light fastness test was conducted to determine the number of days until an abnormality occurred in writing and reading. The colored disc had better lightfastness than the uncolored disc.

Examples 8 to 11 and Comparative Example 4 In the same manner as in Example 1, the colorant master pellets and the main material pellets were automatically conveyed to the hopper of the injection molding machine.

On the other hand, a mold dedicated to DVD was attached to the injection molding machine, and a nickel DVD-ROM stamper containing information such as address signals was attached to this mold. Then, the pellets were heated at a cylinder temperature of 380 ° C, a mold temperature of 115 ° C, an injection speed of 300 mm / sec, and a holding pressure of 3.
An optical disk substrate having a diameter of 120 mm and a thickness of 0.6 mm was obtained under the conditions of 9 MPa. Thereafter, an aluminum film was sputtered on the substrate, and a UV curable adhesive was applied by spin coating and adhered to obtain a two-layered optical disc. Table 5 shows the evaluation results of the obtained DVD-ROM disks.

[0129]

[Table 5]

Further, with respect to such a DVD disk, P
When the error rate of the I error was measured on a deck (DDU-1000 manufactured by Pulstec), the DVD disk obtained in the example of the present invention showed characteristics equivalent to those of a disk having a normal transparent substrate. On the other hand, Comparative Example 4 showed a high error rate.

Symbols and items indicating the components shown in Tables 1 to 5 are as follows. (A component) PC-1: Polycarbonate resin pellet for optical recording medium "Panlite AD-5503" (Teijin Chemical Co., Ltd.)
The polycarbonate resin pellets had a viscosity average molecular weight of 15,300.

PC-2: bisphenol A polycarbonate resin powder having a viscosity average molecular weight of 15,800 obtained by a phosgene method without using an amine catalyst; p-tert-butylphenol was used as a terminal stopper, and tris-butylphenol was used as a stabilizer. It contains 0.0025% by weight of 2,4-di-tert-butylphenyl phosphite.

PC-3: A bisphenol A polycarbonate resin powder having a viscosity average molecular weight of 17,500 obtained under the same polymerization conditions as PC-2 described above; p-tert-butylphenol was used as a terminal stopper, and a stabilizer was used as a stabilizer. It contains 0.0025% by weight of tris-2,4-di-tert-butylphenyl phosphite.

PC-4: Bisphenol A polycarbonate resin powder having a viscosity average molecular weight of 13,300 obtained under the same polymerization conditions as PC-2 described above; p-tert-butylphenol was used as a terminal stopper, and a stabilizer was used as a stabilizer. It contains 0.0025% by weight of tris-2,4-di-tert-butylphenyl phosphite.

PC-5: As a transesterification catalyst having a terminal hydroxyl group concentration of 34 mol% and a viscosity average molecular weight of 15,300, bisphenol A was used per mol of the starting bisphenol A.
Bisphenol A polycarbonate resin pellets obtained by a melt transesterification method using 2 × 10 ⁻⁷ mol of disodium salt of the above; an acid value of 0.8 and a purity of 9 as a releasing agent
0.05% by weight of 7.5% stearic acid monoglyceride and Tris-2,4-di-ter as stabilizer
0.0025% by weight of t-butylphenyl phosphite
contains.

PCC-1: Among the wholly aromatic dihydroxy components obtained by the phosgene method using an amine catalyst,
1,1-bis (4-hydroxyphenyl) -3,3,5
-Trimethylcyclohexane [bisphenol TMC]
Is 45 mol%, 4,4 ′-(m-phenylenediisopropylidene) diphenol [bisphenol M] is 55 mol%, and an aromatic polycarbonate copolymer powder having a viscosity average molecular weight of 14,800; As p
It uses -tert-butylphenol and contains 0.0025% by weight of tris-2,4-di-tert-butylphenylphosphite as a stabilizer.

PCC-2: PCC-1 was added with an acid value of 0.1.
8 and 97.5% pure stearic acid monoglyceride at 0.055% by weight and trimethyl phosphate at 0.1% by weight.
Aromatic polycarbonate copolymer pellets blended to give a 005% by weight ratio and manufactured under the same apparatus and environment as in the case of manufacturing PC-1

(Component B) Red dye F-1: perylene fluorescent red dye, manufactured by BASF
Lumogen F Red300 red dye F-2: coumarin fluorescent red dye, manufactured by Bayer AG
Macrolex Fluorescent Red
G Red dye F-3: Thioindigo fluorescent red dye, Arimoto Chemical Co., Ltd. Plast Red D54 Yellow dye F-1: Coumarin fluorescent yellow dye, manufactured by Bayer AG
Macrolex Fluorescent Yellow
ow 10GN Red dye-4: Perinone red dye, Arimoto Chemical Co., Ltd. P
last Red 8315 Red dye-5 Perinone red dye, Kp manufactured by Kiwa Chemical Co., Ltd.
Plast RedHG red dye-6 Perinone red dye, Kp manufactured by Kiwa Chemical Co., Ltd.
Plast RedH2G Red Dye-7: Anthraquinone red dye, Arimoto Chemical Co., Ltd.
Plast Red8320 orange dye-1: perinone-based orange dye, Arimoto Chemical Co., Ltd. Plast Orange 8150-2 yellow dye-2: heterocyclic (nitrogen-containing quinoline-based) yellow dye, Arimoto Chemical Co., Ltd. Plast Yellow 8010 Blue dye-1: Anthraquinone blue dye, manufactured by Bayer AG
Macrolex Blue RR Green Dye-1: Anthraquinone green dye, Sumitomo Chemical Co., Ltd.
SumiplastGreen G red dye F-1: perylene fluorescent red dye, manufactured by BASF
Lumogen F Red300 red dye F-2: coumarin fluorescent red dye, manufactured by Bayer AG
Macrolex Fluorescent Red
G

[0139]

By using the colorant masterbatch of the present invention, it is possible to obtain good colored optical resin molded products. In particular, such a masterbatch is suitable for coloring an optical recording medium such as a DVD, which is a high-density optical recording medium, or a CD-R or the like in which protection of a recording layer is important. In view of the above, the present invention has a special industrial effect in the field of optical resin molded products, which have conventionally had poor design properties, particularly in the field of high-density optical recording media for which great demand is expected in the future.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hisaga Shiga 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Teijin Chemicals Limited F-term (reference) 4F070 AA50 AC45 AC50 AC50 AE04 FA03 FB03 4J002 BB011 BC031 BG001 CF001 CF161 CG011 CG021 DA036 EU026 EU036 EU116 FD096 5D029 KA19

Claims (5)

[Claims] 1. A colorant masterbatch for obtaining a colored optical resin molded product by mixing with an optical resin material made of a thermoplastic resin, wherein the viscosity of the optical resin material is specified in the text. A colorant masterbatch for an optical molded product that satisfies the following formula (1) when the average molecular weight is Mv1 and the viscosity average molecular weight defined in the text of the masterbatch is Mv2. (Equation 1) 2. A colorant master batch comprising a thermoplastic resin (A component) and a colorant (B component), wherein the B component is an anthraquinone dye, a perinone dye, a quinoline dye, a perylene dye, a coumarin dye. The colorant masterbatch for an optical molded product according to claim 1, wherein the colorant masterbatch is at least one selected from thioindigo dyes and thioindigo dyes. 3. A colored optical resin molded product substantially comprising an aromatic polycarbonate resin.
The colorant masterbatch for an optical molded product according to any one of the above. 4. The colorant masterbatch for an optical molded product according to claim 1, wherein the colored optical resin molded product is an optical recording medium substrate. 5. An optical recording medium substrate formed by using the colorant masterbatch for an optical molded product according to claim 4.