JP2001192447A - Thermoplastic resin molding material having high transfer precision and optical disk base made of the material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin molding material having high transfer precision exhibiting excellent transferability in the production of an optical disk base as a high-density recording medium by injection molding. SOLUTION: The objective thermoplastic resin molding material having high transfer precision has a storage elastic modulus G' of <=2×108 Pa measured at Tg+10 deg.C and a measurement frequency of 100 rad/sec and of <=3×105 Pa measured at Tg+50 deg.C and a frequency of 10 rad/sec.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-precision transferable thermoplastic resin molding material for an optical disk substrate, and more particularly to a high-precision transferable thermoplastic resin molding material for an optical disk substrate which is a high-density storage medium when manufactured by injection molding. The present invention relates to a precision transferable thermoplastic resin molding material.

[0002]

2. Description of the Related Art CD, CD-ROM, CD-R, CD-
RW, DVD-ROM, DVD-R, DVD-RAM,
Various types of optical disks, such as MOs, are already widely used as information recording media for characters, music, videos, and the like. However, the market development is remarkable, and an optical disk (high-density optical disk) capable of recording a vast amount of information is expected in the future.

An optical disk is formed by forming an information recording layer on a transparent substrate. The material forming the substrate should have excellent transparency, low birefringence when forming the substrate, excellent moldability, excellent dimensional stability, and excellent heat resistance. Various characteristics such as excellent moisture resistance are required, and a characteristic which is particularly important in the future is said to be excellent transferability. Generally, the substrate is obtained by injection-molding a transparent thermoplastic resin molding material.However, in order to manufacture the high-density optical disk described at the beginning by injection molding, it is necessary to use the fine irregularities imprinted on the stamper faithfully. This is because whether or not transfer is possible is the first requirement. Recently, for example, an optical disk has been introduced in which the depth of the guide groove is as deep as 150 nm or more and the pitch interval between the guide grooves is as narrow as 0.85 μm or less. Is needed. Especially DVD-ROM, DVD-R, DVD-
Substrates such as RAMs have a single plate thickness of 0.6 mm, which is thinner than a CD of 1.2 mm, so that it is difficult to perform higher-level transfer.

[0004] Various approaches have been made to such a demand for transferability from both sides of molding technology and material modification. Regarding the former, for example, when transferring high-density irregularities onto an optical disk substrate by injection molding using a polycarbonate resin, it is effective to set the cylinder temperature of the molding machine to 380 ° C. or higher and the mold temperature to 130 ° C. or higher. It has been confirmed that there is. Regarding the latter, for example, Japanese Patent Application Laid-Open No. H11-035671 discloses that by controlling the content of a low molecular weight substance in a polycarbonate resin used for molding an optical disk substrate, the low molecular weight substance is added to a surface layer called a skin layer at the time of molding the substrate. Disperses easily, improves the fluidity of the substrate surface layer, and thus improves the transferability. Japanese Patent Application Laid-Open No. 9-54983 discloses that transferability is improved by widening the molecular weight distribution of a resin used for molding a substrate (the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn is increased). ing.

[0005]

According to the above prior art, for example, in the former case, the substrate is warped due to high-temperature molding, the cooling time in the mold is long, and the molding cycle is extended, resulting in poor productivity. The problem occurs. In the latter case, the use of a specific amount of a low-molecular-weight component is used to improve the fluidity.However, due to a decrease in the thermal stability of the resin, mold contamination during molding and a decrease in the strength of the substrate. It was not satisfactory enough. As described above, all of the conventional technologies discuss the effect of improving the transferability by improving the fluidity, and do not consider the mechanism by which the transfer occurs, but leave ample room for reconsideration in this regard. I was

When an optical disk substrate is manufactured by injection molding in the first place, sub-micron irregularities (pits, guide grooves, etc.) formed on the substrate are filled with resin in a cavity formed by a mold and pressurized. In this case, a pattern obtained by inverting the structure enters a groove of a stamper which has been stamped in advance, and is then formed by cooling and solidifying after being held for a certain period of time. In the above scheme, the resin filled in the cavity is the mold wall surface (stamper surface)
Immediately after contact with, heat is taken away. As a result, a cooling solidified layer called a skin layer is generated near the cavity wall,
In addition, a decrease in the resin temperature and an increase in the viscosity due to the decrease also occur inside. Therefore, the quality of the transferability depends on the deformability of the skin layer and the transmission of pressure for deforming the skin layer.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a high precision transfer heat having extremely high transferability (high precision transferability) from a stamper when a high-density optical disk is manufactured by injection molding. An object of the present invention is to provide a plastic resin molding material.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, specified the storage elastic modulus which governs viscoelasticity in a transparent thermoplastic resin molding material within a specific range. By doing so, it has been found that a high-precision transfer thermoplastic resin material having excellent high-precision transferability to a stamper shape, suitable for high-cycle molding, and having sufficient strength can be obtained. The present invention has been completed based on this finding.

According to the present invention, the storage elastic modulus G 'is 100
When measured at Tg + 10 ° C. while applying a frequency of rad / sec, it is 2 × 10 ⁸ Pa or less and 10 rad / s
ec frequency was applied and measured at Tg + 50 ° C.
The present invention relates to a high-precision transferable thermoplastic resin molding material comprising a resin having a pressure of 10 ⁵ Pa or less.

In the present invention, "high-precision transferability" means that when an optical disc substrate is manufactured by injection molding using a transparent thermoplastic resin molding material, the fine irregularities stamped on the stamper are faithfully formed under ordinary molding conditions. This is the property that can be transferred to Therefore, for example, a case where good transferability is not achieved only by means of high-temperature molding is not included in this category.

According to the present invention, in order to obtain sufficient signal characteristics as a disk substrate used for a high-density optical disk having a larger capacity, including a digital versatile disk (DVD), a molding process for molding the substrate is required. The material has a storage elastic modulus of 2 × 10 ⁸ Pa or less when measured at Tg + 10 ° C. by applying a frequency of 100 rad / sec and applying a frequency of 10 rad / sec to Tg + 5.
It is necessary to satisfy the requirement of being 3 × 10 ⁵ Pa or less when measured at 0 ° C. Here, Tg indicates the glass transition temperature of the resin.

The requirements of the present invention will be described in more detail.
The storage elastic modulus G ′ when a frequency of 100 rad / sec is applied is 2 × 1 when measured at a temperature of Tg + 10 ° C.
It is necessary that the pressure be not more than 0 ⁸ Pa, but preferably 1
× 10 ⁸ Pa or less, more preferably 2 × 10 ⁷ Pa
It is as follows. If the storage elastic modulus is greater than 2 × 10 ⁸ Pa, the deformation resistance of the skin layer is large and the transferability is reduced. In the present invention, the storage elastic modulus G ′ when a frequency of 10 rad / sec is further applied is required to be 3 × 10 ⁵ Pa or less when measured at a temperature of Tg + 50 ° C., and preferably 1 × 10 ⁵ Pa. Pa or less, more preferably 5 × 10 ⁴ Pa or less. If the storage elastic modulus is more than 3 × 10 ⁵ Pa, the fluidity of the resin inside the substrate is reduced, the pressure transmission is deteriorated, and the transferability is reduced.

The high-precision transferable thermoplastic resin molding material of the present invention is not particularly limited as long as it satisfies the above-mentioned viscoelastic conditions, but is usually an aromatic polycarbonate resin, a polymethyl methacrylate resin, an amorphous cyclic polyolefin. A resin or the like is used. Among them, an aromatic polycarbonate resin or a polymethyl methacrylate resin is preferable, and an aromatic polycarbonate resin is particularly preferable.

The aromatic polycarbonate resin may be any one which is usually used as a thermoplastic aromatic polycarbonate resin molded article, and is generally obtained by reacting a carbonate precursor with a dihydric phenol by an interfacial polymerization method or a melt polymerization method. Manufactured and obtained by any method can be used as well.

Representative examples of the dihydric phenol used in the production of the aromatic polycarbonate resin include hydroquinone, resorcinol, 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} (3,5-dibromo- 4-hydroxy) 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,
3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide,
Examples thereof include 4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenyl ester, and these can be used alone or in combination of two or more.

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-hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α′-bis ( 4-hydroxyphenyl)
Homopolymers or copolymers obtained from at least one bisphenol selected from the group consisting of -m-diisopropylbenzene are preferred, and in particular, a homopolymer of bisphenol A and 1,1-bis (4-hydroxyphenyl) ) -3,3,5-Trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene Is preferably used.

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

In producing the polycarbonate resin by reacting the dihydric phenol with the carbonate precursor by an interfacial polymerization method or a melt polymerization method, if necessary, a catalyst, a terminal stopper and an antioxidant for the dihydric phenol may be used. Etc. 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.

The reaction by the interfacial polymerization 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).

[0021]

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[Wherein A is a hydrogen atom or a carbon number of 1 to 9]
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 an aliphatic polyester group as a substituent, or long-chain alkyl carboxylic acid chlorides can be used. When blocked, these not only function as a terminal terminator or a molecular weight regulator, but also improve the melt flowability of the resin, not only facilitate the molding process, but also reduce the physical properties as a substrate, especially the water absorption of the resin. And the effect of reducing the birefringence of the substrate is preferably used. Among them, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

[0025]

Embedded image

[0026]

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. In the substituted phenols of the formula (2), n is 10 to 3
0, and particularly preferably 10 to 26, and specific examples thereof include, for example, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and tricontylphenol. Can be.

As the substituted phenols of the formula (3), compounds wherein X is -R-CO-O- and R is a single bond are suitable, and n is 10-30, especially 10-26. Those are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and tricontyl hydroxybenzoate. .

These terminal stoppers are desirably introduced at least at 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained polycarbonate resin. Or a mixture of two or more.

The reaction by the melt polymerization method is usually a transesterification reaction between a dihydric phenol and a carbonate ester. The dihydric phenol and the carbonate ester are mixed while heating in the presence of an inert gas to form an alcohol. Alternatively, it is carried out by a method of distilling 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 1330 to 13.3 Pa (10
The pressure is reduced to about 0.1 Torr to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

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, ditolyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be mentioned, among which diphenyl carbonate is preferable.

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 , 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, manga 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 these polymerization catalysts to be used is preferably 1 × 10 ⁻⁸ to 1 × 1 with ^respect to 1 mol of the dihydric phenol used as the raw material.
It is selected in the range of 0 ^-3 equivalents, more preferably 1 × 10 ^{-7 to} 5 × 10 ^-4 equivalents.

The polycarbonate resin has a viscosity average molecular weight (M) of preferably 10,000 to 22,000, more preferably 12,000 to 18,000, and more preferably 13,000.
000 to 17,000 are particularly preferred. A polycarbonate resin having such a viscosity average molecular weight is preferable because sufficient strength is obtained as an optical material, and the melt fluidity during molding is good, and molding distortion is not generated. The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (η _sp ) obtained from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 mL of methylene chloride at 20 ° C. into the following equation. η
_sp / c = [η] + 0.45 × [η] ² c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 ^-4 M ^0.83 c = 0.7 Furthermore, storage in the resin of the present invention As a method for controlling the elastic modulus, for example, (a) a polycarbonate resin solution (in the interfacial polymerization method, a polycarbonate resin solution after completion of polymerization is preferable) is added to n-heptane, acetone, MEK
A method of adding a poor solvent to a high-molecular-weight polycarbonate resin, such as a high-molecular-weight polycarbonate resin, filtering a precipitate containing a large amount of the high-molecular-weight polycarbonate resin, and drying and solidifying the remaining solution to remove high-molecular-weight components; (b) a moderately good solvent Solvents having properties such as methylene chloride / acetone, methylene chloride / n
Most of the polycarbonate resin (60 to 98% by weight, preferably 70 to 95% by weight) is dissolved using a mixed solvent of heptane, dioxolane / MEK, dioxane / acetone and the like, and the solution is dried and solidified. Examples of the method include a method in which a medium molecular weight component is contained in a large amount, and a method in which a high molecular weight polycarbonate resin is removed by fractionation and fractionation using (c) gel permeation chromatography (GPC). However, there is no particular limitation.

The raw material polycarbonate resin is produced by a conventionally known method (interfacial polymerization method, melt polymerization method, etc.), and then filtered in a solution state, or the granulated raw material after granulation (desolvent removal) is heated, for example. It is preferable to remove impurities and foreign substances such as low molecular weight components and unreacted components by washing with a poor solvent such as acetone under the conditions. Further, in the extrusion step (pelletizing step) of obtaining a pellet-shaped polycarbonate resin for use in injection molding, it is preferable to remove foreign substances by passing through a sintered metal filter having a filtration accuracy of 10 μm in a molten state. If necessary, it is also preferable to add an additive such as a phosphorus-based antioxidant. In any case, it is necessary to minimize the content of foreign materials, impurities, solvents and the like in the raw material resin before injection molding.

Further, an internal release agent can be added to the polycarbonate resin. The internal release agent in the present invention is a compound that is incorporated into a resin composition in order to improve the releasability of a resin molded product from a mold during melt molding. Examples of such an internal release agent include an ester of a monohydric alcohol and a fatty acid, a partial ester or a whole ester of a polyhydric alcohol and a fatty acid, an olefin wax,
Examples include olefin-based waxes containing a carboxyl group and / or a carboxylic anhydride group, silicone oil, organopolysiloxane, paraffin wax, and beeswax. Among them, esters of a monohydric alcohol and a fatty acid, and partial or total esters of a polyhydric alcohol and a fatty acid are preferably used. Such an ester of a monohydric alcohol and a fatty acid is an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. The partial ester or total ester of a polyhydric alcohol and a fatty acid is a partial ester or a total ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

Specific examples of the ester of a monohydric alcohol and a saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Stearyl stearate is preferred.

Specific examples of the partial or total ester of a polyhydric alcohol and a saturated fatty acid include monoglyceride stearate, diglyceride stearate, triglyceride stearate, monosorbate stearate, monoglyceride behenate, and pentaerythritol monostearate. , Pentaerythritol tetrastearate, pentaerythritol tetraperargonate,
Examples thereof include all or partial esters of dipentaerythritol such as propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, and dipentaerythritol hexastearate.

Among these esters, monoglyceride stearate, triglyceride stearate, pentaerythritol tetrastearate, and a mixture of triglyceride stearate and stearyl stearate are preferably used. Particularly, stearic acid monoglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used. This mixture of stearic acid triglyceride and stearyl stearate has a weight ratio of 6%.
The latter is preferably in the range of 20 to 40 with respect to 0 to 80.

The amount of the fatty acid ester in the internal release agent is preferably 90% by weight or more, more preferably 95% by weight or more, and more preferably one consisting essentially of the fatty acid ester, when the internal release agent is 100% by weight. .

The internal release agent of the present invention is added in an amount of 0.001 to 0.00 based on 100 parts by weight of the aromatic polycarbonate resin.
2 parts by weight is preferable, and 0.005 to 0.08 parts by weight is more preferable.

The polymethyl methacrylate resin is a resin obtained by polymerizing a methyl methacrylate monomer as a main raw material. For optical applications, usually a homopolymer is used, but other copolymerizable monomers,
Specifically, acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, and methacrylates such as ethyl methacrylate, propyl methacrylate, and butyl methacrylate were copolymerized in an amount of 10 mol% or less. Things can also be used. The polymerization method is not particularly limited, and a production method such as bulk polymerization, suspension polymerization, solution polymerization, or emulsion polymerization is used.

Examples of the amorphous cyclic polyolefin resin include hydrogenated ring-opened polymers of norbornene monomers. Examples of such norbornene-based monomers include norbornene, dimethanooctahydronaphthalene, trimethanododecahydroanthracene and their alkyl-substituted or alkylidene-substituted products, dicyclopentadiene, 2,3-dihydrodicyclopentadiene, dimethanooctahydrobenzoin Examples thereof include den, dimethanodecahydrobenzoindene, dimethanodecahydrofluorene, and alkyl-substituted products thereof. Further, those having a polar substituent such as a halogen atom, an ester-type residue, an ether-type residue, and a cyano group may be used. Among them, those having two or more functionalities make injection molding difficult, and those having one or more functionalities are preferably used.

Each of these norbornene monomers may be used alone, or two or more of these may be used in combination. Further, as a copolymer component, other cycloolefins such as cyclopropene, cyclobutene,
Cyclopentene, cycloheptene, cyclooctene,
5,6-dihydrodicyclopentadiene or the like can be usually used in a range of 30% by weight or less.

Acyclic olefins may be used as the molecular weight regulator. Among them, 1-butene and 1-butene are particularly preferred.
Α-olefins such as pentene and 1-hexene are preferred.

The ring-opened polymer of the norbornene monomer is
Although it is produced by a normal norbornene polymerization method, it is preferable to use a well-known metathesis catalyst as a polymerization catalyst. As the metathesis catalyst, a catalyst system containing a transition metal compound such as titanium tetrahalide and an organic metal such as an organoaluminum compound, or a catalyst system in which a third component such as an aliphatic or aromatic tertiary amine is combined therewith is preferable. .

The ring-opening polymerization can be carried out without using a solvent. Usually, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, and alicyclic hydrocarbons such as cyclohexane are used. And an inert organic solvent such as a halogenated hydrocarbon such as dichloroethane.
Further, the polymerization temperature is usually selected from the range of -20 ° C to 100 ° C, and the polymerization pressure is selected from the range of 0 to 4.9 MPa (0 to 50 kg / cm ² ) or less.

The ring-opened polymer of the norbornene monomer is
In order to use the hydrogenated product as a material for the optical transparent substrate, the Tg is desirably 120 to 200 ° C.

The hydrogenated product of the ring-opened polymer of a norbornene-based monomer is produced by using a well-known hydrogenation catalyst. Here, as the hydrogenation catalyst, those generally used in hydrogenation of olefin compounds can be used. For example, Wilkinson complex, cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, palladium-carbon , Ruthenium-carbon, nickel-diatomaceous earth and the like. The hydrogenation reaction is carried out at 0 to 250 ° C. under a hydrogen pressure of 1 to 200 atm in a homogeneous or heterogeneous system depending on the type of the catalyst. The hydrogenation rate is preferably 95% or more from the viewpoint of heat deterioration resistance and light deterioration resistance.
% Is more preferable.

An addition polymer of a norbornene monomer is also mentioned as an example of the amorphous cyclic polyolefin resin.
A homopolymer of a norbornene-based monomer is also used,
A copolymer obtained by copolymerizing ethylene is preferably used. As the norbornene-based monomer, the same ones as described above are used.

When an optical disk substrate is manufactured from the high precision transferable thermoplastic resin molding material, an injection molding machine (including an injection compression molding machine) is used. As this injection molding machine, a commonly used one may be used, but from the viewpoint of suppressing the generation of carbides and increasing the reliability of the disk substrate, the adhesion to the resin as a cylinder or a screw is low, and the corrosion resistance and abrasion resistance are low. It is preferable to use a material made of a material having properties. Injection molding conditions include a cylinder temperature of 3 when the material is, for example, an aromatic polycarbonate resin.
00-400 ° C, mold temperature 50-140 ° C is preferable,
Thus, an optically excellent optical disk substrate can be obtained. The environment in the molding step is preferably as clean as possible from the viewpoint of the present invention. Also,
It is also important to sufficiently dry the material to be subjected to molding to remove water, and to take care not to cause stagnation which may cause decomposition of the molten resin.

[0051]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The evaluation was performed according to the following method.

(1) Relaxation modulus viscoelasticity measuring device (Rhe
Ometric Scientific, rotary type rheometer, product name: RDAII), the sample is held between two parallel disks (diameter: 8 mm or 25 mm), and the strain is reduced by the gap loading method that applies periodic rotational deformation. The stress was measured and the storage modulus was calculated.

(2) Transferable injection molding machine (Meiki Seisakusho M
35B-D-DM), cavity thickness 0.6mm, diameter 1
20 mm mold, depth 145 nm, width 0.74μ
mold temperature of 125 using a stamper with a groove of
° C, filling time 0.2 seconds, cooling time 15 seconds, mold clamping force 343
A disk substrate was molded at × 10 ³ N. Next, r = 5 using an atomic force microscope (Seiko Electronics Industries SPI3700).
The groove depth of the disk substrate at 5 mm was measured, and the reproducibility of the groove shape (= 100 × disk groove depth / stamp groove depth (%)) was determined. In addition, the molded substrate
00 sheets were visually observed to check for cracks.

Example 1 In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 315.3 parts of ion-exchanged water and a 48% aqueous sodium hydroxide solution 57.
After charging 8 parts, 83.2 parts of 2,2-bis (4-hydroxyphenyl) propane and 0.17 parts of hydrosulfite were dissolved therein, 260.5 parts of methylene chloride was added, and the mixture was stirred. 40.8 parts of phosgene at 40 ° C
I blew it in a minute. After the injection of phosgene, 10.4 parts of a 48% aqueous sodium hydroxide solution and p-tert-
3.83 parts of butylphenol were added, stirring was started, and after emulsification, 0.08 parts of triethylamine was added.
The reaction was completed by stirring at 3 ° C. for 1 hour. After the completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and washed with water.When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, an isolation chamber having a foreign substance take-out port in the bearing was formed. The methylene chloride was evaporated with a provided kneader to obtain a powder. Then, Tris (2,4-di-te) was added to this powder.
0.0025% by weight of (rt-butylphenyl) phosphite and 0.05% by weight of stearic acid monoglyceride were added. Thereafter, the powder was melt-kneaded with a vent-type twin-screw extruder [KTX-46 manufactured by Kobe Steel Co., Ltd.] at a cylinder temperature of 240 ° C. to obtain a viscosity average molecular weight of 1
2,500 pellets were obtained. Further, the pellets were injection molded to produce a molded plate having a thickness of 2 mm, cut into a desired shape, and used as a test piece for measuring viscoelasticity. Table 1 shows the evaluation results of viscoelasticity and transferability.

Example 2 A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 175.5 parts of ion-exchanged water and a 48% aqueous sodium hydroxide solution.
2 parts were charged, and after dissolving 46 parts of 2,2-bis (4-hydroxyphenyl) propane and 0.10 parts of hydrosulfite, 145 parts of methylene chloride was added, and phosgene 22 was added under stirring at 15 to 25 ° C. .6 parts were blown in for 40 minutes. After the phosgene blowing was completed, 5.7 parts of a 48% aqueous sodium hydroxide solution and 1.97 parts of p-tert-butylphenol were added, stirring was started, and after emulsification, 0.05 parts of triethylamine was added.
For 1 hour to complete the reaction. After the completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, 170 parts of acetone was added to form a precipitate. The high molecular weight polycarbonate resin was removed by filtration to obtain a powder. Tris (2,4-di-ter)
0.0028% by weight of t-butylphenyl) phosphite and 0.05% by weight of stearic acid monoglyceride were added. Next, the powder was subjected to a cylinder temperature of 24 with a vent-type twin-screw extruder [KTX-46 manufactured by Kobe Steel Ltd.].
Melt kneading while degassing at 0 ° C., viscosity average molecular weight 151
00 pellets were obtained. Table 1 shows the evaluation results of the viscoelasticity and transferability at this time.

Comparative Example 1 A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 164.6 parts of ion-exchanged water and 30% of a 48% aqueous sodium hydroxide solution.
After charging 2 parts, 43.1 parts of 2,2-bis (4-hydroxyphenyl) propane and 0.09 parts of hydrosulfite were dissolved therein, 135.8 parts of methylene chloride was added, and the mixture was stirred with 15 to 25 parts. 21.2 parts of phosgene at 40.degree.
I blew it in a minute. After the injection of phosgene was completed, 5.4 parts of a 48% aqueous sodium hydroxide solution and 1.34 parts of p-tert-butylphenol were added, stirring was started, and after emulsification, 0.05 parts of triethylamine was added.
The reaction was completed by stirring at 1 ° C. for 1 hour. The subsequent steps were performed in the same manner as in Example 1 to obtain pellets having a viscosity average molecular weight of 21,700. Table 1 shows the evaluation results of the viscoelasticity and transferability at this time.

[0057]

[Table 1]

[0058]

According to the high-precision transferable thermoplastic resin molding material of the present invention, precision transferability to fine irregularities on a stamper is required for the production of an optical disk substrate, particularly a high-density optical disk substrate, obtained by injection-molding the material. Therefore, an optical disk substrate having extremely high signal characteristics can be obtained. Further, since the material of the present invention is suitable for high cycle molding and the molded substrate has sufficient strength, especially a digital versatile disk (D
VD) and more than 4.7 GB on one side, 40 GB
Hereinafter, the effect achieved by providing a high-density optical disk of preferably 20 GB or less is exceptional.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Masato Ando 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo F-term in Teijin Chemicals Limited (reference) 4J029 AA09 AA10 AB01 AB02 AB07 AC01 AD01 AD10 AE05 BB04A BB05A BB09A BB10A BB12A BB13A BD09A BE05A BF14A BH02 HC01 HC02 HC04A HC05A JA091 JB192 JC021 JC231 JF031 KD02 KD06 KD07 KE02 KE03 KE05 5D029 KA07 KC09

Claims (5)

[Claims] 1. The storage elastic modulus G ′ is 100 rad / sec.
When applying a frequency of c and measuring at Tg + 10 ° C., 2 ×
When measured at Tg + 50 ° C. by applying a frequency of 10 ⁸ Pa or less and 10 rad / sec, 3 × 10 ⁵ P
a high-precision transferable thermoplastic resin molding material comprising a resin having a value of a or less. 2. The highly precise transferable thermoplastic resin molding material according to claim 1, wherein the highly precise transferable thermoplastic resin molding material is an aromatic polycarbonate resin having a viscosity average molecular weight of 12,000 to 18,000. 3. An optical disk substrate made of the high-precision transferable thermoplastic resin molding material according to claim 1. 4. An optical disc substrate for digital versatile, comprising the high-precision transferable thermoplastic resin molding material according to claim 1. 5. An optical disk manufactured from the optical disk substrate according to claim 4, having a storage capacity of 4.7 GB or more on one side.