JPH09265663A - Digital video disk substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a disk substrate having little cracks during forming, small double refraction and excellent transfer property by specifying the structural units and compounding ratios of polycarbonate and polyorganosiloxane as the compsn. of a digital video disk substrate. SOLUTION: This substrate contains 5 to 100wt.% polycarbonate- polyorganosiloxane copolymer comprising a polycarbonate structural unit expressed by formula I and a polyorganosiloxane structural unit expressed by formula II, and 95 to 0wt.% polycarbonate resin. Moreover, the resin compsn. contains 0.1 to 10wt.% polyorganosiloxane structural unit to the whole amt. of the resin compsn. In formula I, R<1> , R<2> are independently halogen atoms or 1 to 6C alkyl groups or phenyl groups. In formula II, R<3> to R<6> are independently 1 to 6C alkyl groups or phenyl groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a digital video disk substrate, and more particularly to a digital video disk substrate made of a polycarbonate resin composition which has few cracks during molding, has small birefringence and is excellent in transferability. Is.

[0002]

2. Description of the Related Art CDs and CD-Rs which are conventional optical disks
Standards such as OM are disk diameter: 120 mm, disk thickness: 1.2 mm, structure: single-sided single side. On the other hand, the standard of the digital video disc (DVD) is that the disc diameter is 120 mm, the disc thickness is 1.2 mm, and the structure is double-sided attachment. Therefore, the disc substrate has a thickness of 0.
It will be 6 mm. Thus, the thickness of the disc substrate is 1.2
If the thickness is reduced from mm to 0.6 mm, it may cause an unfavorable situation such as damage during molding and increase in birefringence. This disk substrate material is transparent, heat resistant,
In recent years, polycarbonate has been widely used because of its excellent impact resistance and water resistance. If the molecular weight of the polycarbonate of the substrate material is increased in order to prevent cracking during molding of the disk substrate, birefringence will be further increased. Also, in order to reduce the birefringence, attempts have been made to mold the digital video disk substrate by using methods such as ultrasonic molding, multi-stage compression molding, and high-speed filling molding. There is a problem that the reduction is not sufficient, and rather, damage is more likely to occur as compared with the usual molding method.

[0003]

Under the circumstances, the present invention has a small number of cracks during molding and a small birefringence.
Moreover, it is an object of the present invention to provide a digital video disk substrate having excellent transferability.

[0004]

The inventor of the present invention has conducted extensive studies on a digital video disk substrate which has few cracks during molding and has small birefringence. As a result, the substrate material has a specific structure excellent in releasability. It has been found that the above object can be achieved by using a polycarbonate resin composition containing a polycarbonate-polyorganosiloxane copolymer. The present invention has been completed based on such findings. That is, the present invention provides (a) general formula (I)

[0005]

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(In the formula, R ¹ and R ² each represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different from each other;
Is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylidene group, a cycloalkylene group having 5 to 20 carbon atoms or a cycloalkylidene group, -O-, -S-, -SO.
-, - SO ₂ or -CO- indicates, p and q each represent an integer of 0 to 4, m is an integer of 1 to 150. ) Polycarbonate structural unit and general formula (II)

[0007]

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(In the formula, each of R ^{3 to} R ⁶ has 1 carbon atom.
~ 6 alkyl groups or phenyl groups, which may be the same or different from each other, A is a divalent organic residue, R is a monovalent or divalent organic residue, n is 1-60 Indicates an integer. 5) 100% by weight of a polycarbonate-polyorganosiloxane copolymer comprising a polyorganosiloxane structural unit represented by the formula (b) and (b) 95-0% by weight of a polycarbonate resin, and the polyorganosiloxane structural unit is a resin. It is intended to provide a digital video disk substrate made of a resin composition containing 0.1 to 10% by weight based on the total amount of the components.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In a resin composition used as a material for a digital video disk substrate (DVD substrate) of the present invention, as the component (a), a compound represented by the general formula (I) is used.

[0010]

[Chemical 6] A polycarbonate structural unit represented by and a general formula (II)

[0011]

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A polycarbonate-polyorganosiloxane copolymer having a polyorganosiloxane structural unit represented by the following (hereinafter abbreviated as PC-POS copolymer).
Is used. In the above general formula (I), R ¹ and R
² represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, respectively. Here, examples of the halogen atom include chlorine, bromine, fluorine and iodine atoms, and the alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, for example, a methyl group. , Ethyl group,
Examples thereof include n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, hexyl group, isohexyl group and cyclohexyl group. R ¹ and R ² may be the same or different. Further, when R ¹ is more than one, a plurality of R ¹ may be the same or different, when R ² is more than one, a plurality of R ² may be the same or different. p and q are integers of 0 to 4, respectively. Z is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylidene group, a cycloalkylene group having 5 to 20 carbon atoms or a cycloalkylidene group, -O-, -S-, -SO-,-.
Indicates SO ₂ — or —CO—. Here, the number of carbon atoms is 1 to 20
Examples of the alkylene group or alkylidene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an ethylidene group, an isopropylidene group, and the like. Examples of the alkylidene group include a cyclopentylene group, a cyclohexylene group,
Examples thereof include a cyclopentylidene group and a cyclohexylidene group. m represents an integer of 1 to 150.

On the other hand, in the general formula (II), R ³ to
R ⁶ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. Here, the alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Isobutyl group, t-butyl group, amyl group, isoamyl group, hexyl group, isohexyl group,
And a cyclohexyl group. This R ³ ~ R
⁶ may be the same or different. A represents a divalent organic residue, and examples thereof include:

[0014]

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Examples include groups represented by:
In this divalent group, it means that the bond on the side marked with * is bonded to Si. R represents a monovalent or divalent organic residue. Here, as the divalent organic residue, the same ones as exemplified in the above description of A can be mentioned, and as the monovalent organic residue, the number of carbon atoms is 1 to 1
8 alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, amyl group, hexyl group) or aryl group having 6 to 20 carbon atoms (eg, phenyl group, tolyl group) Groups, xylyl groups, naphthyl groups, etc.) are preferred.
n is 1 to 60, preferably 5 to 40, more preferably 1
The integer of 0-30 is shown. When n exceeds 60, the transparency of the resin is lowered and it becomes unsuitable as a DVD substrate material.

The PC-POS copolymer of the component (a) is preferably a block copolymer or a graft copolymer, and its type is not particularly limited, and any type may be used. For example, as the block copolymer, when the polycarbonate structural unit represented by the general formula (I) is A block and the polyorganosiloxane structural unit represented by the general formula (II) is B block, AB type, A
Examples thereof include BA type, BAB type and multi-block type. Among these, AB type and ABA type block copolymers are preferable, and ABA type block copolymers are particularly preferable. When the PC-POS copolymer is an ABA type block copolymer, R in the general formula (II) is a divalent organic residue, while in the case of an AB type block copolymer, R is a monovalent organic residue. It becomes an organic residue. Further, as both end groups in the ABA type block copolymer, or the end groups bonded to A in the AB type block copolymer, the general formula
(III)

[0017]

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A group represented by: In the general formula (III), R ⁷ is a halogen atom and has 1 carbon atom.
Is an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. here,
Examples of the halogen atom include chlorine, bromine, fluorine and iodine atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic and includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl group,
And a cyclohexyl group. On the other hand, carbon number 6 ~
The aryl group of 20 may have no substituent on the aromatic ring or may have an appropriate substituent such as a lower alkyl group, for example, phenyl group, tolyl group, xylyl group. Group, naphthyl group, methylnaphthyl group and the like. The arylalkyl group having 7 to 20 carbon atoms may have no substituent on the aromatic ring, or may have an appropriate substituent such as a lower alkyl group, for example, Examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a cumyl group. The ABA type PC-POS copolymer can be produced by various methods, and for example, the compound represented by the general formula (I
V)

[0019]

Embedded image (In the formula, R ¹ , R ² , Z, p and q are the same as above.), And a divalent phenol represented by the general formula (V).

[0020]

Embedded image (In the formula, R ^{3 to} R ⁶ , A and n are the same as above,
¹ represents a divalent organic residue of the same type as A. ) In the liquid medium, a polyorganosiloxane represented by the formula

[0021]

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(In the formula, R ⁷ and r are the same as above.) The reaction can be carried out in the presence of a monohydric phenol end-stopper, whereby the product can be efficiently produced. As the reaction method, a known interfacial polycondensation method, pyridine method or the like can be applied. For example, a solution obtained by dissolving the polyorganosiloxane of the general formula (V) in an inert organic solvent such as methylene chloride, chloroform, chlorobenzene or carbon tetrachloride, and an alkaline aqueous solution (sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution). And the like) is mixed with a solution of the dihydric phenol of the general formula (IV) dissolved therein, and a carbonate ester-forming derivative such as phosgene is blown into the mixture to carry out an interfacial polycondensation reaction. In this reaction, it is preferable to add the terminal stopper of the general formula (VI) to the reaction system in advance or at a stage where the reaction has advanced to some extent. It is also effective to add a tertiary amine such as triethylamine as a catalyst to the reaction system.

A polycarbonate oligomer is prepared in advance from a dihydric phenol of the general formula (IV) and a carbonic acid ester-forming derivative, and the oligomer, the polyorganosiloxane of the general formula (V) and the terminal of the general formula (VI) are prepared. It is also effective to carry out the interfacial polycondensation reaction by mixing and stirring the terminating agent, the above-mentioned inert organic solvent and alkaline aqueous solution, and further the catalyst in a predetermined ratio. According to the pyridine method, the dihydric phenol of the general formula (IV), the polyorganosiloxane of the general formula (V) and the general formula (VI) are used as raw materials.
The end-capping agent is dissolved in pyridine or a mixed solvent of pyridine and an inert solvent, and a carbonic acid ester-forming derivative such as phosgene is blown into this solution to obtain the desired ABA-type PC.
A POS copolymer is obtained. On the other hand, AB type PC-P
The OS copolymer can also be produced by various methods. For example, the polycarbonate oligomer in the presence of the dihydric phenol represented by the general formula (IV) and the monohydric phenol represented by the general formula (VI) can be used. And the general formula (VII)

[0024]

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(In the formula, R ′ represents a monovalent organic group such as an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ^{3 to} R ⁶ , A and n are the same as above. It is.)
By reacting a polyorganosiloxane of which one end is blocked, represented by, can be efficiently produced. The polycarbonate oligomer is prepared by a solvent method, that is, in the presence of a known acid acceptor, a divalent phenol of the general formula (IV) and phosgene in an organic solvent such as methylene chloride in the presence of a known endcapper of the general formula (VI). It can be prepared by a reaction with a precursor or a transesterification reaction between the dihydric phenol and a carbonic acid diester (for example, diphenyl carbonate).

There are various dihydric phenols represented by the above general formula (IV), but 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable. Examples of the dihydric phenol other than bisphenol A include bis (4-hydroxyphenyl)
Methane; bis (3,5-dichloro-4-hydroxyphenyl) methane; bis (3,5-dimethyl-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane; 2-methyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-
1,1-bis (4-hydroxyphenyl) propane;
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4)
-Hydroxyphenyl) propane; 2,2-bis (3-
Chloro-4-hydroxyphenyl) propane; 2,2-
Bis (3-methyl-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) butane; 2,2-bis (4 -Hydroxyphenyl)
Butane; 1,4-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) pentane; 4-methyl-2,2-bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane; 1,1 -Bis (4-hydroxyphenyl)
-3,3,5-trimethylcyclohexane; 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3
Dihydroxydiarylalkanes such as 3-hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane; 1,1-
Dihydroxydiarylcycloalkanes such as bis (4-hydroxyphenyl) cyclodecane, bis (4-hydroxyphenyl) sulfone; bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; bis (3-chloro-4-hydroxyphenyl) ) Dihydroxydiarylsulfones such as sulfone, bis (4-hydroxyphenyl) ether; dihydroxydiarylethers such as bis (3,5-dimethyl-4-hydroxyphenyl) ether, 4,4′-dihydroxybenzophenone;
Dihydroxydiarylketones such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide;
Bis (3-methyl-4-hydroxyphenyl) sulfide; dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, dihydroxydiaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, and the like. Can be mentioned. These dihydric phenols may be used alone or in combination of two or more.

Examples of the terminal stopper for the monohydric phenol represented by the general formula (VI) include phenol;
-Butylphenol; mn-butylphenol; p-
n-butylphenol; o-isobutylphenol; m
-Isobutylphenol; p-isobutylphenol;
o-t-butylphenol; m-t-butylphenol; p-t-butylphenol; o-n-pentylphenol; m-n-pentylphenol; p-n-pentylphenol; o-n-hexylphenol; m-n-
Hexylphenol; pn-hexylphenol; o
-Cyclohexylphenol; m-cyclohexylphenol; p-cyclohexylphenol; o-phenylphenol; m-phenylphenol; p-phenylphenol; o-n-nonylphenol; m-n-nonylphenol; p-n-nonylphenol; Millphenol; m-cumylphenol; p-cumylphenol; o-naphthylphenol; m-naphthylphenol; p-naphthylphenol; 2,6-di-t-butylphenol; 2,5-di-t-butylphenol; Two
4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-
Examples include dicumylphenol. These may be used alone or in combination of two or more.

Regarding the ratio of the polycarbonate structural unit represented by the general formula (I) to the polyorganosiloxane structural unit represented by the general formula (II) in the PC-POS copolymer as the component (a), There is no particular limitation as long as the polyorganosiloxane structural unit is contained in a proportion of at least 0.1% by weight. When the content of this polyorganosiloxane structural unit is less than 0.1% by weight, when the resin composition is prepared, the content of the polyorganosiloxane structural unit is in the range of 0.1 to 10% by weight based on the total amount of the resin component. Cannot be controlled. A homopolycarbonate containing no polyorganosiloxane structural unit is also produced during the production of this PC-POS copolymer, and it is essentially a blended product of the PC-POS copolymer and the homopolycarbonate. This blended product is also called a copolymer.

In the resin composition used as the material for the DVD substrate of the present invention, a polycarbonate resin is used as the component (b). This polycarbonate resin is not particularly limited in its production method, and may be one obtained by directly reacting a dihydric phenol and phosgene by an interfacial polycondensation method, or by melting a dihydric phenol and a carbonic acid diester. It may be obtained by a method (melt polymerization method) of transesterification in the state.
As the dihydric phenol, PC-PO as the component (a) is used.
The same as those exemplified in the description of the production of the S copolymer can be mentioned, and in addition, hydroquinone, 9,9-bis (4-hydroxyphenyl) fluorene and halogen derivatives thereof can also be used. . These may be used alone or in combination of two or more, and of these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable. Preferred examples of carbonic acid diesters include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. These may be used alone or in combination of two or more, and among these, diphenyl carbonate is particularly preferable.

When producing this polycarbonate resin, a terminal stopper is usually used. This terminal stopper may be a monohydric phenol and is not particularly limited, and for example,
In the description of the production of the PC-POS copolymer as the component (a), the same ones as exemplified as the terminal terminator can be mentioned. These may be used alone or in combination of two or more. Furthermore, when producing this polycarbonate resin, a branching agent may be used in combination with the dihydric phenol, if necessary, within the range in which the effects of the present invention are not impaired. As the branching agent, a compound having three or more functional groups, for example, 1,1,1-tris (4-hydroxyphenyl) ethane; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,3. 5-triisopropylbenzene; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; phloroglycine; tri Mellitic acid; isatin bis (o-cresol) and the like. These may be used alone or in combination of two or more.

In the resin composition used as the material of the DVD substrate of the present invention, PC-PO of the above-mentioned component (a) is used.
The proportion of the S copolymer and the polycarbonate resin of the component (b) is in the range of 5 to 100% by weight of the component (a) and 95 to 0% by weight of the component (b). If the amount of the component (a) is less than 5% by weight, a DVD substrate having desired physical properties cannot be obtained. The content of the polyorganosiloxane structural unit represented by the general formula (II) in this resin composition is
It is in the range of 0.1 to 10% by weight based on the total amount of the resin component. If this amount is less than 0.1% by weight, cracks may occur during the molding of the DVD substrate, and if it exceeds 10% by weight, the heat resistance and rigidity are lowered, making it unsuitable as a DVD substrate material. From the viewpoint of the balance of crack resistance, heat resistance, and rigidity at the time of molding a substrate, the preferable content of this polyorganosiloxane structural unit is 0.3 to 8 based on the total amount of the resin component.
It is in the range of% by weight, and particularly preferably in the range of 0.5 to 6% by weight.

The viscosity average molecular weight of this resin composition is preferably in the range of 10,000 to 17,000. If the viscosity average molecular weight is less than 10,000, cracking may occur during molding of the DVD substrate, and if it exceeds 17,000, the birefringence of the obtained DVD substrate increases. A more preferable range of the viscosity average molecular weight is 1200 from the viewpoints of preventing cracks during molding of a DVD substrate and birefringence of the DVD substrate.
It is 0-16000, and the range of 13500-15500 is particularly preferable. The resin composition may be a blend of the PC-POS copolymer as the component (a) and a polycarbonate resin as the component (b) in an appropriate kneader, or may be simply a dry blend. Good.
Furthermore, if desired, various additives such as an antioxidant, a lubricant (release agent), an inorganic filler, a flame retardant, and a colorant are appropriately added to the resin composition within the range where the object of the present invention is not impaired. You may mix.

As the above-mentioned antioxidant, a phosphorus-based antioxidant is preferable, for example, trimethylphosphite, triethylphosphite, tributylphosphite, trioctylphosphite, trinonylphosphite, tridecylphosphite, trioctadecylphosphite. , Distearyl pentaerythryl diphosphite, tris (2
-Chloroethyl) phosphite, trialkylphosphite such as tris (2,3-dichloropropyl) phosphite; tricycloalkylphosphite such as tricyclohexylphosphite; triphenylphosphite, tricresylphosphite, tris (ethyl Triaryl phosphites such as phenyl) phosphite, tris (butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphite; monoalkyldiarylphosphites such as 2-ethylhexyldiphenylphosphite;
Trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate,
Trialkyl phosphates such as tris (2-chloroethyl) phosphate and tris (2,3-dichloropropyl) phosphate; tricycloalkylphosphates such as tricyclohexylphosphate; triphenylphosphate, tricresylphosphate, tris (nonylphenyl) phosphate, Triaryl phosphates such as 2-ethylphenyl diphenyl phosphate and the like can be mentioned. These may be used alone or in combination of two or more.

As the lubricant (release agent), for example, stearyl alcohol, stearic acid monoglyceride,
Examples thereof include stearic acid esters such as pentaerythritol stearic acid esters, and beeswax.
These lubricants have the function of improving the releasability during molding. The DVD substrate of the present invention is molded using a material comprising the above polycarbonate and various optional components used as desired. The molding method is not particularly limited, and a disk molding die is used for injection molding. Alternatively, in addition to the usual molding method of compression molding, methods such as ultrasonic molding, multi-stage compression molding, and high-speed filling molding can be used.

The molding temperature is usually in the range of 300 to 345 ° C, and the mold temperature is usually in the range of 80 to 125 ° C. In order to reduce birefringence and improve transferability, it is necessary to improve the fluidity of the resin, but if the molding temperature exceeds 345 ° C., the polycarbonate may deteriorate and the transparency may decrease. It is essential that the DVD substrate has excellent transparency. Also, the mold temperature is preferably high from the viewpoint of improving the fluidity, but if it exceeds 125 ° C., the shape of the substrate may collapse. Further, with respect to the injection rate, 150 cm ³ / sec or more, preferably 200 cm ³ / sec or more is advantageous. If the injection rate is less than 150 cm ³ / sec, the molding material is rapidly cooled in the mold, the flow pressure loss increases, the orientation of the resin increases, and as a result, defects such as distortion may occur in the molded product. . The material of the mold is not particularly limited, and metal, ceramics, graphite or the like is used.

The DVD substrate of the present invention thus obtained is suitable as a substrate for various digital video disks (DVD family) such as a read-only type, a write-once type and a rewritable type. The method for manufacturing a digital video disk substrate using the DVD substrate of the present invention is not particularly limited, and the same method as in the case of a normal compact disk can be used. For example, by a film forming process, a protective layer and a recording layer are provided on the substrate, and a hard coat layer and, if necessary, an overcoat layer are further provided on the substrate to prepare two disc veneers. The desired digital video disk can be obtained by any other method, for example, using a hot-melt type adhesive or a pressure-sensitive adhesive sheet for attachment and hub attachment if necessary. Examples of the hot melt adhesive used at this time include ethylene-vinyl acetate copolymer (E
VA) type, polyolefin type, synthetic rubber type, polyester type, polyamide type and the like. On the other hand, examples of the adhesive for the adhesive sheet include rubber-based, acrylic-based, and silicone-based adhesives, and the sheet material includes
Examples thereof include polyester-based, polyimide-based, polyurethane-based, polyolefin-based resin sheets and metal sheets such as aluminum foil.

[0037]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Production Example 1 Preparation of Polycarbonate Oligomer 60 kg of bisphenol A was dissolved in 400 liter of a 5 wt% sodium hydroxide aqueous solution to prepare a sodium hydroxide aqueous solution of bisphenol A. Then, the sodium hydroxide aqueous solution of bisphenol A kept at room temperature was supplied at a flow rate of 138 liters / hour, and methylene chloride was supplied at a flow rate of 69 liters / hour, with an inner diameter of 10 mm,
It was introduced into a tubular reactor having a tube length of 10 m through an orifice plate, and phosgene was co-currently flown into the reactor at a flow rate of 10.7 kg / hour for continuous reaction for 3 hours. The tubular reactor used here was a double tube, and the outlet temperature of the reaction solution was kept at 25 ° C. by passing cooling water through the jacket. Further, the pH of the discharged liquid was adjusted so as to show 10 to 11.
By allowing the reaction solution thus obtained to stand,
The aqueous phase was separated and removed, and the methylene chloride phase (220 liters) was collected to obtain a polycarbonate oligomer solution.

Production Example 2 Production of Reactive Polydimethylsiloxane (PDMS) Octamethylcyclotetrasiloxane 1483 g, 1,
96 g and 86 of 1,3,3-tetramethyldisiloxane
After mixing 35 g of wt% sulfuric acid and stirring at room temperature for 17 hours, the oil phase was separated, 25 g of sodium hydrogen carbonate was added, and the mixture was stirred for 1 hour. Then, the mixture was filtered, and the filtrate was vacuum distilled at 150 ° C. at 3 torr to remove low-boiling substances. To a mixture of 60 g of 2-allylphenol and 0.0014 g of platinum as a platinum chloride-alcoholate complex, 294 g of the oil obtained above was added at 90 ° C., and then the mixture was kept at a temperature of 90 to 115 ° C. for 3 times. Stir for hours. The product was extracted with methylene chloride and washed 3 times with 80% by weight aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulfate,
The solvent was distilled off by raising the temperature to 115 ° C. in vacuum. According to the measurement of nuclear magnetic resonance spectrum (NMR), the number of repeating dimethylsilanooxy units in the obtained terminal phenol PDMS was 30.

Production Example 3 Production of PC-PDMS Copolymer A 185 g of the reactive PDMS obtained in Production Example 2 was dissolved in 2 liters of methylene chloride and mixed with 10 liters of the polycarbonate oligomer solution obtained in Production Example 1. Next, 26 g of sodium hydroxide dissolved in 1 liter of water and 5.7 ml of triethylamine were added thereto, and the mixture was stirred at 500 rpm for 1 hour at room temperature. Then, 600 g of bisphenol A was dissolved in 5 liters of a 5.2 wt% sodium hydroxide aqueous solution,
8 L of methylene chloride and 123.5 g of p-tert-butylphenol were added, and the mixture was stirred at 500 rpm for 1 hour at room temperature. Next, add 5 liters of methylene chloride and 5 liters of water, and add 1 at room temperature at 500 rpm.
After stirring for 0 minutes, the mixture was allowed to stand and the organic phase was separated. The organic phase was washed with 5 liters of 0.03N aqueous sodium hydroxide solution in an alkaline solution, with 5 liters of 0.2N hydrochloric acid in acid, and then with 5 liters of water (twice) in this order, and then methylene chloride was distilled off. Then, a flaky polycarbonate-polydimethylsiloxane (PC-PDMS) copolymer A was obtained. The viscosity average molecular weight (Mv) of this PC-PDMS copolymer A and the content of the PDMS structural unit were first determined.
It is shown in the table.

Production Example 4 Production of PC-PDMS Copolymer B In Production Example 3, 93 g of 185 g of reactive PDMS was added.
Then, 123.5 g of p-tert-butylphenol was added to p-
Production Example 3 except that the amount of cumylphenol was changed to 174.5 g.
A PC-PDMS copolymer B was obtained in the same manner as. This P
C-PDMS Copolymer B viscosity average molecular weight and PDMS
The content of the structural unit is shown in Table 1.

Production Example 5 Production of Polycarbonate Resin C Polycarbonate oligomer solution 1 obtained in Production Example 1
P-tert-butylphenol 123 to 0.0 liter.
5 g was dissolved. Next, to this, 8 liters of methylene chloride, a sodium hydroxide aqueous solution of bisphenol A (bisphenol A: 800 g, NaOH: 420
g, water: 6.55 liters) and triethylamine 1.17
After adding milliliter, the mixture was stirred at 500 rpm at room temperature for 1 hour. Thereafter, 5 liters of methylene chloride and 5 liters of water were added, and the mixture was stirred at 500 rpm for 10 minutes at room temperature. After the stirring was stopped, the mixture was stood and separated to obtain an organic phase. This organic phase was washed with 5 liters of 0.03N aqueous sodium hydroxide solution in an alkaline solution, washed with 5 liters of 0.2N hydrochloric acid in acid and washed with 5 liters of water (twice), and then methylene chloride was distilled off. After that, a flaky polycarbonate resin C was obtained. The viscosity average molecular weight of this polycarbonate resin C is shown in Table 1.

Production Example 6 Production of Polycarbonate Resin D In Production Example 5, p-tert-butylphenol 1
Polycarbonate resin D was obtained in the same manner as in Production Example 5, except that 23.5 g was changed to 174.5 g of p-cumylphenol. The viscosity average molecular weight of this polycarbonate resin D is shown in Table 1.

[0043]

[Table 1]

Note 1) PDMS structural unit content In the measurement of proton nuclear magnetic resonance spectrum ( ¹ H-NMR), the peak of the isopropyl methyl group of bisphenol A seen at 1.7 ppm and the dimethylsiloxane seen at 0.2 ppm. The intensity ratio of the peak of the methyl group of 2) Viscosity average molecular weight (Mv) The intrinsic viscosity [η] of a methylene chloride solution at 20 ° C. was measured with an Ubbelohde type viscosity tube and calculated from the following relational expression [η] = 1.23 × 10 ⁻⁵ · Mv ^0.83

Examples 1 to 5 and Comparative Examples 1 to 3 were dry blended with the respective components at the blending ratios shown in Table 2,
It was extruded at 230 ° C. and pelletized. Tris (2,4-di-tert-butylphenyl) phosphite was used as the antioxidant, and stearic acid monoglyceride was used as the release agent. Table 2 shows the viscosity average molecular weight (Mv), PDMS structural unit content and release pressure of the obtained pellets. The mold release pressure was measured at 280 ° C. using a cylindrical mold, and the mold release resistance at the time of projecting (mold release) was measured. Next, the obtained pellets were molded into a molding machine: IS80EPN manufactured by Toshiba Machine Co., Ltd., mold clamping force: 50 tons, injection rate: 2
50 cm ³ / sec, injection pressure: 1500 kg / cm ² , mold material: duralumin 2024, molding temperature: 340 ° C.,
Mold temperature: 115 ° C, cooling time 5 seconds: Cavity part: injection molding under conditions of electroless nickel plating, diameter 120m
A DVD substrate having a thickness of 0.6 mm and a thickness of 0.6 mm was prepared.

100 DVD substrates were molded, and the number of unbroken substrates is shown in Table 3. Here, the cracking means that the sprue portion and the disc are cut and the sprue portion remains in the molding machine. Also, after molding, the falling weight impact strength of the molded product after 48 hours has passed is 3.76 kg, speed 1 m / sec,
The length of the pedestal was 50 mm. In addition, the inside of a place having a radius of 18 mm was hit. Energy (J) of falling weight impact strength is shown in Table 3. Further, the transferability and the birefringence (Δn) of the example 1 and the comparative example 1 were measured. Here, the transferability means [the height of the convex portion of the molded product / the depth of the concave portion of the mold surface (5 μm)] × 100, and the average value of 20 points was used. The measurement is made by Nikon measure scope UM.
-3 was used. The results are shown in Table 4. Also, the birefringence (Δ
The measurement of n) was carried out using a double reflection measurement system ADR-2000 manufactured by Oak Co., Ltd. at arbitrary points on the circumference of 10 mm, 30 mm and 50 mm from the center of the disk. Table 4 shows the values of retardation (R = Δn · t). Here, t is the disc thickness (nm).

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

The digital video disk substrate of the present invention has few cracks during molding, has small birefringence, and is excellent in transferability. Therefore, this digital video disc substrate is preferably used as a substrate for a digital video disc (DVD family) of a read-only type, a write-once type, a rewritable type, or the like.

Claims (3)

[Claims] 1. (a) General formula (I): (In the formula, R ¹ and R ² each represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different, and Z is a single bond, 1 to 1 carbon atoms. 20 alkylene groups or alkylidene groups,
C5-C20 cycloalkylene group or cycloalkylidene group, -O-, -S-, -SO-, -SO ₂ or -CO- is shown, p and q are respectively integers of 0 to 4, and m is An integer of 1 to 150 is shown. ) And a polycarbonate structural unit represented by the general formula (II) (In the formula, R ^{3 to} R ⁶ each represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different, A is a divalent organic residue, and R is a monovalent organic residue. A polyvalent or divalent organic residue, n is an integer of 1 to 60), and a polycarbonate-polyorganosiloxane copolymer 5 to 10 composed of a polyorganosiloxane structural unit represented by
Digital containing a resin composition containing 0% by weight and (b) 95 to 0% by weight of a polycarbonate resin, and 0.1 to 10% by weight of the above polyorganosiloxane structural unit based on the total amount of the resin component. Video disc board. 2. The component (a) comprises a polycarbonate structural unit represented by the general formula (I) as an A block and a general formula (II).
When the polyorganosiloxane structural unit represented by the following is a B block, the polyorganosiloxane structural unit represented by the general formula (III): (In the formula, R ⁷ is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms.
And an r is an integer of 0 to 5. The digital video disk substrate according to claim 1, which is an ABA type block copolymer having a terminal group represented by the formula (1). 3. The polycarbonate-polyorganosiloxane copolymer as the component (a) and the polycarbonate resin as the component (b) are each derived from 2,2-bis (4-hydroxyphenyl) propane. 1
The described digital video disk substrate.