Polycarbonate and optical disc substrate

The present invention relates to a polycarbonate resin containing from 25 to 100% by weight, based on the total carbonate bond-constituting units, of carbonate bond-constituting units each containing at least one pendant aromatic group. Particularly, it relates to a material useful for the production of a molded product having excellent heat resistance and optical characteristics, and in particular, to a material useful for the production of an optical disc substrate having excellent transparency and a minimum optical distortion.
Heretofore, polycarbonate resins containing carbonate bond-constituting units having at least one pendant aromatic group, have been disclosed in literatures. However, their physical properties are described usually in terms of Tg or Tm, and it is not known whether they have practically suitable physical properties as molded products, or whether they can practically be processed.
A molded product to be used for optical purposes, such as a molded product in the form of a plate or sheet, is required to be transparent and to have a minimum optical distortion. Particularly when used as an optical information material i.e. an optical disc with use of digital signals, such as a digital audio disc, a digital video disc or a disc for information readout or writing in, the requirement for the transparency is extremely strict, and with respect to the optical distortion, the double refraction of the molded product is required to be not higher than 5.times.10.sup.-5.
It is common to employ injection molding as a simple method for molding a product of this type. However, as a method for minimizing the optical distortion, it is common to raise the molten resin temperature or reduce the molecular weight of the resin to improve the melt flow characteristics.
Furthermore, in the case of a disc intended for continuous use over a long period of time, the requirement for heat resistance is also strict with a view to providing adequate durability for use under severe environmental conditions. If the molten resin temperature is raised to minimize the optical distortion, various troubles are likely to be led resulting from the thermal deterioration of the resin. On the other hand, if the molecular weight of the resin is reduced, the strength of the disc will be inadequate, and it becomes difficult to obtain a satisfactory molded product.
With respect to the glass transition temperature representing the heat resistance, each resin has its own value, and there is no room for improvement.
Thus, the conventional technology does not provide a satisfactory solution.
The present inventors have conducted extensive researches on polycarbonate resins which may be molded by melt-molding and which have superior optical characteristics and heat resistance to polycarbonates prepared from 2,2-bis(4-hydroxyphenyl)propane, and have found that such an object of the present invention can be accomplished by a polycarbonate resin containing carbonate bond-constituting units each having at least one pendant aromatic group and which has a certain specific molecular weight, whereby the problems of the conventional technique can be solved.
Namely, the present invention provides a polycarbonate containing from 25 to 100% by weight, based on the total carbonate bond-constituting units, of carbonate bond-constituting units each containing at least one pendant aromatic group, and having an average molecular weight of from 9,500 to 14,000.
Now, the present invention will be described in detail with reference to the preferred embodiments.
The polycarbonate resin of the present invention contains from 25 to 100% by weight, preferably from 60 to 100% by weight, based on the total carbonate bond-constituting units, of carbonate bond-constituting units each containing at least one pendant aromatic group (hereinafter referred to simply as "carbonate bond units A"), and has an average molecular weight of from 9,500 to 14,000.
The pendant aromatic group is meant for an aryl or aralkyl group.
For the purpose of the present invention, the "carbonate bond" is meant for a ##STR1## bond obtained by the reaction of an alcoholic hydroxyl group or a phenolic hydroxyl group with e.g. phosgene. The "carbonate bond-constituting unit" is meant for a structural unit between such carbonate bonds. Further, the structural unit between the carbonate bonds may contain other types of bonds such as ester bonds, amide bonds, carbamate bonds or ether bonds.
As the carbonate bond-constituting unit containing at least one pendant aromatic group, there may be mentioned the one having the formula: ##STR2## wherein each of X and Y is a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 6 carbon atoms, or an aryl or aralkyl group having from 6 to 12 carbon atoms, provided that at least one of X and Y is an aryl or aralkyl group having from 6 to 12 carbon atoms, and each of Z and W is a hydrogen atom or an aliphatic hydrocarbon group having from 1 to 6 carbon atoms.
Further, as a structural unit which may be contained together with the above structural unit, there may be mentioned one having the formula: ##STR3## wherein X' is a bivalent group of ##STR4## (wherein each of R.sup.1 and R.sup.2 is a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, and R.sup.3 is an alkylene group having from 4 to 5 carbon atoms), and the aromatic rings may be substituted by an alkyl group or a halogen atom.
For the production of such a polycarbonate, there may be employed a conventional method for interfacial or solution polymerization, wherein phosgene is blown into at least one of diol compounds, particularly aromatic diol compounds, containing at least one pendant aromatic group.
As the diol having at least one pendant aromatic group, particularly an aromatic diol capable of presenting the structural unit of the formula I, there may be mentioned, for instance, bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-phenylpropane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)dibenzylmethane, o-cumyl resorcinol, or phenolphthalein.
In the present invention, carbonate bond-constituting units containing no pendant aromatic group may also be introduced. Such introduction improves the melt flow characteristics of the resulting polycarbonate and thus is preferred for the improvement of moldability. However, if the amount of the units containing pendant aromatic groups is less than 25% by weight, the glass transition temperature of the polymer lowers to a great extent, such being undesirable not only from the viewpoint of heat resistance, but also from the viewpoint of the preparation of an optical disc substrate having a minimum optical distortion. As the comonomer to be used in such a case, there may be mentioned as the one capable of presenting the structural unit of the formula II, 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane (i.e. bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide or a bivalent phenol compound such as resorcinol or o-methyl resorcinol. Further, in some cases, a small amount of an acid chloride such as isophthalic acid chloride, adipic acid chloride or sebacic acid chloride, or a diamine such as piperazine, may be present for the copolymerization to introduce a bond other than the carbonate bond into the carbonate bond-constituting unit.
For the introduction of carbonate bond-constituting units other than the carbonate bond units A, copolymerization may be conducted within a range which satisfies the requirements of the present invention, or polymers separately produced may be mixed to satisfy the requirements of the present invention.
The method for the production of a polycarbonate resin from a diol containing at least one pendant aromatic group and phosgene, may be carried out by introducing into the diol an aqueous alkaline solution or pyridine as an acid acceptor in the presence of an inert solvent such as methylene chloride or 1,2-dichloromethane and introducing and reacting phosgene therewith. When an aqueous alkaline solution is used as the acid acceptor, the reaction rate can be increased by using as the catalyst a tertiary amine such as trimethylamine or triethylamine or a quarternary ammonium compound such as tetrabutyl ammonium chloride or benzyltributyl ammonium bromide. If necessary, a monovalent phenol such as phenol or p-tert-butylphenol may be used as a molecular weight modifier. The reaction is conducted usually at a temperature of from 0.degree. to 100.degree. C. The catalyst may be present from the initial stage, or may be added after the preparation of an oligomer, followed by further polymerization.
For the copolymerization of the above-mentioned copolymerizable compound with a diol having at least one pendant aromatic group, there may be employed (a) a method wherein they may be simultaneously reacted with phosgene and polymerized, (b) a method wherein one of them is firstly reacted with phosgene, and after the reaction has proceeded to some extent, the other compound is introduced for polymerization, or (c) a method wherein the two compounds are reacted with phosgene separately to produce the respective oligomers, which are then reacted for polymerization.
As a method for mixing the polymers separately prepared, there may be mentioned a method wherein the respective powders or granules are mixed, and then meltmixed by means of e.g. an extruder, a kneader or mixing rolls, or a solution blending method.
The polycarbonate to be used in the present invention preferably has an average molecular weight of 9,500 to 14,000. The average molecular weight here is meant for a value obtained from .eta.sp as measured at 20.degree. C. by using a methylene chloride solution containing 6.0 g/liter of the polymer, by calculation in accordance with the following formula 1 and formula 2.
.eta. sp/c=[.eta.] (1+K' .eta.sp) (1)
[.eta.]=KM.sup..alpha. ( 2)
In the above formulas, c is the polymer concentration (g/liter), [.eta.] is the intrinsic viscosity, K'is 0.28, K is 1.23.times.10.sup.-5, .alpha. is 0.83, and M is the average molecular weight.
Namely, if the average molecular weight is less than 9,500, the mechanical properties will be inferior, and if the average molecular weight exceeds 14,000, it will be difficult to obtain a molding material having a minimum optical distortion.
When the polycarbonate of the present invention is to be molded, it is preferred to add from 0.01 to 2% by weight of a phosphite to the resin, whereby the coloring or the deterioration of transparency due to the decomposition of the resin can be controlled. As such a phosphite, there may be mentioned tributyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, tristearyl phosphite, triphenyl phosphite, tricresyl phosphite, 2-ethylhexyldiphenyl phosphite, decyldiphenyl phosphite, tricylohexyl phosphite or distearyl pentaerythrityl diphosphite. Such a phosphite may be incorporated by dry blending, by melt mixing at the time of pelletizing by means of an extruder, or by preparing master pellets having a high phosphite concentration and dry blending them with pellets containing no phosphite.
The molding material of the present invention is a polycarbonate resin which has excellent heat resistance and optical characteristics and which is capable of being molded by melt molding, and thus is useful for the production of an optical information material such as an optical disc, lens or optical fiber. The polycarbonate of the present invention is particularly useful as a material for the optical disc. The optical disc here includes a disc for replay only such as a compact disc or a laser disc, a write-once type disc useful for a document file, a still image file or a moving image file, and an erasable type disc such as a photomagnetic disc. The present invention is particularly useful for e.g. the erasable optical disc where the heat resistance is particularly important.
Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted by these specific Examples.
The Examples illustrate specific manners for the preparation of the polycarbonates of the present invention and their oligomers. In the Examples, the "parts" represents "parts by weight".
The resin obtained in each Example or Comparative Example was, after an addition of 130 ppm of 2-ethylhexyl diphenylphosphite, molded into a disc having a thickness of 1.2 mm and a diameter of 10 cm at a molding temperature of 340.degree. C. by means of a 1 ounce injection molding machine (manufactured by Nissei Jushi) under the molding conditions identified in Table 1.
At the same time, the apparent melt viscosity .eta.a was measured at 280.degree. C. at a shear rate of 10.sup.3 sec.sup.-1 by a flow tester, and used as a reference for the melt flow characteristics.
The double refraction was evaluated by the double refraction at positions of 2.0 cm and 4.5 cm from the center of the disc (hereinafter referred to as ".DELTA.n.sub.2.0 " and ".DELTA.n.sub.4.5 ", respectively). The double refraction was measured by polarizing microscope manufactured by Nippon Kogaku K.K.
The tensile property was measured by a tensile tester at a tensile speed of 5 mm/min in accordance with ASTM D638.
The glass transition temperature (Tg) was measured by a differential scanning calorimeter (manufactured by Perkin Elmer Co.).
The results of the measurements in each Example are shown in Table 1.

EXAMPLE 1
______________________________________Preparation of polycarbonate______________________________________1,1-bis(4-hydroxyphenyl)-1-phenylethane 100 partsp-tert-Butylphenol 1.3 partsPyridine 200 partsMethylene chloride 1000 parts______________________________________
The above mixture was charged into a reactor equipped with a stirrer and stirred at 500 rpm.
Then, 50 parts of phosgene was blown into it over a period of one hour, whereby solution polymerization was conducted.
After the completion of the reaction, excess pyridine was neutralized by an aqueous hydrochloric acid solution, and the product was washed with water, an aqueous hydrochloric acid solution and then water, and finally methylene chloride was evaporated to obtain the resin.
The average molecular weight of this resin was 10,400.
EXAMPLE 2
______________________________________Preparation of polycarbonate______________________________________1,1-bis(4-hydroxyphenyl)-1-phenylethane 100 parts2,2-bis(4-hydroxy-3-methylphenyl)- 30 partspropanep-tert-Butylphenol 1.0 partPyridine 500 partsMethylene chloride 2300 parts______________________________________
The above mixture was charged into a reactor equipped with a stirrer and stirred at 500 rpm.
Then, 50 parts of phosgene was blown into it over a period of one hour, whereby solution polymerization was conducted. After the completion of the reaction, excess pyridine was neutralized by an aqueous hydrochloric acid solution, and the product was washed with water, an aqueous hydrochloric acid solution and then water, and finally methylene chloride was evaporated to obtain the resin.
The average molecular weight of this resin was 11,000. From the result of the NMR analysis, copolymerized 2,2-bis(4-hydroxy-3-methylphenyl)propane was found to be 23% by weight.
EXAMPLE 3
______________________________________Preparation of polycarbonate oligomer______________________________________1,1-bis(4-hydroxyphenyl)-1-phenylethane 100 partsSodium hydroxide 40 partsWater 600 partsMethylene chloride 375 parts______________________________________
The above mixture was charged into a reactor equipped with a stirrer and stirred at 800 rpm. Then, 57 parts of phosgene was blown into it over a period of one hour, whereby interfacital polymerization was conducted. After the completion of the reaction, the methylene chloride solution containing a polycarbonate oligomer was separated. The methylene chloride solution of the oligomer thus obtained was analyzed. The results were as follows.
______________________________________Oligomer concentration 22.5% by weight (Note 1)Terminal chloroformate group 0.42 N (Note 2)concentrationTerminal phenolic hydroxyl 0.020 N (Note 3)group concentration______________________________________
The oligomer solution obtained by the above process will be referred to as "oligomer solution A".
Note 1: Measured by evaporation to dryness.
Note 2: The aniline hydrochloride obtained by the reaction with aniline was measured by neutralization titration with a 0.2 N sodium hydroxide aqueous solution.
Note 3: The color development when dissolved in an acetic acid solution of titanium tetrachloride was measured by colorimetry at 546 nm.
EXAMPLE 4
______________________________________Preparation of polycarbonate______________________________________Polycarbonate oligomer solution A 140 partsp-tert-Butylphenol 1.9 partsMethylene chloride 80 parts______________________________________
The above mixture was charged into a reactor equipped with a stirrer and stirred at 550 rpm. Then, an aqueous solution having the following composition was added:
______________________________________7.3% Aqueous solution of sodium hydroxide 80 parts2% Aqueous solution solution of triethyl- 1 partamine______________________________________
Interfacial polymerization was conducted for 3 hours. The reaction mixture was subjected to liquid separation. The methylene chloride solution containing a polycarbonate resin was washed with water, an aqueous hydrochloric acid solution and then water, and finally methylene chloride was evaporated to obtain the resin.
The average molecular weight of this resin was 11,200.
COMPARATIVE EXAMPLE 1
Preparation of polycarbonate
A polycarbonate was prepared in the same manner as in Example 4 except that the amount of p-tert-butylphenol was changed to 1.5 parts. The average molecular weight of this resin was 7,800.
COMPARATIVE EXAMPLE 2
Preparation of polycarbonate
A polycarbonate was prepared in the same manner as in Example 4 except that the amount of p-tert-butylphenol was changed to 0.5 part. The average molecular weight of this resin was 16,900.
COMPARATIVE EXAMPLE 3
______________________________________Preparation of polycarbonate oligomer______________________________________16.6% aqueous solution of a sodium salt of bisphenol 100 partsA prepared by dissolving bisphenol A in an aqueoussodium hydroxide solutionp-tert-Butylphenol 0.23 partMethylene chloride 40 partsPhosgene 7 parts______________________________________
The mixture having the above composition was quantitatively supplied to a pipe reactor, and interfacial polymerization was conducted.
The reaction mixture was subjected to liquid separation. The methylene chloride solution containing a polycarbonate oligomer was separated.
The methylene chloride solution of the oligomer thus obtained was analyzed. The results are as shown below.
______________________________________Oligomer concentration 24.5% by weightTerminal chloroformate group 1.3 NconcentrationTerminal phenolic hydroxyl group 0.3 Nconcentration______________________________________
The oligomer solution obtained by the above process will be referred to as "oligomer solution B".
COMPARATIVE EXAMPLE 4
______________________________________Preparation of polycarbonate______________________________________Polycarbonate oligomer solution B 160 partsp-tert-Butylphenol 0.7 partMethylene chloride 130 parts______________________________________
The above mixture was charged into a reactor equipped with a stirrer and stirred at 550 rpm. Then, an aqueous solution having the following composition was added:
______________________________________16.6% Aqueous solution of a sodium salt of bisphenol A 80 parts 25% Aqueous solution of sodium hydroxide 8 parts 2% Aqueous solution of triethylamine 1 part______________________________________
Interfacial polymerization was conducted for about 1.5 hours. The reaction mixture was subjected to liquid separation. The methylene chloride solution containing a polycarbonate resin was washed with water, an aqueous hydrochloric acid solution and then water, and finally methylene chloride was evaporated to obtain the resin.
The average molecular weight of this resin was 17,400.
COMPARATIVE EXAMPLE 5
Preparation of polycarbonate
A polycarbonate was prepared in the same manner as in Comparative Example 4 except that the amount of p-tert-butylphenol was changed to 1.3 parts. The average molecular weight of this resin was 14,700.
COMPARATIVE EXAMPLE 6
Preparation of polycarbonate
A polycarbonate was prepared in the same manner as in Comparative Example 4 except that the amount of p-tertbutylphenol was changed to 2.0 parts. The average molecular weight of this resin was 13,000.
TABLE 1__________________________________________________________________________ Injection pressure Tensile properties Average (kg/cm.sup.2) Tensile Tensile molecular Primary pressure/ Double refraction strength elongation weight .eta.a (poise) Tg (.degree.C.) Secondary pressure .DELTA.n.sub.2.0 (.times. 10.sup.4) .DELTA.n.sub.4.5 (.times. 10.sup.4) (kg/cm.sup.2) (%)__________________________________________________________________________Example 1 10,400 2.0 .times. 10.sup.3 177 50/20 -0.2 -0.2 740 10 50/25 0.1 -0.2Example 2 11,000 2.5 .times. 10.sup.3 160 50/20 -0.2 -0.15 730 12 50/25 0.1 -0.2Example 4 11,200 6.0 .times. 10.sup.3 178 50/20 -0.2 -0.2 750 13 50/25 0.1 -0.2Comparative 7,800 1.0 .times. 10.sup.3 175 Too brittle to mold 360 3.3Example 1Comparative 16,900 2.0 .times. 10.sup.4 190 60/25 3.5 -2.3 740 80Example 2 60/30 3.6 -2.5Comparative 17,400 2.5 .times. 10.sup.3 150 50/20 1.8 -0.7 590 140Example 4 50/25 2.5 -0.8Comparative 14,700 1.5 .times. 10.sup.3 148 40/10 0.6 -0.6 590 60Example 5 30/10 0.6 -0.5Comparative 13,000 1.0 .times. 10.sup.3 146 Too brittle to mold 220 3.0Example 6__________________________________________________________________________
It is evident from the above Table that as compared with the polycarbonate resins of bisphenol A (Comparative Examples 4 to 6), in the polycarbonate resins of the present invention, the double refraction is substantially low, and the variation in .DELTA.n is extremely small in spite of the fact that the melt flow characteristics are lowered, and further the heat resistance is substantially improved.
On the other hand, if the average molecular weight is less than 9,500 (Comparative Example 1), no adequate strength will be obtained, and if the average molecular weight exceeds 14,000 (Comparative Example 2), it will be difficult to obtain a molding material having a minimum optical distortion.

Number	Name	Date	Kind
4495345	Kawakami et al.	Jan 1985
4529791	Glass	Jul 1985

Number	Date	Country
0089801	Sep 1983	EPX
3343898	Jun 1984	DEX
3423864	Jan 1985	DEX
2377267	Jan 1978	FRX

Polycarbonate and optical disc substrate

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