Polycarbonate capped with phenolic chain terminator mixture

A polycarbonate having a principal chain comprising a repeating unit represented by the formula: ##STR1## (a) a substituted phenoxy group represented by the formula (II) ##STR2## (wherein A is as defined in the appended specification) and (b) p-tert-butyl phenoxy group represented by the formula (III) ##STR3## and/or the phenoxy group represented by the formula (IV) ##STR4## bonded to the terminals thereof in the ratio of (a) 10 to 99 mole percent of the said substituted phenoxy group, and (b) 90 to 1 mole percent of p-tert-butylphenoxy group and/or phenoxy group. This polycarbonate has so high a fluidity and an impact resistance that it is moldable into thin or complex shapes.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a polycarbonate, a process for production 
thereof, and a polycarbonate resin composition containing the said 
polycarbonate, and more particularly to a polycarbonate with an improved 
balance of fluidity and impact resistance, to a process for an efficient 
production thereof and to a polycarbonate resin composition comprising the 
said polycarbonte, the composition being excellent in various physical 
properties. 
2. Description of the Related Arts. 
Among the conventional polycarbonate products, some have high grade of 
fluidity with simply reduced molecular weight for being molded into 
complexed and thinner products. The said polycarbonates having the high 
fluidity, however, suffer from a disadvantage in that mechanical strength, 
in particular, Izod impact strength is insufficiently high at low 
temperature. To overcome this disadvantage, extensive investigations have 
been made to develop a polycarbonate having a high mechanical strength 
maintained even when reduced in molecular weight. 
As a result of the said investigations, it has been found that the 
polycarbonate employing both cumylphenol (i.e., .alpha., 
.alpha.-dimethylbenzylphenol) or tert-octylphenol (i.e., 
1,1,3,3-tetramethylbutylphenol). and p-tert-butylphenol or phenol a 
molecular weight modifiers in a predetermined ratio, which are bonded to 
the terminals of the molecules, has the desired properties suitable for 
the said polycarbonate. The present invention has been attained based on 
the above findings. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide a polycarbonate having an 
improved balance of fluidity and impact resistance. 
Another object of the present invention is to provide a polycarbonate 
having superior Izod impact strength at low temperatures. 
Still another object of the present invention is to provide the 
polycarbonate having superior moldability into the thinner or complex 
products. 
A further object of the present invention is to provide a process for 
efficiently producing the said polycarbonate. 
A still further object of the present invention is to provide a resin 
composition comprising the said polycarbonate and being excellent in 
various properties. 
The present invention is to provide a polycarbonate having a principal 
chain comprising a repeating unit represented by the formula: 
##STR5## 
(a) A substituted phenoxy group represented by the formula: 
##STR6## 
wherein A is an .alpha., .alpha.-dimethylbenzyl group represented by the 
formula: 
##STR7## 
or a 1,1,3,3-tetramethylbutyl group represented by the formula: 
##STR8## 
and 
(b) a p-tert-butylphenoxy group represented by the formula: 
##STR9## 
and/or a phenoxy group represented by the formula: 
##STR10## 
bonded to the terminals of the molecules in the ratio of (a) 10 to 99 mole 
percent of the said substituted phenoxy group and (b) 90 to 1 mole percent 
of a p-tert-butylphenoxy group and/or a phenoxy group. 
The present invention also provides a process for producing the 
polycarbonate using a molecular weight modifier comprising: 
(a) 10 to 99 mole percent of a substituted phenol represented by the 
formula: 
##STR11## 
(wherein A is the same as defined above) and 
(b) 90 to 1 mole percent of p-tert-butylphenol and/or phenol. 
The present invention also provides a polycarbonate resin composition 
comprising 100 parts by weight of the said polycarbonate and 0.01 to 0.13 
part by weight of phosphoric antioxidant.

DESCRIPTION OF PREFERRED EMBODIMENTS 
The polycarbonate of the present invention has the principal chain 
comprising a repeating unit represented by the said formula (I), and 
terminators comprising both a substituted phenoxy group (end group (a)) 
represented by the formula (II), and p-tert-butylphenoxy group represented 
by the formula (III) and/or phenoxy group represented by the formula (IV) 
(end group (b)) in the following ratio: 10 to 99 mole percent of end group 
(a) and 90 to 1 mole percent of end group (b), preferably 20 to 99 mole 
percent of end group (a) and 80 to 1 mole percent of end group (b). If end 
group (a) is below 10 mole percent, the mechanical strength is not 
sufficient. 
The substituted phenoxy groups i.e., the abovementioned end group (a) 
represented by the formula (II) can be classified into: cumylphenoxy group 
represented by the formula: 
##STR12## 
(i.e., .alpha.,.alpha.-dimethylbenzyl phenoxy group) (p-cumylphenoxy 
group, o-cumylphenoxy group, and m-cumylphenoxy group; particularly, 
p-cumylphenoxy group is preferred.); and tert-octylphenoxy group 
represented by the formula: 
##STR13## 
(i.e., p-tert-octylphenoxy group, o-tert-octylphenoxy group, and 
m-tert-octylphenoxy group; particularly, p-tert-octylphenoxy group is 
preferred.) End group (a) of the polycarbonate of the present invention is 
cumylphenoxy group represented by the formula (II-1), tert-octylphenoxy 
group represented by the formula (II-2), or a mixture thereof. 
The polycarbonate of the present invention comprises the mixture of (1) the 
principal chain comprising the repeating unit represented by the formula 
(I), bonded to an end group (a) at one terminal thereof and to an end 
group (b) at the other terminal (2) the principal chain comprising the 
repeating unit represented by the formula (I), bonded to end groups (a) at 
both terminals thereof, (3) the principal chain having the repeating unit 
represented by the formula (I), bonded to end groups (b) at both the 
terminals thereof (for example, mixtures of (1) to (3), mixtures of (1) 
and (2), mixtures of (1) and (3), or mixtures of (2) and (3)). The average 
values of these end groups are assumed to be the ratio as mentioned above 
(mole%). 
The molecular weight of the polycarbonate of the present invention is not 
critical. Usually, the viscosity average molecular weight is 10,000 or 
more, preferably 10,000 to 50,000, and the most preferably 15,000 to 
30,000. 
The polycarbonate of the present invention has the principle chain 
comprising the repeating unit represented by the said formula (I) bonded 
to end groups (a) and (b) at the terminals of the molecules. The molecular 
chain may contain a small amount of a repeating unit other than the said 
repeating unit of the formula (I). 
The polycarbonate of the present invention can be produced by various 
methods, including two typical ones as follows. Method I: a method in 
which used are the molecular weight modifier comprising (a) 10 to 99 mole 
percent of substituted phenol represented by the formula (II') 
(specifically, p-cumylphenol, o-cumylphenol, m-cumylphenol, or 
p-tertoctylphenol, o-tert-octylphenol, m-tert-octylphenol). and (b) 90 to 
1 mole percent of p-tert-buthylphenol and/or phenol. Method II: a method 
in which (a) 10 to 99 mole percent of polycarbonate with the said 
substituted phenoxy group represented by the formula (II) at the terminals 
of the molecules, and (b) 1 to 90 mole percent of polycarbonate with 
p-tert-butylphenoxy group and/or phenoxy group at the terminals of the 
molecules are kneaded. 
In the said Method I, the desired polycarbonate can be obtained by 
performing interfacial polycondensation reaction adding the said molecular 
weight modifier (comprising (a) 10 to 99 mole percent of substituted 
phenol of the formula (II') and (b) 90 to 1 mole percent of 
p-tert-butylphenol and/or phenol) to the reaction system before or after 
bisphenol A and phosgene dissolved in alkali solution are reacted with 
each other in the presence of the inert organic solvent. This can be 
achieved also by the pyridine method in which bisphenol A and the said 
molecular weight modifier are dissolved in pyridine or the mixed solvent 
of pyridine and inert organic solvent and phosgene is blown in this 
solution for reaction. 
Instead of bisphenol A used as a raw material or together with the said 
bisphenol A, another bivalent phenol can be used. In this case, the 
polycarbonate has the principal chain comprising the repeating unit 
corresponding to the bivalent phenol used. 
The polycarbonate resulted by Method I mainly comprises the mixture of (1) 
to (3) described above. 
On the other hand, in Method II, the desired polycarbonate can be obtained 
by producing polycarbonate (A.sub.1) having the substituted phenoxy group 
of the formula (II) at the molecular terminal by reacting bisphenol A with 
phosgene using the substituted phenol of the formula (II') as a molecular 
weight modifier; producing polycarbonate (A.sub.2) having 
p-tert-butylphenoxy group and polycarbonate (A.sub.3) having phenoxy group 
at molecular terminal by reacting bisphoenol A with phosgene using 
p-tert-butylphenol and/or phenol as a molecular weight modifier; and 
kneading 10 to 99 mole percent of polycarbonate A.sub.1 and/or 90 to 1 
mole percent of polycarbonate A.sub.2 and/or A.sub.3. Instead of or in 
addition to the said polycarbonates A.sub.2 and A.sub.3, a polycarbonate 
having a p-tert-butylphenoxy group at a molecular end and a phenoxy group 
at the other end can also be used. 
The polycarbonate obtained by the above described Method II mainly 
comprises the mixture of (2) and (3). 
The polycarbonate itself of the present invention has sufficient mechanical 
properties and moldability because the specific substituents are bonded to 
the terminals at a definite ratio, and the polycarbonate resin composition 
made by adding 0.01 to 0.13 parts by weight of phosphoric antioxidant per 
100 parts by weight of polycarbonate has still superior properties. This 
composition can be obtained by mixing the said polycarbonate with the 
phosphoric antioxidant by a conventional method. 
Examples of the phosphoric antioxidant used are as follows: 
trialkyl phosphites such as tris(nonylphenyl)phosphites, 
2-ethylhexydiphenylphosphite, trimethylphosphite, triethylphosphite, 
tributylphosphite, trioctylphosphite, trinonylphosphite, 
tridecylphosphite, trioctadecylphosphite, 
distearilpentaerythrityldiphosphite, tris(2-chloroethyl) phosphite, 
tris(2,3-dichloropropyl)phosphite; 
tricycloalkylphosphites such as tricyclohexylphosphite; 
triarylphosphites such as triphenylphosphite, tricresylphosphite, 
tris(ethylphenyl)phosphite, tris(butylphenyl)phosphite, 
tris(hydroxyphenyl)phosphite; 
trialkylphosphates such as trimethylphosphate, triethylphosphate, 
tributylphosphate, trioctylphosphate, tridecylphosphate, 
trioctadecylphosphate, distearylpentaerythrityldiphosphate, 
tris(2-chloroethyl) phosphate, tris(2,3-dichloropropyl)phosphate; 
tricycloalkylphosphates such as tricyclohexylphosphate; 
triarylphosphates such as triphenylphosphate, tricresylphosphate, 
tris(nonylphenyl)phosphate. 2-ethylphenyldiphenylphosphate. These can be 
used solely or in combination with one another. 
The amount of phosphoric antioxidant must be determined within the range of 
0.01 to 0.13 part by weight per 100 parts by weight of the polycarbonate 
of the present invention as mentioned above. If the amount of phosphoric 
antioxidant is less than 0.01 part by weight, the resulting resin 
composition is not sufficiently improved in mechanical strength and is 
liable to be colored. Alternatively, if it exceeds 0.13 parts by weight, 
the polycarbonate resin composition tends to be lowered in mechanical 
strength. 
The polycarbonate resin composition of the present invention can be added 
with other additives such as lubricant if necessary. The lubricants used 
are stearylalcohol, stearic acid monoglyceride. pentaerythritolstearic 
acid ester, beeswax, etc. This lubricant should be added within the range 
of 2,000 to 4,000 ppm per the composition to improve mold-releasing 
property. 
The composition of the present invention can also be added with inorganic 
filler, flame retardant, stabilizer, colorant, etc. 
According to the present invention, a polycarbonate resin and polycarbonate 
resin composition having high fluidity and high impact-resistance, 
excellent in fluidity and impact strength, particularly in impact strength 
at low temperatures can be obtained. 
The polycarbonate resin and polycarbonate resin compositions of the present 
invention can therefore be molded into thin film or complex shapes that 
has been difficult, and can maintain sufficient mechanical strength even 
if reduced in molecular weight to be of high fluidity grade. 
The polycarbonate resin and its compositions are used widely and 
efficiently for industrial materials such as home electric appliances, 
office automation equipment, building materials, etc. 
The present invention is described in more detail by referring to examples 
and comparative examples. 
PREATION EXAMPLES 
(Preparation of Polycarbonate Oligomer) 
Sixty kilograms of bisphenol A was dissolved in 400 liters of 5 percent 
sodium hydroxide aqueous solution to prepare sodium hydroxide aqueous 
solution containing bisphenol A. 
Then, the said sodium hydroxide aqueous solution containing bisphenol A 
maintained at room temperature and methylene chloride were introduced into 
the tubular reactor having inner diameter of 10 mm and the length of 10 m 
through the orifice plate at flow rates of 138 liters/hour and of 69 
liters/hour, respectively. Thereafter, phosgene was blown at flow rate of 
10.7 kg/hour concurrently for three hours. The tubular reactor was duplex 
and the exhaust temperature of reaction fluid was maintained to 25.degree. 
C. by passing coolant through the jacket. pH of the exhaust fluid was 
adjusted to 10 to 11. The reaction fluid was allowed to stand to separate 
and remove the aqueous phase. To the methylene chloride phase (220 liters) 
collected, 170 liters of methylene chloride was added, then agitated 
sufficiently to produce polycarbonate oligomer (317 g/liter in 
concentration). The polycarbonate oligomer has degree of polymerization of 
3 to 4. 
Production Example 1 (Production of polycarbonate resin A.sub.1) 
p-cumylphenol (0.51 mole) was dissolved as a molecular weight modifier in 
9.0 liters of the polycarbonate oligomer obtained in the Preparation 
Example. On the other hand, 23.5 g (0.59 mole) of sodium hydroxide was 
dissolved in 600 cc of water and 5.2 cc of triethylamine was added to the 
solution. Then the resulting solution was added to the polycarbonate 
oligomer in which the said molecular weight modifier was dissolved, and 
agitated for one hour at 500 rpm at ordinary temperature. 
Then 9.6 liters of methylene chloride and sodium hydroxide aqueous solution 
containing bisphenol A (consisting of 611 g of bisphenol A and 357 g of 
sodium oxide) were added, and the resulting mixture was stirred at 500 rpm 
for two hours at ordinary temperature. 
After that, 3 liters of methylene chloride was added thereto, washed with 5 
liters of water, alkali-cleaned with 5 liters of 0.01 normal sodium 
hydroxide aqueous solution, acid-cleaned with 5 liters of 0.1 normal 
hydrochloric acid aqueous solution, and cleaned with 5 liters of water in 
this Finally, the methylene chloride was removed to obtain the chipped 
polycarbonate (i.e., polycarbonate resin A.sub.1) 
This polycarbonate resin A.sub.1 has a viscosity average molecular weight 
of 1.9.times.10.sup.4. 
Production Example 2 (Production of polycarbonate resin A.sub.2) 
The chipped polycarbonate (polycarbonate resin A.sub.2) was obtained in the 
same manner as in Production Example 1 except that the molecular weight 
modifier was replaced from p-cumylphenol to p-tert-butylphenol. The 
resulting polycarbonate resin A.sub.2 had a viscosity average molecular 
weight of 1.9.times.10.sup.4. 
Production Example 3 (Production of polycarbonate resin A.sub.3) 
The chipped polycarbonate (polycarbonate resin A.sub.3) was obtained in the 
same manner as in Production Example 1 except that the molecular weight 
modifier was replaced from p-cumylphenol to phenol. The resulting 
polycarbonate resin A.sub.3 had a viscosity average molecular weight of 
1.9.times.10.sup.4. 
Production Example 4 (Production of polycarbonate resin A.sub.4) 
The chipped polycarbonate (polycarbonate resin A.sub.4) was obtained in the 
same manner as in Production Example 1 except that the molecular weight 
modifier was replaced to 0.255 mole of p-cumylphenol and 0.255 mole of 
p-tert-butylphenol instead of 0.51 mole of p-cumylphenol. The resulting 
polycarbonate resin A.sub.4 had a viscosity average molecular weight of 
1.9.times.10.sup.4. 
Production Example 5 (Production of polycarbonate resin A.sub.5) 
The chipped polycarbonate (polycarbonate resin A.sub.5) was obtained in the 
same manner as in Production Example 1 except that the molecular weight 
modifier was replaced to 0.459 mole of p-cumylphenol and 0.051 mole of 
phenol instead of 0.51 mole of p-cumylphenol. The polycarbonate resin 
A.sub.5 had a viscosity average molecular weight of 1.9.times.10.sup.4. 
EXAMPLES 1 TO 9, COMATIVE EXAMPLE 1, AND REFERENCE EXAMPLES 1 TO 3 
The polycarbonate resins obtained in Preparation Examples described above 
were mixed in the ratios by weight shown in Table 1 and granulated by an 
extruder at temperatures of 220.degree. to 270.degree. C. The pellet thus 
obtained was injection-molded, and Izod impact strength was measured. The 
results are shown in Table 2. 
TABLE 1 
______________________________________ 
Example 1 A.sub.1 :98%, 
A.sub.2 :2% 
Example 2 A.sub.1 :95%, 
A.sub.3 :5% 
Example 3 A.sub.1 :85%, 
A.sub.2 :15% 
Example 4 A.sub.1 :70%, 
A.sub.3 :30% 
Example 5 A.sub.1 :50%, 
A.sub.2 :50% 
Example 6 A.sub.1 :30%. 
A.sub.3 :70% 
Example 7 A.sub.1 :15%, 
A.sub.2 :85% 
Example 8 A.sub.4 :100%, 
-- 
Example 9 A.sub.5 :100%, 
-- 
Comparative A.sub.1 : 5%, 
A.sub.2 :95% 
Example 1 
Reference A.sub.1 :100%, 
-- 
Example 1 
Reference A.sub.2 :100%, 
-- 
Example 2 
Reference A.sub.3 :100%, 
-- 
Example 3 
______________________________________ 
TABLE 2 
______________________________________ 
Izod impact strength*.sup.1 
No. 5.degree. C. 
0.degree. C. 
-5.degree. C. 
-10.degree. C. 
______________________________________ 
Example 1 10 10 8 3 
Example 2 10 10 8 3 
Example 3 10 10 9 4 
Example 4 10 10 9 4 
Example 5 10 10 8 3 
Example 6 10 10 8 3 
Example 7 10 9 7 1 
Example 8 10 10 9 4 
Example 9 10 10 8 4 
Comparative 10 8 3 0 
Example 1 
Reference 10 10 7 2 
Example 1 
Reference 9 6 2 0 
Example 2 
Reference 9 5 1 0 
Example 3 
______________________________________ 
*.sup.1 According to JISK-7110. Each value indicates the number of 
ductilefractured samples total 10 samples were tested for Izod impact 
resistance. Other samples were brittlefractured. All the samples used wer 
notched and 3 mm in thickness and measured at weigher 4.0 J. 
EXAMPLES 10 TO 15, COMATIVE EXAMPLE 2, AND REFERENCE EXAMPLES 4 AND 5 
The polycarbonate resins obtained in the Production Examples 1 to 4 and 
phosphoric antioxidant (B.sub.1 : tris (nonylphenyl)phosphite, and B.sub.2 
: 2-ethylhexyldiphenylphosphite) were mixed in the ratios shown in Table 3 
and granulated by an extruder at temperatures of 220.degree. to 
270.degree. C. The resulting pellet was injection-molded to be measured 
for Izod impact strength. The results are shown in Table 4. 
TABLE 3 
______________________________________ 
% by*.sup.2 % by*.sup.2 
Parts by*.sup.3 
No. weight weight weight 
______________________________________ 
Example 10 A.sub.1 :98 A.sub.2 :2 
B.sub.1 :0.02 
Example 11 A.sub.1 :95 A.sub.3 :5 
B.sub.2 :0.02 
Example 12 A.sub.1 :85 A.sub.2 :15 
B.sub.1 :0.05 
Example 13 A.sub.1 :50 A.sub.2 :50 
B.sub.2 :0.05 
Example 14 A.sub.5 :100 
-- B.sub.1 :0.02 
Example 15 A.sub.1 :15 A.sub.2 :85 
B.sub.1 :0.02 
Comparative 
A.sub.1 :5 A.sub.2 :95 
B.sub.1 :0.02 
Example 2 
Reference A.sub.1 :100 
-- B.sub.1 :0.02 
Example 4 
Reference A.sub.2 :100 
-- B.sub.1 :0.02 
Example 5 
______________________________________ 
*.sup.2 Indicates the portion of the polycarbonates used. 
*.sup.3 Indicates the parts of phosphoric antioxidants per 100 parts by 
weight of polycarbonate. 
TABLE 4 
______________________________________ 
Izod impact strength*.sup.1 
No. 5.degree. C. 
0.degree. C. 
-5.degree. C. 
-10.degree. C. 
______________________________________ 
Example 10 10 10 10 7 
Example 11 10 10 10 8 
Example 12 10 10 10 7 
Example 13 10 10 10 7 
Example 14 10 10 10 8 
Example 15 10 10 9 4 
Comparative 10 9 5 2 
Example 2 
Reference 10 10 9 4 
Example 4 
Reference 10 9 4 1 
Example 5 
______________________________________ 
*.sup.1 Same as in Table 2. 
The molar ratios of p-cumylphenoxy group, p-tert-butylphonoxy group, and 
phenoxy group contained in the polycarbonate resin or its compositions 
shown in the said Examples and Comparative Examples were calculated based 
on the measured values of the proton nuclear magnetic resonance spectrum 
(heavy chloroform solvent). The results are shown in Table 5. 
TABLE 5 
______________________________________ 
No. Mole ratio (%) 
______________________________________ 
Example 1 
p-cumylphenoxy:p-tert-butylphenoxy = 98.2:1.8 
Example 2 
P-cumylphenoxy:phenoxy = 94.7:5.3 
Example 3 
p-cumylphenoxy:p-tert-butylphenoxy = 85.1:14.9 
Example 4 
P-cumylphenoxy:phenoxy = 70.4:29.6 
Example 5 
p-cumylphenoxy:p-tert-butylphenoxy = 50.0:50.0 
Example 6 
P-cumylphenoxy:phenoxy = 30.5:69.5 
Example 7 
p-cumylphenoxy:p-tert-butylphenoxy = 15.4:84.6 
Example 8 
p-cumylphenoxy:p-tert-butylphenoxy = 50.1:49.9 
Example 9 
P-cumylphenoxy:phenoxy = 79.9:20.1 
Example 10 
p-cumylphenoxy:p-tert-butylphenoxy = 98.1:1.9 
Example 11 
P-cumylphenoxy:phenoxy = 94.8:5.2 
Example 12 
p-cumylphenoxy:p-tert-butylphenoxy = 85.0:15.0 
Example 13 
p-cumylphenoxy:p-tert-butylphenoxy = 50.1:49.9 
Example 14 
P-cumylphenoxy:phenoxy = 79.9:20.1 
Example 15 
p-cumylphenoxy:p-tert-butylphenoxy = 15.0:85.0 
Comparative 
p-cumylphenoxy:p-tert-butylphenoxy = 4.9:95.1 
Example 1 
Comparative 
p-cumylphenoxy:p-tert-butylphenoxy = 4.9:95.1 
Example 2 
______________________________________ 
FIG. 1 shows the relationship between the Izod impact strength of samples 
obtained from the polycarbonate resin or its compositions shown in the 
said Examples, Comparative Examples, and Reference Examples at the 
temperature of -5.degree. C. and the mole ratio of p-cumylphenoxy group 
and p-tert-butylphenoxy group in the said samples. 
Production Example 6 (Production of polycarbonate resin A'.sub.1) 
Into 9.0 liters of the said polycarbonate oligomer obtained in the above 
Preparation Example, 0.51 mole of p-tert-octylphenol (that is, 
4-(1,1,3,3-tetramethylbutyl)phenol) was dissolved as molecular weight 
modifier. 23.5 g (0.59 mole) of sodium hydroxide was dissolved in 600 c of 
water, 5.2 cc of triethylamine was added to the said solution, and the 
resulting solution was added to the polycarbonate oligomer in which the 
said molecular weight modifier was dissolved, and then agitated for one 
hour at 500 rpm at the ordinary temperature. 
Then, 9.6 liters of methylene chloride and aqueous sodium hydroxide 
solution of bisphenol A (containing 611 g of bisphenol A and 357 g of 
sodium hydroxide) were added and agitated for two hours at 500 rpm at the 
ordinary temperature. 
Thereafter, 3 liters of the methylene chloride was added, cleaned with 5 
liters of water, alkali-cleaned with 0.01 normal sodium hydroxide aqueous 
solution, acid-cleaned with 0.1 normal hydrochloric acid aqueous solution, 
and cleaned with 5 liters of water in this order. Finally, chipped 
polycarbonate (polycarbonate resin A'.sub.1) was obtained after the 
metylene chloride was removed. The viscosity average molecular weight of 
the resulting polycarbonate resin A'.sub.1 was 1.9.times.10.sup.4. 
Production Example 7 (Production of polycarbonate A'.sub.4) 
The chipped polycarbonate (polycarbonate resin A'.sub.4) was obtained in 
the same manner as in Production Example 6 except that 0.255 mole of 
p-tert-octylphenol and 0.255 mole of p-tert-butylphenol were used as 
molecular weight modifier instead of 0.51 mole of p-tert-octylphenol in 
Production Example 6. The viscosity average molecular weight of the 
resulting polycarbonate resin A'.sub.4 was 1.9.times.10.sup.4. 
Production Example 8 (Production of polycarbonate resin A'.sub.5) 
The chipped polycarbonate resin (polycarbonate resin A'.sub.5) was obtained 
in the same manner as in Production Example 6 except that 0.459 mole of 
p-tert-octylphenol and 0.051 mole of phenol were used as molecular weight 
modifiers instead of 0.51 mole of p-tert-octylphenol in Production Example 
6. The viscosity average molecular weight of the resulting polycarbonate 
resin A'.sub.5 was 1.9.times.10.sup.4. 
EXAMPLES 16 TO 24, COMATIVE EXAMPLE 3 AND REFERENCE EXAMPLES 6 
The polycarbonate resins obtained in the above Production Examples were 
mixed in the ratio by weight shown in Table 6 and granulated by an 
extruder at temperatures of 220.degree. to 270.degree. C. The resulting 
pellet was injection-molded to be measured for Izod impact strength. The 
results are shown in Table 7. 
TABLE 6 
______________________________________ 
Example 16 A'.sub.1 :98%, 
A.sub.2 :2% 
Example 17 A'.sub.1 :95%, 
A.sub.3 :5% 
Example 18 A'.sub.1 :85%. 
A.sub.2 :15% 
Example 19 A'.sub.1 :70%, 
A.sub.3 :30% 
Example 20 A'.sub.1 :50%, 
A.sub.2 :50% 
Example 21 A'.sub.1 :30%, 
A.sub.3 :70% 
Example 22 A'.sub.1 :15%, 
A.sub.2 :85% 
Example 23 A'.sub.4 :100%, 
-- 
Example 24 A'.sub.5 :100%, 
-- 
Comparative A'.sub.1 :5%, 
A.sub.2 :95% 
Example 3 
Reference A'.sub.1 :100%, 
-- 
Example 6 
______________________________________ 
TABLE 7 
______________________________________ 
Izod impact strength*.sup.1 
No. 5.degree. C. 
0.degree. C. 
-5.degree. C. 
-10.degree. C. 
______________________________________ 
Example 16 10 10 8 4 
Example 17 10 10 8 4 
Example 18 10 10 8 3 
Example 19 10 10 9 4 
Example 20 10 10 9 4 
Example 21 10 10 8 3 
Example 22 10 9 6 1 
Example 23 10 10 9 4 
Example 24 10 10 8 3 
Comparative 10 7 4 0 
Example 3 
Reference 10 10 7 3 
Example 6 
______________________________________ 
*.sup.1 Same as *1 shown in Table 1. 
EXAMPLES 25 TO 30, COMATIVE EXAMPLE 4, AND REFERENCE EXAMPLE 7 
The polycarbonate resin obtained in the above Production Example and 
phosphoric antioxidant (B.sub.1 : tris(nonylphenyl)phosphite and B.sub.2 : 
2-ethylhexyldiphenylphosphite) were mixed and granulated by an extruder at 
temperatures of 220.degree. to 270.degree. C. The pellet resulted was 
injection-molded to be measured for Izod impact strength. The results are 
shown in Table 9. 
TABLE 8 
______________________________________ 
% by*.sup.2 % by*.sup.2 
Parts by 
No. weight weight weight 
______________________________________ 
Example 25 A'.sub.1 :98 A.sub.2 :2 
B.sub.1 :0.02 
Example 26 A'.sub.1 :95 A.sub.3 :5 
B.sub.2 :0.02 
Example 27 A'.sub.1 :85 A.sub.2 :15 
B.sub.1 :0.05 
Example 28 A'.sub.1 :50 A.sub.2 :50 
B.sub.2 :0.05 
Example 29 A'.sub.1 :15 A.sub.2 :85 
B.sub.1 :0.02 
Example 30 A'.sub.5 :100 
-- B.sub.1 :0.02 
Comparative 
A'.sub.1 :98 A.sub.2 :2 
B.sub.1 :0.02 
Example 4 
Reference A'.sub.1 :100 
-- B.sub.1 :0.02 
Example 7 
______________________________________ 
*.sup.2 Indicates the portion of the polycarbonate used. 
*.sup.3 Indicates the parts by weight of the phosphoric antioxidant per 
100 parts by weight of the polycarbonate. 
TABLE 9 
______________________________________ 
Izod impact strength*.sup.1 
No. 5.degree. C. 
0.degree. C. 
-5.degree. C. 
-10.degree. C. 
______________________________________ 
Example 25 10 10 10 7 
Example 26 10 10 10 7 
Example 27 10 10 10 8 
Example 28 10 10 10 8 
Example 29 10 10 8 3 
Example 30 10 10 10 8 
Comparative 10 8 4 1 
Example 4 
Reference 10 10 9 3 
Example 7 
______________________________________ 
*.sup.1 Same as *1 shown in Table 7. 
Next, the mole ratios of p-tert-octylphenoxy group, p-tert-butylphenoxy 
group and phenoxy group contained in the polycarbonate resin or its 
compositions shown in the said Examples and Comparative Examples were 
calculated based on tbe measured value of the proton nuclear magnetic 
reasonance spectrum (heavy chloroform solvent). The (calculation) results 
are shown in Table 10. 
TABLE 10 
______________________________________ 
No. Mole ratio (%) 
______________________________________ 
Example 16 
p-tert-octylphenoxy:p-tert-butylphenoxy = 98.1:1.9 
Example 17 
P-tert-octylphenoxy:phenoxy = 94.8:5.2 
Example 18 
p-tert-octylphenoxy:p-tert-butylphenoxy = 85.0:15.0 
Example 19 
P-tert-octylphenoxy:phenoxy = 70.3:29.7 
Example 20 
p-tert-octylphenoxy:p-tert-butylphenoxy = 50.1:49.9 
Example 21 
P-tert-octylphenoxy:phenoxy = 30.5:69.5 
Example 22 
p-tert-octylphenoxy:p-tert-butylphenoxy = 15.4:84.6 
Example 23 
p-tert-octylphenoxy:p-tert-butylphenoxy = 50.0:50.0 
Example 24 
P-tert-octylphenoxy:phenoxy = 80.1:19.9 
Example 25 
p-tert-octylphenoxy:p-tert-butylphenoxy = 98.2:1.8 
Example 26 
P-tert-octylphenoxy:phenoxy = 94.7:5.3 
Example 27 
p-tert-octylphenoxy:p-tert-butylphenoxy = 85.1:14.9 
Example 28 
p-tert-octylphenoxy:p-tert-butylphenoxy = 49.9:50.1 
Example 29 
p-tert-octylphenoxy:p-tert-butylphenoxy = 15.1:84.9 
Example 30 
P-tert-octylphenoxy:phenoxy = 80.0:20.0 
Com- p-tert-octylphenoxy:p-tert-butylphenoxy = 5.0:95.0 
parative 
Example 3 
Com- p-tert-octylphenoxy:p-tert-butylphenoxy = 4.9:95.1 
parative 
Example 4 
______________________________________ 
FIG. 2 shows the relationship between the Izod impact strength of samples 
obtained from the polycarbonate resin or resin composition shown in the 
said Examples, Comprative Examples and Reference Examples at the 
temperature of -5.degree. C. and the mole ratio of p-tert-octylphenoxy 
group and p-tert-butylphenoxy group in the said samples.