JPH06136248A - Copolycarbonate composition - Google Patents

Abstract

PURPOSE:To provide a copolycarbonate composition excellent in, e.g. mechanical properties such as stiffness and heat resistance and more improved in moldability such as fluidity and capable of producing a molding excellent in visual appearance such as hue and surface gloss. CONSTITUTION:This copolycarbonate composition is composed of [A] a copolycarbonate synthesized by copolymerizing (i) resorcin and/or a substituted resorcin, (ii) an aromatic dihydroxy compound except resorcin and substituted resorcins and (iii) a compound capable of reacting with the aromatic dihydroxy compounds (i) and (ii) and of forming a carbonate bond and [B] a filler. This copolycarbonate composition contains preferably [C] an additive in addition to the above-mentioned [A] and [B].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to mechanical properties such as rigidity,
The present invention relates to a copolycarbonate composition which has excellent heat resistance and improved moldability such as fluidity, and can form a molded product having excellent hue and surface gloss.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate has excellent mechanical properties such as impact resistance, heat resistance and transparency, and is widely used in various mechanical parts, optical discs, automobile parts and the like. ing.

Conventional polycarbonates having the above-mentioned characteristics are usually produced by an interfacial polymerization method in which an aromatic dihydroxy compound such as bisphenol A is directly reacted with phosgene. Also known is a method for producing a polycarbonate by melt polycondensation of a carbonic acid diester and the above aromatic dihydroxy compound.

By the way, such a polycarbonate is
Usually, the glass transition temperature (Tg) is high, and when the polycarbonate is molded into, for example, an optical disk,
It is used by melting it at a high temperature to improve fluidity.

Generally, the longer the melting time of a polymer at a high temperature, the more the polymer tends to be deteriorated in transparency or hue. Therefore, if the flowability of the polycarbonate can be improved, a molded product that is less affected by heat during molding can be obtained, and the molding cycle can be shortened and the production yield can be improved, and the moldability can be improved.

[0006] Conventionally, a polycarbonate may be blended with a filler (reinforcing agent) such as glass fiber in order to improve mechanical properties such as rigidity. There is a problem in that the fluidity is further lowered, and the appearance such as surface glossiness of the obtained molded product is significantly reduced.

Therefore, the mechanical properties such as rigidity are improved without deteriorating the properties inherently possessed by polycarbonate, and the molded product is excellent in moldability such as fluidity and has excellent surface gloss and hue. It was desired to have a polycarbonate that can form

In view of the above-mentioned conventional techniques, the inventors of the present invention have conducted extensive studies to obtain a polycarbonate composition having excellent mechanical properties and the like and also having excellent fluidity. As a result, as a constitutional unit of an aromatic dihydroxy compound, It was found that the copolymerized polycarbonate containing at least a constitutional unit derived from resorcin or a substituted resorcin is excellent in flowability and moldability as well as excellent mechanical properties inherent in polycarbonate, heat resistance, transparency and the like. Further, a copolymerized polycarbonate composition obtained by blending a filler with such a copolymerized polycarbonate is
The inventors have found that they have excellent mechanical properties such as rigidity as well as fluidity, and have completed the present invention.

[0009]

The object of the present invention is to form a molded article which is excellent in mechanical properties such as rigidity and heat resistance, and further improved in moldability such as flowability, and which is excellent in appearance such as hue and surface gloss. It is an object of the present invention to provide a copolymerizable polycarbonate composition that can be used.

[0010]

SUMMARY OF THE INVENTION A copolycarbonate composition according to the present invention comprises [A] (i) resorcin and / or substituted resorcin, (ii) an aromatic dihydroxy compound other than resorcin and substituted resorcin, and (iii) these fragrances. It is characterized by comprising a copolymerized polycarbonate obtained by copolymerizing a group dihydroxy compound (i) and a compound capable of forming a carbonic acid bond by reacting with (ii), and a [B] filler.

The filler [B] is preferably glass fiber. The copolycarbonate composition according to the present invention preferably further contains a [C] additive in addition to the above [A] and [B].

This [C] additive has a (a) pKa value of 3
The following sulfur-containing acidic compound and / or a derivative formed from the acidic compound, (b) phosphorus compound,
It is preferably selected from the group consisting of (c) epoxy compounds and (d) phenolic stabilizers.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The copolymerized polycarbonate composition according to the present invention will be described below. First, the [A] copolymerized polycarbonate used in the present invention will be described.

This [A] copolymerized polycarbonate is
(i) resorcin and / or substituted resorcin, and (ii)
Aromatic dihydroxy compounds other than resorcin and substituted resorcin, and (iii) these aromatic dihydroxy compounds
(i) and (ii) are copolymerized with a compound capable of forming a carbonic acid bond, and (i) a structural unit derived from resorcin and / or substituted resorcin, and (ii) resorcin and substituted resorcin Containing a structural unit derived from an aromatic dihydroxy compound other than (iii) a structural unit derived from a compound capable of reacting with these aromatic dihydroxy compounds (i) and (ii) to form a carbonic acid bond. ing.

The structural unit derived from such (i) resorcin or substituted resorcin is represented by the following general formula [I].

[0016]

[Chemical 1]

In the above formula [I], R is a hydrocarbon group having 1 to 10 carbon atoms or a halide thereof, or halogen, and may be the same or different. n is an integer of 0-4.

Specific examples of such (i) resorcin and / or substituted resorcin include resorcin, 3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin. ,
3-phenylresorcin, 3-cumylresorcin, 2,3,4,5-
Tetrafluororesorcin, 2,3,4,5-tetrabromoresorcin and the like can be mentioned.

Of these, resorcin is particularly preferred. In the [A] copolymerized polycarbonate used in the present invention, the structural unit derived from such (i) resorcin and / or substituted resorcin is such that the structural unit derived from an aromatic dihydroxy compound is 100 mol%. , But is contained in an amount of less than 100 mol%, preferably 2 to 90 mol%, more preferably 2 to 40 mol%.

(Ii) The constitutional unit derived from an aromatic dihydroxy compound other than resorcin and / or a substituted resorcin is not particularly limited, and is usually derived from the following aromatic dihydroxy compound forming a polycarbonate. It may be a constituent unit.

[0021]

[Chemical 2]

Wherein R ¹ and R ² are hydrogen atoms or a monovalent hydrocarbon group, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are halogen or a monovalent hydrocarbon group, and these may be the same or different. p and q represent the integer of 0-4. ) Such (ii) other aromatic dihydroxy compounds include, for example, bis (4-hydroxyphenyl) methane, 1,
1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-
Hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy) -1-Methylphenyl)
Propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis Bis (hydroxyaryl) cycloalkanes such as (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3 Dihydroxy aryl ethers such as'-dimethyl phenyl ether, 4,4'-dihydroxy diphenyl sulfide, dihydroxy diaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, 4,4'-dihydroxy diphenyl Sulfoxide, dihydroxydiaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4, Examples thereof include dihydroxydiarylsulfones such as 4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferable. Further, as the compound (iii) capable of reacting with the aromatic dihydroxy compound to form a carbonic acid bond, specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, Examples thereof include carbonic acid diesters such as dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate, and carbonyl halide compounds such as phosgene.

Of these, diphenyl carbonate is particularly preferable. The copolycarbonate [A] used in the present invention may contain a structural unit derived from a dicarboxylic acid, a dicarboxylic acid ester or a dicarboxylic acid halide, in addition to the above structural units. This constituent unit is polyester polycarbonate.

Examples of such dicarboxylic acid or dicarboxylic acid ester and dicarboxylic acid halide include terephthalic acid, isophthalic acid, sebacic acid, decanedioic acid,
Dodecanedioic acid, diphenyl sebacate, diphenyl terephthalate, diphenyl isophthalate, diphenyl decanedioate, diphenyl dodecanedioate, terephthalic acid chloride, isophthalic acid chloride, sebacic acid chloride, decanedioic acid chloride, dodecanedioic acid chloride, etc. be able to.

Such polyester polycarbonate units may be present in the copolymerized polycarbonate [A] in an amount of 50 mol% or less, preferably 30 mol% or less.

The copolycarbonate [A] may contain a constitutional unit derived from a polyfunctional compound having three or more functional groups in one molecule, as long as the object of the present invention is not impaired. Good.

As such a polyfunctional compound, a compound having 3 or more phenolic hydroxyl groups or carboxyl groups is preferable, and a compound having 3 or more phenolic hydroxyl groups is particularly preferably used. Specifically, for example, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,
2 ', 2 "-Tris (4-hydroxyphenyl) diisopropylbenzene, α-methyl-α, α', α'-tris (4-hydroxyphenyl) -1,4-diethylbenzene, α, α ', α"- Tris (4
-Hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane-2,1,3,5-tri (4 -Hydroxyphenyl) benzene, 2,2-bis- [4,4- (4,4'-dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, etc. Is mentioned.

Of these, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like are preferable. Such a structural unit is usually 3 mol% or less, preferably 0.1 to 2 mol%, and more preferably 100 mol% when the structural unit derived from the aromatic dihydroxy compound in the copolymerized polycarbonate is 100 mol%. 0.1-1
It may be present in an amount of mol%.

The [A] copolymerized polycarbonate used in the present invention as described above has a glass transition temperature (Tg) of
Usually, 100 to 150 ° C, preferably 110 to 135 ° C
Is.

The thermal decomposition temperature is usually 350 to 380.
C., preferably 360 to 380.degree. Further JIS
According to K 7210, temperature 300 ℃, load 1.2K
The melt flow rate (MFR) measured under the condition of g is
Usually 5 to 100 g / 10 min, preferably 8 to 50 g / 10
Minutes.

The copolycarbonate [A] used in the present invention is excellent in mechanical properties, heat resistance, transparency and hue, as well as in chemical resistance and in moldability such as fluidity.

Particularly, the [A] copolymerized polycarbonate used in the present invention has a large MFR (g / 10 min) as compared with the conventional polycarbonate containing no structural unit derived from (i) resorcin or substituted resorcin, Excellent moldability such as fluidity.

The above-mentioned [A] copolymerized polycarbonate has (i) resorcin and / or substituted resorcin together with
(ii) Another aromatic dihydroxy compound, and (iii) a compound capable of reacting with these aromatic dihydroxy compounds (i) and (ii) to form a carbonic acid bond. There is no particular limitation. Specifically, it is produced by an interfacial method and a solution method using a carbonyl halide such as phosgene as a compound capable of reacting with an aromatic dihydroxy compound to form a carbonic acid bond, a melting method using a carbonic acid diester, and a solid-state polymerization method. It

Of these, the melt polymerization method is preferred in the present invention, and the details thereof will be described below. In the present invention, in producing the copolymerized polycarbonate by the melt polymerization method, (i) resorcin and / or substituted resorcin,
(ii) An aromatic dihydroxy compound other than resorcin and / or substituted resorcin and a carbonic acid diester are used.

The resorcin and the substituted resorcin used in the present invention are represented by the following general formula [III].

[0037]

[Chemical 3]

In the above formula [III], R is a hydrocarbon group having 1 to 10 carbon atoms or a halide thereof, or a halogen, which may be the same or different. n is an integer of 0-4.

As such a substituted resorcin, the above compounds are specifically used. Of these,
Resorcin is preferably used. These may be used alone or in combination.

In the present invention, when producing a copolymerized polycarbonate, such (i) resorcin and / or substituted resorcin is used in an aromatic dihydroxy compound.
It is used in an amount of less than 00%, preferably 2-90 mol%, more preferably 2-40 mol%.

The aromatic dihydroxy compound other than (ii) resorcin and / or substituted resorcin is preferably 98 to 10 mol%, more preferably 98 to 60 mol, based on 100 mol% of the aromatic dihydroxy compound.
Used in an amount of mol%.

The aromatic dihydroxy compound other than such resorcin and / or substituted resorcin is not particularly limited, but it is usually a compound represented by the following formula [IV], and further an phenyl group of the following [IV] is an aliphatic group. And a compound in which a halogen group is substituted.

[0043]

[Chemical 4]

Wherein R ¹ and R ² are hydrogen atoms or a monovalent hydrocarbon group, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are halogen or a monovalent hydrocarbon group, and these may be the same or different. p and q are integers of 0-4. ) Specific examples of the aromatic dihydroxy compound include the compounds described above.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. Specific examples of the carbonic acid diester include the compounds described above.

Of these, diphenyl carbonate is particularly preferably used. In the present invention, when producing the copolycarbonate, when the carbonic acid diester is 100 mol%, the carbonic acid diester is preferably 50 mol% or less, more preferably 30 mol% or less, and the dicarboxylic acid or dicarboxylic acid ester is added. It may be contained.

Specific examples of the dicarboxylic acid or dicarboxylic acid ester include the compounds described above. In the present invention, when a polycarbonate is produced, the carbonic acid diester as described above is 0.95 to 1.95 per 1 mol of the total amount of the aromatic dihydroxy compound.
It is desirable to use 30 moles, preferably 1.01 to 1.20 moles.

In the present invention, when a polycarbonate is produced, the aromatic dihydroxy compound and the carbonic acid diester as described above are used together with 3 parts in one molecule as described above.
It is also possible to use a polyfunctional compound having one or more functional groups.

When a polyfunctional compound is used, it is usually 0.03 per 1 mol of the total amount of the aromatic dihydroxy compound.
It is used in an amount of not more than 0.001 mol, preferably 0.001 to 0.02 mol, and more preferably 0.001 to 0.01 mol.

In the present invention, an aromatic dihydroxy compound containing resorcin and / or a substituted resorcin as described above and a carbonic acid diester are added in the presence of a catalyst (a) an alkali metal compound and / or an alkaline earth gold compound. It is preferable to perform melt polycondensation.

Specific examples of such alkali metal compounds and alkaline earth metal compounds (a) include organic acid salts and inorganic acid salts of alkali metals and alkaline earth metals,
Preferable examples include oxides, hydroxides, hydrides and alcoholates.

More specifically, such alkali metal compounds include sodium hydroxide, potassium hydroxide,
Lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride , Lithium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium Salts, dilithium salts, sodium salts of phenol, potassium salts, lithium salts and the like are used.

Specific examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate and carbonic acid. Calcium, barium carbonate,
Magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like are used.

These compounds may be used alone or in combination.
Can be used. Such alkali metal compounds
And / or the alkaline earth metal compound (a) is an aromatic diamine.
Usually 1 × 10 with respect to 1 mol of the total amount of the hydroxy compound.
^-8~ 1 x 10 ^-3Mol, preferably 1 × 10^-7~ 1 x 10
^-FiveMol, particularly preferably 1 × 10^-7~ 2.5 × 10^-6Mo
Used in the amount of le.

When the amount of the alkali metal compound or the alkaline earth metal compound (a) used is 1 × 10 ⁻⁸ to 1 × 10 ⁻³ mol per 1 mol of the total amount of the aromatic dihydroxy compound, the polymerization activity is high. An acidic compound (which will be described later) can be added in an amount that does not adversely affect the properties of the obtained copolycarbonate while being maintained, and the basicity of these compounds can be sufficiently neutralized or weakened,
It is possible to obtain a copolycarbonate having excellent hue, heat resistance, water resistance, and weather resistance, and excellent melt stability for a long time.

In the present invention, the catalyst as described above is used.
(a) together with an alkali metal compound and / or an alkaline earth metal compound, (b) a basic compound and / or
(c) A boric acid compound can be used.

Examples of the basic compound (b) include nitrogen-containing basic compounds that are easily decomposable or volatile at high temperature, and specifically, the following compounds can be mentioned.

Tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), trimethylbenzylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH ) Such as alkyl, aryl,
Ammonium hydroxides having araryl groups, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, R ₂ NH (wherein R is an alkyl group such as methyl or ethyl, an aryl group such as phenyl or toluyl). Etc.)
Secondary amines represented by RNH ₂ (wherein R is the same as above), pyridines such as pyridine, dimethylaminopyridine, pyrrolidinopyridine, 2-methylimidazole, 2-phenyl Imidazoles such as imidazole, or ammonia, tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Bu ₄ N
BPh _4), tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄₎ basic salts, such as.

Of these, tetraalkylammonium hydroxides, especially electronic tetraalkylammonium hydroxides containing few metal impurities, are preferably used.

Examples of the boric acid compound (c) include boric acid and boric acid esters represented by the following general formula. In the formula B (OR) _n (OH) _3-n , R is alkyl such as methyl or ethyl, aryl such as phenyl, and n is 1, 2 or 3.

Specific examples of such borate ester include trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and trinaphthyl borate. Is mentioned.

The preferred combination used as the catalyst in the present invention is a combination of (a) an alkali metal compound and / or an alkaline earth metal compound and (b) a nitrogen-containing basic compound.

At this time, (a) an alkali metal compound and / or
Alternatively, the alkaline earth metal compound is used in the amount as described above, and (b) the nitrogen-containing basic compound is 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, relative to 1 mol of the total amount of the aromatic dihydroxy compound, It is preferably used in an amount of 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol. (b) The amount of the nitrogen-containing basic compound used is 1 × 10 ⁻⁶ to 1 × 1 with respect to 1 mol of the total amount of the aromatic dihydroxy compound.
It is preferable that the content is 0 ^-1 mol because the transesterification reaction and the polymerization reaction proceed at a sufficient rate and a copolycarbonate excellent in hue, heat resistance and water resistance can be obtained.

As described above, the catalyst obtained by combining (a) an alkali metal compound and / or an alkaline earth metal compound with (b) a nitrogen-containing basic compound is excellent in heat resistance and water resistance and has improved color tone. A high-molecular weight copolycarbonate having excellent transparency can be produced with high polymerization activity.

Further, in the present invention, a catalyst comprising a combination of (a) an alkali metal compound and / or an alkaline earth metal compound and (c) boric acid or boric acid ester, and (a) an alkali metal compound and / or Alternatively, a catalyst composed of a combination of an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c) boric acid or a borate ester is preferably used.

In a catalyst composed of such a combination,
The alkali metal compound or alkaline earth metal compound (a) and the nitrogen-containing basic compound (b) are preferably used in the amounts described above.

(C) Boric acid or boric acid ester is 1 × 10 ^{−8 with} respect to 1 mol of the total amount of the aromatic dihydroxy compound.
~ 1 x 10 ^-1 mol, preferably 1 x 10 ^-7 to 1 x 10 ^-2
It is used in an amount of 1 mol, more preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol.

(C) The amount of boric acid or boric acid ester used is 1 × with respect to 1 mol of the total amount of the aromatic dihydroxy compound.
It is preferable that it is 10 ⁻⁸ to 1 × 10 ⁻¹ mol because the molecular weight does not easily decrease after heat aging, and a copolymerized polycarbonate excellent in hue, heat resistance and water resistance can be obtained.

In particular, (a) an alkali metal compound or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c)
The catalyst composed of boric acid or boric acid ester is excellent in transparency, heat resistance and water resistance and has an improved color tone, and can produce a high molecular weight copolycarbonate with high polymerization activity.

The polycondensation reaction of an aromatic dihydroxy compound containing resorcin and / or a substituted resorcin with a carbonic acid diester using such a catalyst is carried out under the polycondensation reaction condition of a conventionally known aromatic dihydroxy compound and a carbonic acid diester. It can be performed under the same conditions as.

Specifically, it is 80 to 250 ° C., preferably 100 to 230 ° C., more preferably 120 to 190 ° C.
At the temperature of 0 to 5 hours, preferably 0 to 4 hours, more preferably 0 to 3 hours, under normal pressure, the aromatic dihydroxy compound and the carbonic acid diester are reacted. Then, the reaction temperature is raised while reducing the pressure of the reaction system to carry out the reaction between the aromatic dihydroxy compound and the carbonic acid diester, and finally, under a reduced pressure of 5 mmHg or less, preferably 1 mmHg or less.
A polycondensation reaction of an aromatic dihydroxy compound and a carbonic acid diester is carried out at a temperature of 320 ° C.

The polycondensation reaction as described above may be carried out continuously or batchwise. Further, the reaction apparatus used for carrying out the above reaction may be a tank type, a tube type or a column type.

The copolycarbonate thus obtained usually has an intrinsic viscosity [η] of 0.2 to 1.2 dl.
/ G, preferably 0.3 to 1.0 dl / g. The production method as described above is preferable from the viewpoint of environmental hygiene since toxic substances such as phosgene and methylene chloride are not used in the melt polycondensation of the copolymerized polycarbonate.

According to this melt polymerization method, in the copolymer polycarbonate obtained, (i) resorcin and / or
Alternatively, even if (i) resorcin or substituted resorcin is used in an amount such that the substituted resorcin constitutional unit exceeds 90 mol%, it is excellent in hue, water resistance and heat resistance as compared with other methods such as interfacial polymerization. A copolymerized polycarbonate is obtained.

The copolycarbonate composition according to the present invention comprises the above-mentioned [A] copolycarbonate and [B] filler. In the present invention, as such a [B] filler, those generally known as fillers and reinforcing agents are widely used. Like this [B]
As the filler, specifically, silica, alumina, silica-alumina, talc, diatomaceous earth, clay, barium sulfate, calcium silicate, kaolin, quartz, glass,
Mica, graphite, molybdenum disulfide, gypsum,
Red iron oxide, titanium dioxide, zinc oxide, aluminum,
Powdery or plate-like inorganic compounds such as copper and stainless steel, glass fiber, carbon fiber, boron fiber, ceramic fiber,
Secondary processed products such as fibrous inorganic compounds such as asbestos fiber, stainless steel fiber or these cloth-like products,
Nylon, wholly aromatic polyamide such as aramid, polyamideimide, polyimide, polyester, polybenzimidazole, heterocycle-containing compound such as polyimidazophenanthroline, polytetrafluoroethylene, etc., or powder, plate, or fiber of these Alternatively, these secondary processed products such as cloth-shaped products may be mentioned.

These may be treated with a silane coupler, a titanium coupler or the like. Among these, glass, glass fiber and carbon fiber are preferable. These fillers may be used alone or in combination of two or more.

The copolymerized polycarbonate composition according to the present invention preferably contains the above-mentioned [B] filler in an amount of 2 to 90% by weight, though it may vary depending on the purpose. .

The copolycarbonate composition of the present invention preferably contains an additive [C] together with them. As such a [C] additive, (a)
a sulfur-containing acidic compound having a pKa value of 3 or less, and / or
Alternatively, a derivative formed from the acidic compound, (b) phosphorus compound, (c) epoxy compound, (d) phenolic stabilizer and the like can be mentioned.

These may be used alone or in combination,
It is added to the composition separately or simultaneously. Specific examples of such (a) sulfur-containing acidic compound having a pKa value of 3 or less and derivatives formed from the acidic compound include sulfurous acid, sulfuric acid, sulfinic acid compounds, sulfonic acid compounds and derivatives thereof. Is mentioned.

As the sulfite derivative, dimethyl sulfite,
Diethyl sulfite, dipropyl sulfite, dibutyl sulfite,
Examples thereof include diphenyl sulfite. Examples of the sulfuric acid derivative include dimethyl sulfuric acid, diethyl sulfuric acid, dipropyl sulfuric acid, dibutyl sulfuric acid and diphenyl sulfuric acid.

Examples of the sulfinic acid compound include benzenesulfinic acid, toluenesulfinic acid and naphthalene sulphinic acid. Examples of the sulfonic acid compounds and their derivatives include compounds represented by the following general formula [V] and ammonium salts thereof.

[0082]

[Chemical 5]

In the formula, R ⁷ is a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted with halogen), and R 7
⁸ is hydrogen or a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted with halogen), and n is an integer of 0 to 3.

Specific examples of such sulfonic acid compounds and derivatives thereof include sulfonic acids such as benzene sulfonic acid and p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, and benzene. Sulfonic acid esters such as octyl sulfonate, phenyl benzene sulfonate, methyl p-toluene sulfonate, ethyl p-toluene sulfonate, butyl p-toluene sulfonate, octyl p-toluene sulfonate, phenyl p-toluene sulfonate, p -Ammonium sulfonate such as ammonium toluenesulfonate and the like can be mentioned.

In addition to the sulfonic acid compound represented by the above general formula [V], trifluoromethanesulfonic acid,
Examples thereof include sulfonic acid compounds such as naphthalene sulfonic acid, sulfonated polystyrene, and methyl acrylate-sulfonated styrene copolymer.

In the present invention, (a) the sulfur-containing acidic compound and the derivative formed from the acidic compound are preferably the sulfonic acid compounds represented by the above general formula [V] and the derivatives thereof. Furthermore, in the above general formula [V],
R ⁷ and R ⁸ are substituted aliphatic hydrocarbon groups having 1 to 10 carbon atoms,
A compound in which n is an integer of 0 to 1 is preferably used, and specifically, benzenesulfonic acid, butyl benzenesulfonate, p-toluenesulfonic acid, ethyl p-toluenesulfonate, and p-toluenesulfonate are preferable. .

Of these, butyl p-toluenesulfonate is preferable. In the present invention, the above (a) p
The sulfur-containing acidic compound having a Ka value of 3 or less and / or a derivative formed from the acidic compound is represented by the above [A].
0.1 to 10 ppm with respect to the copolymerized polycarbonate,
Preferably 0.1 to 8 ppm, particularly preferably 0.1 to 5 pp
Used in quantities of m.

Examples of (b) phosphorus compounds include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphoric acid ester and phosphorous acid ester. Specific examples of such a phosphoric acid ester include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, tris (2-chloroethyl). Trialkyl phosphates such as phosphate, tris (2,3-dichloropropyl) phosphate, tricycloalkyl phosphates such as tricyclohexyl phosphate, triphenyl phosphate,
Tricresyl phosphate, tris (nonylphenyl)
Triaryl phosphates such as phosphates and 2-ethylphenyldiphenyl phosphate can be mentioned.

Examples of the phosphite ester include compounds represented by the following general formula. P (OR) ₃ (In the formula, R represents an alicyclic hydrocarbon group, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. These may be the same or different.) As the compound represented by, for example, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, tris (2-ethylhexyl) phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, Tristearyl phosphite, tris (2-
Chloroethyl) phosphite, trialkyl phosphite such as tris (2,3-dichloropropyl) phosphite, tricycloalkyl phosphite such as tricyclohexyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl ) Triaryl phosphites such as phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphite, phenyldidecylphosphite,
Diphenyldecyl phosphite, diphenylisooctyl phosphite, phenylisooctyl phosphite,
Examples thereof include arylalkyl phosphites such as 2-ethylhexyl diphenyl phosphite.

Further, as phosphite, distearyl pentaerythrityl diphosphite, bis (2,4-diester
-t-butylphenyl) pentaerythrityl diphosphite and the like.

Of these, the (b) phosphorus compound is preferably a phosphite represented by the above general formula, more preferably an aromatic phosphite, especially tris (2,
4-di-t-butylphenyl) phosphite is preferred.

In the present invention, the (b) phosphorus compound as described above is usually used in an amount of 1 relative to the copolymer polycarbonate [A].
It is used in an amount of 0 to 1000 ppm, preferably 50 to 500 ppm.

(C) As the epoxy compound, a compound having one or more epoxy groups in one molecule is used. Specifically, epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 3 , 4-Epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3', 4'-epoxycyclohexylcarboxylate, 4
-(3,4-epoxy-5-methylcyclohexyl) butyl-3 ',
4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-
Methylsirohexyl carboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, bis-epoxydicyclopentadienyl ether,
Bis-epoxy ethylene glycol, bis-epoxy cyclohexyl adipate, butadiene diepoxide, tetraphenyl ethylene epoxide, octyl epoxytalate, epoxidized polybutadiene, 3,4-dimethyl-1,2-
Epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-
Epoxy-5-methylcyclohexylcarboxylate,
Octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3', 4'-epoxycyclohexylcarboxylate, 4,5-epoxy tetrahydrophthalic anhydride, 3-
t-Butyl-4,5-epoxy tetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy- Examples thereof include cis-1,2-cyclohexyl dicarboxylate.

Of these, alicyclic epoxy compounds are preferably used, and 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate is particularly preferable.

In the present invention, such an epoxy compound (c) is added to the above [A] copolycarbonate,
Usually in an amount of 1 to 2000 ppm, preferably 10 to 100
Used in an amount of 0 ppm.

Specific examples of the (d) phenolic stabilizer include n-octadecyl-3- (4-hydroxy-3 ', 5'.
-Di-t-butylphenyl) propionate, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl- 4-hydroxy-5-t-butylphenyl) butane, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzyl malonate, 4-hydroxymethyl-2,6-di-t-butylphenol, etc. Can be mentioned.

In the present invention, the above-mentioned (d) phenolic stabilizer is usually 10 to 1000 ppm, preferably 50 to 500 ppm, based on the copolymer polycarbonate [A].
Used in ppm amounts.

The copolymerized polycarbonate composition according to the present invention as described above is particularly excellent in moldability such as fluidity as compared with the conventionally known bisphenol homopolycarbonate and further improved in mechanical properties such as rigidity. In addition, it is possible to form a molded product which is excellent in appearance such as hue and surface gloss.

The copolymerized polycarbonate composition according to the present invention can be produced by kneading the respective components by a conventionally known method. For example, after dispersing and mixing each component with a high speed mixer such as Turnbull mixer, Henschel mixer,
It is appropriately produced by a method of melt-kneading with an extruder, a Banbury mixer, a roll or the like.

When the copolymerized polycarbonate composition is produced, it is the reaction product in the reactor or extruder in the molten state obtained after the completion of the polycondensation reaction [A].
While the copolycarbonate is in the molten state, directly
It is preferable to add the [B] filler and the [C] additive and knead. Specifically, for example, [B] and [C] are added to [A] obtained by the polycondensation reaction in the reactor to form a copolycarbonate composition, and then pelletized through an extruder. Alternatively, while [A] obtained by the polycondensation reaction is pelletized from the reactor through the extruder, [B] and [C] are added and kneaded. It may be a copolycarbonate composition.

The order of adding the [B] filler and the [C] additive to the [A] copolymerized polycarbonate is not limited. The copolymerized polycarbonate composition obtained as described above is prepared by adding and kneading the above-mentioned [B] filler and [C] additive while the reaction product of the copolymerized polycarbonate [A] is in a molten state. Therefore, the thermal history of the obtained resin composition can be reduced, and a copolycarbonate composition having less hue deterioration and heat deterioration can be obtained.

Further, as described above, the additive [C], that is, (a) the sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound,
By adding (b) phosphorus compound, (c) epoxy compound or (d) phenolic stabilizer in the above amount, the alkaline catalyst remaining in the copolycarbonate obtained by the polycondensation reaction is neutralized or weakened. If the compounds (a) and (b) remain in excess, they react with (d) and are neutralized, and the retention stability during production (melting) is further improved. A copolycarbonate composition having improved quality is obtained.

Since the copolymeric polycarbonate composition according to the present invention has improved thermal stability upon melting as described above, the copolymeric polycarbonate composition is blended with various additives and molded. Even when the pellets made of the composition are re-melted, thermal decomposition is particularly suppressed and the molecular weight is less likely to decrease, and the copolymerized polycarbonate composition is less likely to be colored even when melted.

Further, the copolymerized polycarbonate composition according to the present invention is a usual heat stabilizer and an ultraviolet absorber other than the above-mentioned [C] additive as long as the object of the present invention is not impaired. , Release agent, colorant, antistatic agent,
Slip agents, anti-blocking agents, lubricants, antifogging agents, natural oils, synthetic oils, waxes, organic fillers, inorganic fillers such as glass fibers, etc. may be contained.

Such other additives may be added to [A] in a molten state together with the above [C], or the copolycarbonate composition once pelletized may be remelted and added. You can also The former method is preferred in the present invention.

Specific examples of such heat resistance stabilizers include organic thioether stabilizers and hindered amine stabilizers. Examples of thioether-based stabilizers include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, ditridecyl-3,3'-
Examples thereof include thiodipropionate and pentaerythritol-tetrakis- (β-lauryl-thiopropionate).

As the hindered amine stabilizer,
For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- {3- ( 3,5-di-t-butyl-
4-Hydroxyphenyl) propionyloxy} ethyl]
-4- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9- Tetramethyl-3-octyl-1,
2,3-Triazaspiro [4,5] undecane-2,4-dione, 4-
Benzoyloxy-2,2,6,6-tetramethylpiperidine, 2
-(3,5-Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetrakis (2,2,2 6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate and the like.

These heat resistance stabilizers are used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the copolymerized polycarbonate,
It is preferably used in an amount of 0.005 to 0.5 part by weight, more preferably 0.01 to 0.3 part by weight, if necessary.

Such heat resistance stabilizer may be added in the form of solid or liquid. Further, as the ultraviolet absorber, a general ultraviolet absorber is used without particular limitation, but salicylic acid-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, etc. Used.

Examples of salicylic acid type ultraviolet absorbers include phenyl salicylate and pt-butylphenyl salicylate. Benzophenone-based UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4.
-Methoxybenzophenone, 2,2'-dihydroxy-4,4'-
Dimethoxybenzophenone, 2-hydroxy-4-methoxy-
2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4- Dodecyloxy-2-hydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and the like can be mentioned.

Examples of the benzotriazole type ultraviolet absorber include 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t-butyl- Phenyl) benzotriazole, 2- (2'-hydroxy-3'-t
-Butyl-5'-methyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl-phenyl) -5-chlorobenzotriazole, 2- (2 '-Hydroxy
-5'-t-octylphenyl) benzotriazole, 2- (2 '
-Hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- [2'-hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5 ' -Methylphenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like.

Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate and ethyl-2-cyano-3,3-diphenyl acrylate.

The ultraviolet absorber is usually 0.001 to 5 parts by weight, preferably 0.005 parts, relative to 100 parts by weight of [A].
To 1.0 part by weight, and more preferably 0.01 to 0.5 part by weight, if necessary.

As the release agent, a general release agent is used without particular limitation. Examples of the hydrocarbon-based releasing agent include natural and synthetic paraffins, polyethylene waxes, fluorocarbons and the like.

As the fatty acid type release agent, stearic acid,
Examples include higher fatty acids such as hydroxystearic acid and oxyfatty acids. Examples of the fatty acid amide release agent include stearic acid amide, fatty acid amides such as ethylene bis stearamide, and alkylene bis fatty acid amides.

Examples of the alcohol-based release agent include aliphatic alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols, polyglycols and polyglycerols.

Examples of the fatty acid ester-based releasing agent include lower aliphatic acid esters such as butyl stearate and pentaerythritol tetrastearate, fatty acid polyhydric alcohol esters, and fatty acid polyglycol esters.

Examples of the silicone type release agent include silicone oils. These release agents are [A]
Generally, 0.001 to 5 parts by weight based on 100 parts by weight,
Preferably 0.005 to 1 part by weight, more preferably 0.00.
It is optionally used in an amount of 01 to 0.5 parts by weight.

The colorant may be a pigment, a dye, an inorganic type or an organic type. Also, these may be used in combination. Specific examples of inorganic colorants include oxides such as titanium dioxide and red iron oxide, hydroxides such as alumina white, sulfides such as zinc sulfide, selenides, ferrocyanides such as navy blue, zinc chromate, molybdenum red. Chromates such as barium sulfate, carbonates such as calcium carbonate, carbonates such as ultramarine blue, silicates such as ultramarine blue, phosphates such as manganese violet, carbon such as carbon black, and metal powders such as bronze powder and aluminum powder. Examples include colorants.

Specific examples of the organic colorant include nitroso type such as naphthol green B, nitro type such as naphthol yellow-S, resole red and bord-10.
Examples thereof include azo colorants such as B, naphthol red, and chromophthal yellow, phthalocyanine colorants such as phthalocyanine blue and fast sky blue, condensed polycyclic colorants such as indanthrone blue, quinacridone violet, and dioxazine violet.

The coloring agent is based on 100 parts by weight of [A].
Usually 1 × 10 ^{-6 to} 5 parts by weight, preferably 1 × 10 ^{-5 to} 3
It is used in an amount of 1 part by weight, more preferably 1 × 10 ^-5 to 1 part by weight.

[0122]

EFFECT OF THE INVENTION The copolymerized polycarbonate composition according to the present invention is excellent in moldability such as fluidity and melt stability as compared with ordinary bisphenol homopolycarbonate, and excellent in mechanical properties such as rigidity. Moreover, it is possible to form a molded article having excellent hue stability and surface gloss over a long period of time.

The copolymerized polycarbonate composition according to the present invention can be used for automobiles, electrical parts, by appropriately adjusting and selecting the composition of the copolymerized polycarbonate [A], the filler [B] and the additive [C]. Communication equipment parts,
It is used in a wide range of applications such as precision equipment and optical applications.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0125]

EXAMPLES In the present specification, the composition of the copolycarbonate, the intrinsic viscosity [IV], the ratio of terminal groups, and the moldability and appearance of the copolycarbonate composition are measured as follows.

[Polycarbonate composition ratio] ¹ H-N
The ratio of the aromatic dihydroxy compound constitutional unit in the resin was measured by MR.

[Intrinsic viscosity [IV]] 2 in methylene chloride
It measured at 0 degreeC using the Ubbelohde viscometer. [Ratio of Terminal Group] The ratio of the phenolic terminal group and the hydroxyl group terminal was measured by ¹³ C-NMR.

[Moldability, Appearance (Hue, Surface Glossiness)] 3
A mm-thick injection-molded plate was molded, and the ease of molding and the appearance were compared with bisphenol A homopolycarbonate.

[0129]

Example 1 0.44 kmole of bisphenol A (manufactured by Japan GE Plastics Co., Ltd.) and 0.44 kmole of diphenyl carbonate (manufactured by Any Inc.)
Charge into a 50-liter tank type stirring tank, melt at 140 ° C,
Bisphenol A and diphenyl carbonate were fed at 0.16 kmol / hr so as to maintain this level, and 0.16 kmol of bisphenol A was fed to the second 50-liter tank-type stirring tank per hour. . The temperature of this tank type stirring tank was maintained at 180 ° C.

Tetramethylammonium hydroxide was added as a catalyst in an amount of 0.04 mol / hr and sodium hydroxide was added in an amount of 0.00016 mol / hr (1 × 10 ⁻⁶ mol / mol-bisphenol A) so that the residence time was 30 minutes. The level was adjusted and stirred.

Next, this reaction solution was heated by 0.16 kilomoles per hour of bisphenol A conversion at the following third temperature 210.
The solution was fed to a 50 liter tank type stirring tank at 200 ° C. and a pressure of 200 mmHg. The level was adjusted so that the residence time was 30 minutes, and the mixture was stirred while distilling and removing phenol.

Next, this reaction solution was added in an amount of 0.16 kilomoles per hour converted to bisphenol A by the following fourth temperature 240
The solution was fed to a 50-liter tank-type stirring tank having a temperature of 15 ° C and a pressure of 15 mmHg. The level was adjusted so that the residence time was 30 minutes, and the mixture was stirred while distilling and removing phenol. The intrinsic viscosity [η] of the reaction product obtained when the reaction became steady was 0.15 dl /
It was g.

Next, the pressure of this reaction product was increased by a gear pump, and 0.16 kilomoles per hour of bisphenol A conversion was fed into the centrifugal thin-film evaporator to advance the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. Gear pump from the bottom of the evaporator at 290 ℃, 0.2
Biaxial horizontal stirring polymerization tank controlled to mmHg (L /
D = 3, a stirring blade rotating diameter of 220 mm, an internal volume of 80 liters, and 0.16 kmoles (about 40 kg / hour) in terms of bisphenol A were fed every hour to carry out polymerization for a residence time of 30 minutes. At this time, the intrinsic viscosity [IV] of the polymer was 0.49 dl / g, and the ratio of the phenol end group and the hydroxyl end group was 50/50.

Next, in the molten state, this polymer was mixed with a gear pump in a twin-screw extruder (L / D = 17.5, barrel temperature 285 ° C.) at a rate of 0.16 in terms of bisphenol A per hour.
Each of them is fed in kilomoles (about 40 kg / hour), and 70 parts by weight of glass fiber having an average length of 6 mm (chip strand CS6PE-231: Nitto Boseki Co., Ltd.) and 100 parts by weight of polycarbonate are added with p- Butyl Toluenesulfonate 1.8ppm, Tris (2,4-di-t-
Butylphenyl) phosphite (Mark 2112: manufactured by ADEKA ARGUS) 300 ppm, n-octadecyl-3- (4-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate (Mark AO 50: manufactured by ADEKA ARGUS) ) 300ppm,
3,4-Epoxycyclohexylmethyl-3, '4'-epoxycyclohexylcarboxylate (Celoxide 2021P:
Continuously kneading 300 ppm (manufactured by Daicel Chemical Co., Ltd.), forming a strand through a die, and cutting with a cutter into pellets.

The results are shown in Table 1.

[0136]

Example 2 In Example 1, 0.22 resorcin was added.
Pellets were obtained in the same manner as in Example 1 except that the amount of KM and bisphenol A was 0.22.

At this time, the intrinsic viscosity [IV] of the copolymerized polycarbonate was 0.49 dl / g, and the ratio of the phenol end group and the hydroxyl end group was 50/50. The results are shown in Table 1.

[0138]

Comparative Example 1 Pellets were obtained in the same manner as in Example 1 except that 0.44 kmole of bisphenol A was used without using resorcin.

The intrinsic viscosity [IV] of the polycarbonate at this time was 0.49 dl / g, and the ratio of the phenol end groups and the hydroxyl end groups was 50/50. The results are shown in Table 1.

[0140]

Example 3 Pellets were obtained in the same manner as in Example 1 except that 40 parts by weight of glass fiber (chip strand CS6PE-231: manufactured by Nitto Boseki Co., Ltd.) having an average length of 6 mm was added.

The results are shown in Table 1.

[0142]

Comparative Example 2 Pellets were obtained in the same manner as in Example 3 except that 0.44 kmole of bisphenol A was used without using resorcin.

The results are shown in Table 1.

[0144]

Example 4 Pellets were obtained in the same manner as in Example 1 except that 20 parts by weight of glass fiber (chip strand CS6PE-231: manufactured by Nitto Boseki Co., Ltd.) having an average length of 6 mm was added.

The results are shown in Table 1.

[0146]

Comparative Example 3 Pellets were obtained in the same manner as in Example 4 except that 0.44 kmole of bisphenol A was used without using resorcin.

The results are shown in Table 1.

[0148]

[Table 1]

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[Procedure amendment]

[Submission date] September 30, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0129

[Correction method] Change

[Correction content]

[0129]

Example 1 Bisphenol A (manufactured by Japan GE Plastics Co., Ltd.) 0.33 kmole, and after distillation and purification, directly
Resorcinol supplied by connecting pipe (Mitsui Petrochemical
0.18 kilomoles (manufactured by Kogyo Co., Ltd.) and 0.44 kilomoles of diphenyl carbonate (manufactured by Any Inc.)
Charge into a 0 liter tank type stirring tank, melt at 140 ° C, and add bisphenol A 0.12 per hour to maintain this level.
This mixed solution was mixed with aromatic dihydroxy compound per hour while feeding kmol, resorcin 0.04 kmol and diphenyl carbonate 0.16 kmol per hour.
0.16 kmole in terms of product was fed to the second 50-liter tank-type stirring tank. The temperature of this tank type stirring tank was maintained at 180 ° C.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0131

[Correction method] Change

[Correction content]

Next, the reaction solution is charged with an aromatic dihydrogen every hour.
0.16 kmoles in terms of xy compound were fed to the following 50 liter tank-type stirring tank at the third temperature of 210 ° C. and pressure of 200 mmHg. The level was adjusted so that the residence time was 30 minutes, and the mixture was stirred while distilling and removing phenol.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0132

[Correction method] Change

[Correction content]

Next, the reaction solution was charged with an aromatic dihydrogen every hour.
0.16 kmoles in terms of xy compound were fed to the following 50-liter tank-type stirring tank having a fourth temperature of 240 ° C. and a pressure of 15 mmHg. The level was adjusted so that the residence time was 30 minutes, and the mixture was stirred while distilling and removing phenol. The intrinsic viscosity [η] of the reaction product obtained when the reaction becomes steady is 0.1
It was 5 dl / g.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0133

[Correction method] Change

[Correction content]

Next, the pressure of this reaction product was increased by a gear pump, and 0.16 kilomoles per hour of the aromatic dihydroxy compound was fed into the centrifugal thin film evaporator to advance the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. 290 ° C from the bottom of the evaporator with a gear pump,
In a biaxial horizontal stirring polymerization tank (L / D = 3, stirring blade rotating diameter 220 mm, internal volume 80 liters) controlled at 0.2 mmHg, an hourly amount of 0.1 was calculated as an aromatic dihydroxy compound.
6 kmoles (approx. 40 kg / hour) fed in, residence time 3
It was polymerized at 0 minutes. At this time, the intrinsic viscosity [IV] of the polymer was 0.49 dl / g, and the ratio of the phenol end group and the hydroxyl end group was 50/50.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0134

[Correction method] Change

[Correction content]

[0134] Next, in a molten state, the polymer biaxial extruder at a gear pump (L / D = 17.5, barrel temperature 285 ° C.) per hour aromatic dihydroxy compound converted to 0.16 kmol (about 40 kg / hour) and 70 parts by weight of glass fiber (chip strand CS6PE-231: Nitto Boseki Co., Ltd.) having an average length of 6 mm per 100 parts by weight of polycarbonate and p-toluenesulfonic acid with respect to the polycarbonate. Butyl 1.8ppm, Tris (2,4-di-t-butylphenyl) phosphite (Mark 211
2: ADEKA ARGUS) 300ppm, n-octadecyl
-3- (4-Hydroxy-3 ', 5'-di-t-butylphenyl) propionate (Mark AO 50: ADEKA ARGUS CORPORATION) 3
00ppm, 3,4-epoxycyclohexylmethyl-3, '4'-epoxycyclohexylcarboxylate (celoxide
2021P: manufactured by Daicel Chemical Co., Ltd.) 300 ppm was continuously kneaded, passed through a die to form a strand, and cut into a pellet with a cutter.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08K 5/15 5/41 KKL 7242-4J 5/52 KKM 7242-4J 7/20

Claims (7)

[Claims] 1. [A] (i) resorcin and / or substituted resorcin, (ii) an aromatic dihydroxy compound other than resorcin and substituted resorcin, (iii) these aromatic dihydroxy compounds (i) and (ii) A copolymerized polycarbonate composition comprising a copolymerized polycarbonate obtained by copolymerizing a compound capable of reacting to form a carbonic acid bond, and a filler [B]. 2. [A] (i) resorcin and / or substituted resorcin, (ii) aromatic dihydroxy compound other than resorcin and substituted resorcin, (iii) these aromatic dihydroxy compounds (i) and (ii) A copolycarbonate composition comprising a copolycarbonate obtained by copolymerizing a compound capable of reacting to form a carbonic acid bond, a [B] filler, and a [C] additive. 3. The [A] copolymerized polycarbonate comprises the structural unit derived from an aromatic dihydroxy compound in an amount of 2 to 90 mol% of the structural unit derived from (i) resorcin and / or substituted resorcin. 3. The copolymerized polycarbonate composition according to claim 1 or 2, characterized in that 4. The copolymerized polycarbonate [A] contains 2 to 40 mol% of the structural unit derived from (i) resorcin and / or substituted resorcin, among the structural units derived from an aromatic dihydroxy compound. 3. The copolymerized polycarbonate composition according to claim 1 or 2, characterized in that 5. The copolycarbonate composition according to claim 1, wherein the (i) resorcin and / or the substituted resorcin is resorcin. 6. The copolymerized polycarbonate composition according to claim 1 or 2, wherein the filler [B] is glass fiber. 7. The additive [C] is (a) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound, (b) phosphorus compound, (c) epoxy compound and (D) The copolymerized polycarbonate composition according to claim 2, which is selected from the group consisting of phenolic stabilizers.