JP3299570B2 - Copolycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention forms a molded article having excellent mechanical properties, heat resistance and transparency, as well as improved moldability such as chemical resistance and fluidity, and excellent in hue and surface gloss. The present invention relates to a copolymerizable polycarbonate resin composition that can be used.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate has excellent mechanical properties such as impact resistance, and also has excellent 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 properties are usually produced by an interfacial polymerization method in which an aromatic dihydroxy compound such as bisphenol A is directly reacted with phosgene. There is also known a method for producing a polycarbonate by melt polycondensation of a carbonic acid diester and the above-mentioned 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 disc,
It is melted and used at high temperature to improve fluidity.

[0005] In general, polymers are more susceptible to moldings, such as a decrease in transparency or hue as the melting time at high temperatures increases. For this reason, if the flowability of the polycarbonate can be improved, a molded product with less influence of heat at the time of molding can be obtained, and the molding cycle is shortened, and the moldability is improved, such as the production yield is increased.

For this reason, there has been a demand for a polycarbonate capable of forming a molded article excellent in fluidity and moldability, and excellent in transparency and hue, without impairing the inherent properties of the polycarbonate.

In view of the above prior art, the present inventors have conducted intensive studies to obtain a polycarbonate composition having excellent mechanical properties and excellent fluidity. Copolymerized polycarbonate containing at least a structural unit derived from resorcinol or substituted resorcinol has been found to have excellent mechanical properties, heat resistance, transparency, etc. inherent to polycarbonate, as well as excellent fluidity and property formation. Further, a copolymerized polycarbonate resin composition obtained by blending another thermoplastic resin with such a copolymerized polycarbonate is excellent in mechanical properties, heat resistance, transparency, etc. and also excellent in fluidity, moldability. And found that the present invention was completed.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has excellent mechanical properties, heat resistance, transparency, etc., as well as excellent chemical resistance, and has molding properties such as flow properties. It is another object of the present invention to provide a copolymerized polycarbonate resin composition which is capable of forming a molded article having further improved properties and excellent appearance such as hue and surface glossiness.

[0009]

SUMMARY OF THE INVENTION The copolymerized polycarbonate resin composition according to the present invention comprises (A) (i) resorcinol and / or substituted resorcinol, (ii) an aromatic dihydroxy compound other than resorcinol and substituted resorcinol, and (iii) A copolymer polycarbonate obtained by copolymerizing a compound capable of forming a carbonic acid bond by reacting with these aromatic dihydroxy compounds (i) and (ii); [B] a thermoplastic resin other than the [A] copolymer polycarbonate; It is characterized by consisting of.

[0010] Such a thermoplastic resin [B] is,
[A] other than polycarbonate resin, polyester resin, polyolefin resin, acrylic resin, polyamide resin, polyoxymethylene resin, thermoplastic polyimide resin or aromatic vinyl / diene / vinyl cyanide copolymer Preferably, there is.

[0011] The copolymerized polycarbonate resin composition according to the present invention preferably further contains an additive [C] in addition to the above [A] and [B]. This [C]
The additives include (a) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound, (b) a phosphorus compound, (c) an epoxy compound, and (d) a phenol-based stabilizer. It is preferable to be selected from the group consisting of:

[0012]

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

This [A] copolymerized polycarbonate is:
(i) resorcinol and / or substituted resorcinol; (ii)
Aromatic dihydroxy compounds other than resorcinol and substituted resorcinol, and (iii) these aromatic dihydroxy compounds
(i) copolymerized with a compound capable of forming a carbonic acid bond by reacting with (ii), (i) a structural unit derived from resorcinol and / or substituted resorcinol, and (ii) resorcinol and substituted resorcinol And (iii) a structural unit derived from a compound capable of forming a carbonic acid bond by reacting with these aromatic dihydroxy compounds (i) and (ii). ing.

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

[0015]

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

Examples of (i) resorcinol and / or substituted resorcinol include resorcinol, 3-methylresorcinol, 3-ethylresorcinol, 3-propylresorcinol, 3-butylresorcinol, and 3-t-butylresorcinol. ,
3-phenylresorcinol, 3-cumylresorcinol, 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 (i) resorcinol and / or substituted resorcinol is based on 100 mol% of the structural unit derived from an aromatic dihydroxy compound. , Less than 100 mol%, but preferably in an amount of 2 to 90 mol%, more preferably 2 to 40 mol%.

(Ii) The structural unit derived from an aromatic dihydroxy compound other than resorcinol and / or substituted resorcinol is not particularly limited, and is usually derived from the following aromatic dihydroxy compound which forms polycarbonate. May be a structural unit.

[0020]

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Wherein R ¹ and R ² are a hydrogen atom or a monovalent hydrocarbon group, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are a halogen or a monovalent hydrocarbon group, which may be the same or different. p and q represent an integer of 0 to 4. Examples of such (ii) other aromatic dihydroxy compounds include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 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, 2,2-
Bis (hydroxyaryl) alkanes such as bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, and 1,1-bis (4-hydroxyphenyl) cyclohexane Bis (hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 '
Dihydroxyaryl ethers such as -dimethylphenyl ether, 4,4'-dihydroxydiphenylsulfide, dihydroxydiarylsulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 4,
Dihydroxydiarylsulfoxides such as 4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-
And dihydroxydiarylsulfones such as dimethyldiphenylsulfone.

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

Of these, diphenyl carbonate is particularly preferred. The [A] copolymerized polycarbonate 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 structural units described above. This structural unit is a polyester polycarbonate.

Such dicarboxylic acids or dicarboxylic acid esters and dicarboxylic acid halides include terephthalic acid, isophthalic acid, sebacic acid, decandioic acid, and the like.
Dodecane diacid, diphenyl sebacate, diphenyl terephthalate, diphenyl isophthalate, diphenyl decane diacid, diphenyl dodecane diacid, terephthalic chloride, isophthalic chloride, sebacic chloride, decane diacid chloride, dodecane dichloride and the like. be able to.

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

The copolymer (A) may contain a structural 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 three or more phenolic hydroxyl groups or carboxyl groups is preferable, and a compound having three or more phenolic hydroxyl groups is particularly preferably used. Specifically, for example, 1,1,1-tris (4-hydroxyphenyl) ethane,
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 preferred. Such structural units are usually 3 mol% or less, preferably 0.1 to 2 mol%, more preferably 100 mol%, when the structural units derived from the aromatic dihydroxy compound in the copolymerized polycarbonate are 100 mol%. 0.1-1
It may be present in an amount of mole%.

The copolymer (A) 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
It is.

The thermal decomposition temperature is usually from 350 to 380.
° C, preferably 360-380 ° C. Further JIS
According to K7210, 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 min
Minutes.

The copolymer (A) used in the present invention has excellent mechanical properties, heat resistance, transparency and hue, excellent chemical resistance, and excellent moldability such as fluidity.

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

The [A] copolymerized polycarbonate as described above is used in combination with (i) resorcinol and / or substituted resorcinol.
(ii) Other aromatic dihydroxy compounds, and (iii) are produced using a compound capable of forming a carbonic acid bond by reacting with these aromatic dihydroxy compounds (i) and (ii). 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 forming a carbonic acid bond by reacting with an aromatic dihydroxy compound, a melting method using a carbonic acid diester, a solid phase polymerization method, and the like. You.

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

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

[0036]

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

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

In the present invention, when producing a copolycarbonate, such (i) resorcinol and / or substituted resorcinol may be used in the aromatic dihydroxy compound.
It is used in an amount of less than 00%, but is preferably used in an amount of 2 to 90 mol%, more preferably 2 to 40 mol%.

(Ii) The aromatic dihydroxy compound other than resorcinol and / or substituted resorcinol is preferably 98 to 10 mol%, more preferably 98 to 60 mol% when the aromatic dihydroxy compound is 100 mol%.
It is used in an amount of mol%.

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

[0042]

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Wherein R ¹ and R ² are a hydrogen atom or a monovalent hydrocarbon group, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are a halogen or a monovalent hydrocarbon group, which may be the same or different. p and q are integers of 0-4. Examples of such aromatic dihydroxy compounds 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, in producing the copolymerized polycarbonate, when the carbonic acid diester is 100 mol%, the carbonic acid diester is preferably 50 mol% or less, more preferably 30 mol% or less, in an amount of dicarboxylic acid or dicarboxylic acid ester. It may be contained.

Specific examples of such dicarboxylic acids or dicarboxylic esters include the compounds described above. In the present invention, when producing a polycarbonate, the above-mentioned carbonic acid diester is used in an amount of 0.95 to 1.95 based on 1 mol of the aromatic dihydroxy compound in total.
It is desirably used in an amount of 30 mol, preferably 1.01 to 1.20 mol.

In the present invention, when producing a polycarbonate, the aromatic dihydroxy compound and the carbonic acid diester are used together with the aromatic dihydroxy compound and the carbonic acid diester in a molecule as described above.
Polyfunctional compounds having more than one functional group can also be used.

When a polyfunctional compound is used, it is usually 0.03 with respect to 1 mol of the total amount of the aromatic dihydroxy compound.
It is preferably used in an amount of 0.001 to 0.02 mol, more preferably 0.001 to 0.01 mol.

In the present invention, the aromatic dihydroxy compound containing resorcinol and / or substituted resorcinol as described above and a carbonic acid diester are reacted with (a) a catalyst comprising an alkali metal compound and / or an alkaline earth gold compound. Is preferably subjected to melt polycondensation.

Specific examples of the alkali metal compound and the alkaline earth metal compound (a) include organic acid salts and inorganic acid salts of alkali metals and alkaline earth metals.
Oxides, hydroxides, hydrides or alcoholates are preferred.

More specifically, such alkali metal compounds include sodium hydroxide, potassium hydroxide,
Lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride , Lithium borohydride, sodium 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, phenol sodium salts, 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 carbon dioxide. 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
And / or an alkaline earth metal compound (a)
Usually, 1 × 10
^-8~ 1 × 10 ^-3Mol, preferably 1 × 10^-7~ 1 × 10
^-FiveMol, particularly preferably 1 × 10^-7~ 2.5 × 10^-6Mo
Used in the amount of oil.

When the amount of the alkali metal compound or 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 increased. While maintaining, it is possible to add an acidic compound (described below) in an amount that does not adversely affect the properties of the obtained copolymerized polycarbonate, thereby sufficiently neutralizing or weakening the basicity of these compounds,
A copolymerized polycarbonate having excellent hue, heat resistance, water resistance, and weather resistance and excellent long-term melt stability can be obtained.

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

Examples of such a basic compound (b) include a nitrogen-containing basic compound which is easily decomposed or volatile at a high temperature, and specific examples include the following compounds.

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 an araryl group and the like, tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine and triphenylamine, R ₂ NH (where R is an alkyl group such as methyl and ethyl, and an aryl group such as phenyl and toluyl) Etc.)
In secondary amines represented, primary amines represented by RNH ₂ (wherein R is as defined above), pyridine, dimethylaminopyridine, pyridine such as 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, particularly tetraalkylammonium hydroxides for electronic use, which contain few metal impurities, are preferably used.

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

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

Preferred combinations used as a catalyst in the present invention include a combination comprising (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 an amount as described above, and (b) the nitrogen-containing basic compound is 1 × 10 ^-6 to 1 × 10 ^-1 mol, based on 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 to be used is 1 × 10 ⁻⁶ to 1 × 1 per 1 mol of the total amount of the aromatic dihydroxy compound.
The amount of 0 to ¹ mol is preferred in that the transesterification reaction and the polymerization reaction proceed at a sufficient rate, and a copolymerized polycarbonate having excellent hue, heat resistance and water resistance can be obtained.

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

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 a borate ester, and (a) an alkali metal compound and / or Alternatively, a catalyst comprising 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 comprising such a combination,
(a) The alkali metal compound or alkaline earth metal compound and (b) the nitrogen-containing basic compound 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.
１1 × 10 ^-1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-2
Mole, more preferably 1 × 10 ^-6 to 1 × 10 ^-4 mole.

(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.
The molar ratio of 10 ^-8 to 1 × 10 ^-1 is preferred because a molecular weight is less likely to be reduced after heat aging, and a copolymer 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 comprising boric acid or boric acid ester is excellent in transparency, heat resistance and water resistance and also has improved color tone, and can produce a high molecular weight copolymerized polycarbonate with high polymerization activity.

The polycondensation reaction between an aromatic dihydroxy compound containing resorcinol and / or substituted resorcinol and a carbonic acid diester using such a catalyst can be carried out by a conventionally known polycondensation reaction condition between an aromatic dihydroxy compound and a carbonic acid diester. Under the same conditions as described above.

Specifically, 80 to 250 ° C., preferably 100 to 230 ° C., and more preferably 120 to 190 ° C.
The aromatic dihydroxy compound is reacted with the carbonic acid diester at a temperature of 0 to 5 hours, preferably 0 to 4 hours, more preferably 0 to 3 hours under normal pressure. Next, the reaction temperature is increased while reducing the pressure of the reaction system, and the reaction between the aromatic dihydroxy compound and the carbonic acid diester is carried out. Finally, the reaction is carried out under a reduced pressure of 5 mmHg or less, preferably 1 mmHg or less.
A polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester is performed at a temperature of about 320 ° C.

The above-mentioned polycondensation reaction may be carried out continuously or batchwise. The reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

The copolymerized polycarbonate 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 in terms of environmental hygiene because toxic substances such as phosgene and methylene chloride are not used in the melt polycondensation of the copolymerized polycarbonate.

Further, according to this melt polymerization method, in the obtained copolymerized polycarbonate, (i) resorcinol and / or
Alternatively, even when (i) resorcinol or substituted resorcinol is used in an amount such that the substituted resorcinol structural unit exceeds 90 mol%, the hue, water resistance, and heat resistance are excellent as compared with other methods such as an interfacial polymerization method. Thus, a copolymerized polycarbonate is obtained.

The copolycarbonate resin composition according to the present invention comprises the above [A] copolycarbonate and the above [B] copolycarbonate [A] other thermoplastic resins.

In the present invention, examples of the thermoplastic resin [B] include those described in JP-A-2-247248, JP-A-2-202545, and JP-A-2-26.
Known resins described in JP-A-1853, JP-A-2-261860, JP-A-3-199255, JP-A-3-7758 and the like can be mentioned. More specifically, a polycarbonate resin containing no structural unit derived from resorcinol and / or substituted resorcinol, a polyester resin such as polyethylene terephthalate and polybutylene terephthalate, and an aromatic vinyl resin such as polystyrene and poly α-methylstyrene Resins, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, polyolefin-based resin such as ethylene-propylene-diene copolymer, acrylic resin such as polymethyl methacrylate,
Diene rubbers such as polybutadiene and polyisoprene,
Polyvinyl cyanide such as polyacrylonitrile, polymethacrylonitrile, polyamide resin such as nylon 6, nylon 66, thermoplastic polyimide, polyamide imide resin, aromatic vinyl-diene-vinyl cyanide such as styrene-butadiene-acrylonitrile copolymer And copolymer resins such as α-olefin-α, β-unsaturated glycidyl ester copolymers such as copolymers and ethylene-glycidyl methacrylate copolymers.

The above resin may have a functional group such as an epoxy group, an oxazolinyl group or an unsaturated carboxyl group introduced therein. One or more of these resins are used.

The copolymerized polycarbonate resin composition according to the present invention comprises the above-mentioned [B] other thermoplastic resin,
Usually, it is contained in an amount of 1 to 2000 parts by weight based on 100 parts by weight of the copolymerized polycarbonate [A].

Further, the copolymerized polycarbonate resin composition of the present invention preferably contains an additive [C] together with these. Such [C] additives include:
(A) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound;
(B) a phosphorus compound, (c) an epoxy compound and (d)
Phenolic stabilizers and the like can be mentioned.

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

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

Examples of the sulfinic acid compound include benzenesulfinic acid, toluenesulfinic acid, and naphthalene sulfinic acid. Examples of the sulfonic acid compound and its derivative include a compound represented by the following general formula [V] and an ammonium salt thereof.

[0082]

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

Examples of such sulfonic acid compounds and derivatives thereof include sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butylbenzenesulfonate and benzene. Sulfonate 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 salts such as ammonium toluene sulfonate.

Further, in addition to the sulfonic acid compound represented by the general formula [V], trifluoromethanesulfonic acid,
Sulfonic acid compounds such as naphthalene sulfonic acid, sulfonated polystyrene, and methyl acrylate-sulfonated styrene copolymer are exemplified.

In the present invention, as the sulfur-containing acidic compound and the derivative formed from the acidic compound, a sulfonic acid-based compound represented by the above general formula [V] and its derivative are preferable. Further, in the general formula [V],
R ⁷ and R ⁸ each represent a substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms;
Compounds in which n is an integer of 0 to 1 are preferably used, and specifically, benzenesulfonic acid, butylbenzenesulfonate, p-toluenesulfonic acid, ethyl p-toluenesulfonate, and butyl p-toluenesulfonate are preferred. .

Of these, butyl p-toluenesulfonate is preferred. In the present invention, (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 the above-mentioned [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 the amount of m.

(B) Examples of the phosphorus compound include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphate ester and phosphite ester. Specific examples of such a phosphate include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, and tris (2-chloroethyl) Phosphate, trialkyl phosphate such as tris (2,3-dichloropropyl) phosphate, tricycloalkyl phosphate such as tricyclohexyl phosphate, triphenyl phosphate,
Tricresyl phosphate, tris (nonylphenyl)
Phosphate and triaryl phosphates such as 2-ethylphenyldiphenyl phosphate and the like.

The phosphites include compounds represented by the following general formula. P (OR) ₃ (wherein, 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-
Trialkylphosphites such as chloroethyl) phosphite and tris (2,3-dichloropropyl) phosphite; tricycloalkylphosphites such as tricyclohexylphosphite; triphenylphosphite; tricresylphosphite; and tris (ethylphenyl). ) Phosphites, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphite and other triaryl phosphites, phenyldidecyl phosphite,
Diphenyldecyl phosphite, diphenylisooctyl phosphite, phenylisooctyl phosphite,
And arylalkyl phosphites such as 2-ethylhexyl diphenyl phosphite.

Further, phosphites such as distearyl pentaerythrityl diphosphite and bis (2,4-di
-t-butylphenyl) pentaerythrityl diphosphite and the like.

Among them, the (b) phosphorus compound is preferably a phosphite represented by the above general formula, more preferably an aromatic phosphite, and particularly preferably 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 to the (A) copolymerized polycarbonate.
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-butylphenylglycidyl 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'-
Methylsilohexyl carboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclopentadienyl ether,
Bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxy tartrate, 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-epoxytetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy- Cis-1,2-cyclohexyldicarboxylate and the like.

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

In the present invention, such an epoxy compound (c) is used for the above (A) copolymerized polycarbonate.
Usually in an amount of 1 to 2000 ppm, preferably 10 to 100 ppm
It is used in an amount of 0 ppm.

(D) Specific examples of the phenolic stabilizer include, for example, 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) benzylmalonate, 4-hydroxymethyl-2,6-di-t-butylphenol, etc. No.

In the present invention, the above-mentioned (d) phenol-based stabilizer is used in an amount of usually 10 to 1000 ppm, preferably 50 to 500 ppm, based on [A] copolymerized polycarbonate.
Used in ppm amounts.

The copolycarbonate resin composition according to the present invention as described above comprises a copolycarbonate containing a structural unit derived from resorcinol or substituted resorcinol and another thermoplastic resin. Compared to the case of containing a bisphenol homopolycarbonate, especially excellent in moldability such as fluidity,
A molded article having excellent appearance such as hue and surface gloss can be formed.

The copolymerized polycarbonate resin composition according to the present invention can be produced by kneading the components by a conventionally known method. For example, the components are dispersed and mixed with a high-speed mixer such as a turn bull mixer or a Henschel mixer, and then appropriately melted and kneaded with an extruder, a Banbury mixer, a roll, or the like.

When the copolymerized polycarbonate resin composition is produced, [A] the copolymerized polycarbonate, which is a reaction product in a molten state reactor or extruder obtained after completion of the polycondensation reaction, is melted. While in
It is preferable to directly add and knead the [B] other thermoplastic resin and the [C] additive. Specifically, for example,
[B] is added to [A] obtained by the polycondensation reaction in the reactor.
And [C] are added to form a copolymerized polycarbonate resin composition, which may then be pelletized through an extruder, or [A] obtained by the polycondensation reaction may be passed through the extruder from the reactor. During pelletization, [B] and [C] may be added, and these may be kneaded to obtain a copolymerized polycarbonate resin composition.

The order of adding the thermoplastic resin [B] and the additive [C] to the copolymerized polycarbonate [A] is not limited. The copolymerized polycarbonate resin composition obtained as described above is characterized in that the copolymerized polycarbonate [A], which is a reaction product, is in a molten state while the other thermoplastic resin [B] and the additive [C] are added. Is added and kneaded, so that the heat history of the obtained resin composition can be reduced,
It is possible to obtain a copolycarbonate resin composition with less hue deterioration and heat deterioration.

As described above, the additive [C], that is, (a) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound;
The alkaline catalyst remaining in the copolymerized polycarbonate obtained by the polycondensation reaction is neutralized or weakened by adding (b) a phosphorus compound, (c) an epoxy compound or (d) a phenolic stabilizer in the above amount. Even if the compounds (a) and (b) remain in excess, they are reacted with (d) and neutralized, and the retention stability during production (melting) is further improved. A copolycarbonate resin composition having improved quality can be obtained.

[0103] Such a copolymerized polycarbonate resin composition according to the present invention has improved thermal stability during melting as described above. Even when the pellets made of the polymerized polycarbonate resin composition are re-melted, the thermal decomposition is particularly suppressed, the molecular weight is hardly reduced, and the copolymerized polycarbonate resin composition is hardly colored even when melted.

Further, the copolymerized polycarbonate resin composition according to the present invention can be used as long as the object of the present invention is not impaired.
Other than the above-mentioned [C] additives, the following ordinary heat stabilizers, ultraviolet absorbers, release agents, coloring agents, antistatic agents, slip agents, antiblocking agents, lubricants, antifogging agents, Natural oils, synthetic oils, waxes, organic fillers, and inorganic fillers such as glass fibers may be contained.

Such other additives can be added to [A] in a molten state together with the above [C], or the pelletized copolymerized polycarbonate resin composition can be remelted once. It can also be added. In the present invention, the former method is preferred.

Specific examples of such a heat-resistant stabilizer include organic thioether-based stabilizers and hindered amine-based stabilizers. Examples of the thioether-based stabilizer include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, and ditridecyl-3,3'-
Thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thiopropionate) and the like.

Further, as the hindered amine-based 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) propionyloxydiethyl]
-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
Bis (1,2,2,6,6-pentamethyl-4-piperidyl)-(3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, tetrakis (2,2, 6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate.

These heat 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 a heat stabilizer may be added in a solid state or a liquid state. As the UV absorber, a general UV absorber is used without any particular limitation. Examples thereof include salicylic acid-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, and cyanoacrylate-based UV absorbers. Used.

Examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate and pt-butylphenyl salicylate. Benzophenone ultraviolet 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.

Examples of the benzotriazole-based 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, ethyl-2-cyano-3,3-diphenyl acrylate and the like.

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

As the release agent, a general release agent is used without any particular limitation. For example, examples of the hydrocarbon release agent include natural and synthetic paraffins, polyethylene waxes, and fluorocarbons.

Examples of the fatty acid release agent include stearic acid,
Higher fatty acids such as hydroxystearic acid, oxy fatty acids and the like can be mentioned. Examples of the fatty acid amide release agent include fatty acid amides such as stearic acid amide and ethylenebisstearamide, and alkylenebisfatty acid amides. Examples of the alcohol release agent include aliphatic alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols, polyglycols, and polyglycerols.

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

Examples of the silicone release agent include silicone oils. These release agents are [A]
Usually, 0.001 to 5 parts by weight with respect to 100 parts by weight,
Preferably it is 0.005 to 1 part by weight, more preferably 0.5 to 1 part by weight.
It is used as needed in an amount of from 0.01 to 0.5 parts by weight.

The colorant may be a pigment or a dye, and may be inorganic or organic. These may be used in combination. Specific examples of the inorganic colorant 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, and molybdenum red. Such as chromate, sulfate such as barium sulfate, carbonate such as calcium carbonate, silicate such as ultramarine blue, phosphate such as manganese violet, carbon such as carbon black, and metal powder such as bronze powder and aluminum powder. Coloring agents and the like.

Specific examples of the organic colorant include nitroso compounds such as naphthol green B, nitro compounds such as naphthol yellow-S, lithol red and bold-10.
B, phthalocyanine such as naphthol red and chromophtal yellow, phthalocyanine such as phthalocyanine blue and fast sky blue, and condensed polycyclic colorants such as indanthrone blue, quinacridone violet, and dioxazine violet.

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

Further, as the filler or reinforcing agent, those generally used widely can be mentioned.
Inorganic fillers such as calcium carbonate, hydrated alumina, clay, barium sulfate, calcium silicate, talc, mica powder, glass fiber, carbon fiber, asbestos, nylon, aramid, polyester, polypropylene, polyethylene, vinylon, and other synthetic fibers And the like.

When the copolymerized polycarbonate resin composition is used together with a release agent such as zinc stearate and calcium stearate, a flame retardant and a thermosetting resin, if necessary, hydroquinone,
Curing stabilizers such as t-butylcatechol, naphthoquinone, p-benzoquinone and the like, and thickeners such as magnesium oxide and calcium hydroxide may be used.

These other additives are used alone or in combination of two or more. The amount of these additives to be used is determined according to the purpose of use, but generally, the total amount of the additives is preferably 5 to 80% by weight based on the total composition.

[0124]

The copolymerized polycarbonate resin composition according to the present invention comprises a copolymerized polycarbonate containing a structural unit derived from resorcinol or a substituted resorcinol and another thermoplastic resin. Compared with the case where the homopolycarbonate is contained, it is particularly excellent in moldability such as fluidity and melt stability, and a molded article excellent in hue stability and surface gloss can be formed for a long time.

The copolycarbonate resin composition of the present invention can be prepared by appropriately adjusting and selecting the composition of the copolycarbonate [A], the [B] other thermoplastic resin and the [C] additive. It is used for a wide range of applications, such as applications, electrical parts, communication equipment parts, precision equipment, and optical applications.

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

[0127]

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

[Composition ratio of polycarbonate] ¹ H-N
The ratio of the aromatic dihydroxy compound constituent unit in the resin was measured by MR.

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

[Moldability, appearance (hue, surface gloss)] 3
An injection molded plate having a thickness of mm was molded, and the ease of molding and the appearance were compared with those of bisphenol A homopolycarbonate.

[0131]

[Reference Example 1] 0.33 mmol of bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) and 0.11 kmol of resorcinol (manufactured by Mitsui Petrochemical Industry Co., Ltd.) directly supplied by piping after distillation and purification. , 0.44 kmole of diphenyl carbonate (manufactured by Any) was added to the first 25
The mixture was charged into a 0-liter stirred tank, melted at 140 ° C., and bisphenol A was added at 0.12 per hour to maintain this level.
While feeding 0.04 mmol / hr of resorcinol and 0.16 mmol / hr of diphenyl carbonate / hour, the mixed solution was fed 0.16 mmol / hr in terms of aromatic dihydroxy compound to a second 50-liter stirred tank. Liquid. The temperature of this tank-type stirring tank was maintained at 180 ° C.

As catalysts, tetramethylammonium hydroxide (0.04 mol / h) and sodium hydroxide (0.00016 mol / h (1 × 10 ⁻⁶ mol / mol-aromatic dihydroxy compound)) were added, and the residence time was 30 minutes. The level was adjusted so as to be stirred.

Next, this reaction solution was fed into a 50-liter stirred tank having a third temperature of 210 ° C. and a pressure of 200 mmHg at a rate of 0.16 kmol / h in terms of an aromatic dihydroxy compound. The level was adjusted so that the residence time was 30 minutes, and the mixture was stirred while phenol was distilled off.

Next, this reaction solution was fed into a 50-liter stirred tank at a fourth temperature of 240 ° C. and a pressure of 15 mmHg at a rate of 0.16 km / h in terms of an aromatic dihydroxy compound. The level was adjusted so that the residence time was 30 minutes, and the mixture was stirred while phenol was distilled off. The intrinsic viscosity [η] of the reaction product obtained after the reaction becomes steady is 0.15 d.
1 / g.

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

Next, in a molten state, this polymer was fed to a twin-screw extruder (L / D = 17.5, barrel temperature of 285 ° C.) using a gear pump at a rate of 0.16 in terms of bisphenol A per hour.
Kilomol (approximately 40 kg / hour), and 60 parts by weight of polycarbonate, 40 parts by weight of polybutylene terephthalate (Valox 315, manufactured by Nippon GE Plastics Co., Ltd.) and butyl p-toluenesulfonate per 100 parts by weight of polycarbonate. 8 ppm, tris (2,4-di-t-butylphenyl) phosphite (Mark 2112: manufactured by Adeka Argus) 300 ppm, n-octadecyl-3- (4-hydroxy-3 ′, 5′-di-t-butyl) Phenyl) propionate (Mark AO 50: manufactured by Adeka Argus) 300 ppm,
3,4-epoxycyclohexylmethyl-3, '4'-epoxycyclohexylcarboxylate (Celloxide 2021P:
300 ppm (manufactured by Daicel Chemical Co., Ltd.) were continuously kneaded, formed into a strand through a die, and cut into a pellet by a cutter.

The results are shown in Table 1.

[0138]

[Reference Example 2] In Reference Example 1 , 0.22 g of resorcinol was used.
Pellets were obtained in the same manner as in Reference Example 1 except that 0.2 mol of bisphenol A and 0.2 mol of bisphenol A were used.

At this time, the intrinsic viscosity [IV] of the copolymerized polycarbonate was 0.49 dl / g, and the ratio of the phenol terminal group to the hydroxyl group was 50/50. Table 1 shows the results.

[0140]

In Comparative Example 1 Reference Example 1, except for using 0.44 kmol of bisphenol A without using the resorcinol ginseng
Pellets were obtained in the same manner as in Example 1 .

At this time, the intrinsic viscosity [IV] of the polycarbonate was 0.49 dl / g, and the ratio of the phenol terminal group to the hydroxyl group was 50/50. Table 1 shows the results.

[0142]

In Example 1 Reference Example 1, except for adding polybutylene terephthalate ABS resin motor flex 610 in place of (manufactured by Mitsubishi Monsanto) may Pellets were obtained by the same method as in Reference Example 1.

Table 1 shows the results.

[0144]

In Comparative Example 2] Example 1, except that the bisphenol A without using the resorcinol using 0.44 kmol real
Pellets were obtained in the same manner as in Example 1 .

Table 1 shows the results.

[0146]

Example 2 In Example 1 , polycarbonate 80 was used.
Pellets were obtained in the same manner as in Reference Example 1 except that 20 parts by weight of Bondfast E (manufactured by Sumitomo Chemical Co., Ltd.), which is an ethylene-glycidyl methacrylate copolymer, was added to parts by weight of polybutylene terephthalate. .

The results are shown in Table 1.

[0148]

In Comparative Example 3 Example 2, except for using 0.44 kmol of bisphenol A without using the resorcinol real
Pellets were obtained in the same manner as in Example 2 .

Table 1 shows the results.

[0150]

Example 3 In Example 1 , polycarbonate 80 was used.
5 parts by weight of polymethyl methacrylate containing oxazoline-based monomer (CX-RPM-100 manufactured by Nippon Shokubai Kogyo Co., Ltd.) instead of polybutylene terephthalate
Pellets were obtained in the same manner as in Reference Example 1 , except that 20 parts by weight of 5) was added.

Table 1 shows the results.

[0152]

In Comparative Example 4] Example 3, except that the bisphenol A without using the resorcinol using 0.44 kmol real
Pellets were obtained in the same manner as in Example 3 .

Table 1 shows the results.

[0154]

[Table 1]

[0155]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takashi Nagai 1-2-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Japan Inside GE Plastics Co., Ltd. (56) References JP-A-2-284953 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 69/00

Claims (6)

(57) [Claims] [A] (A) (i) resorcinol and / or substituted resorcinol, (ii) an aromatic dihydroxy compound other than resorcinol and substituted resorcinol, (iii) these aromatic dihydroxy compounds (i) and (ii) A copolymerized polycarbonate obtained by copolymerizing a compound capable of forming a carbonic acid bond by reacting, and [B] a polycarbonate-based resin containing no structural unit derived from resorcinol or substituted resorcinol, an acrylic resin, a polyamide-based resin, A copolymer polycarbonate resin composition comprising: a thermoplastic resin selected from the group consisting of a polyoxymethylene resin, a thermoplastic polyimide resin, and an aromatic vinyl / diene / vinyl cyanide copolymer. 2. (A) (i) resorcinol and / or substituted resorcinol, (ii) aromatic dihydroxy compound other than resorcinol and substituted resorcinol, (iii) these aromatic dihydroxy compounds (i) and (ii) A copolymerized polycarbonate obtained by copolymerizing a compound capable of forming a carbonic acid bond by reacting, and [B] a polycarbonate-based resin containing no structural unit derived from resorcinol or substituted resorcinol, an acrylic resin, a polyamide-based resin, A copolymer comprising a thermoplastic resin selected from the group consisting of a polyoxymethylene resin, a thermoplastic polyimide resin, an aromatic vinyl / diene / vinyl cyanide copolymer, and [C] an additive. Polycarbonate resin composition. 3. The copolymer (A) comprises 2 to 90 mol% of the structural unit derived from resorcinol and / or substituted resorcinol in the structural unit derived from an aromatic dihydroxy compound. The copolymerized polycarbonate resin composition according to claim 1 or 2, wherein: 4. The copolymer (A) may comprise (i) a structural unit derived from resorcinol and / or substituted resorcinol in an amount of 2 to 40% by mole of structural units derived from an aromatic dihydroxy compound. The copolymerized polycarbonate resin composition according to claim 1 or 2, wherein: 5. The copolymerized polycarbonate resin composition according to claim 1, wherein said (i) resorcinol and / or substituted resorcinol is resorcinol. 6. The additive [C] comprises: (a) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound; (b) a phosphorus compound; (c) an epoxy compound; The copolymer polycarbonate resin composition according to claim 2, wherein the resin composition is selected from the group consisting of (d) a phenolic stabilizer.