JP5021252B2 - Polycarbonate resin composition and molded body - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded body. More specifically, the present invention relates to a flame retardant polycarbonate resin composition having high fluidity and excellent balance with flame retardancy, and a molded product thereof. Furthermore, the polycarbonate resin composition of the present invention can be used in electrical / electronic devices such as office automation equipment, information / communication equipment, and home appliances, in the automobile field, and in the construction field.

Polycarbonate / polyester alloys are excellent in heat resistance and chemical resistance, and have been used especially for automobile parts. In recent years, from the viewpoint of weight reduction, further thinning of parts has been demanded, and improvement in material fluidity has been demanded. Furthermore, corresponding to the thinning of the product, high rigidity of the material, high heat resistance and flame retardance are required.
A polycarbonate / polylactic acid alloy, which is a polycarbonate / polyester alloy, is effective in increasing the fluidity of polycarbonate (hereinafter sometimes abbreviated as PC) due to the high fluidity of polylactic acid as well as the above properties. is there.
In addition, polylactic acid is considered to be less likely to generate toxic gas even if it is alloyed with polycarbonate and burned due to its structure, and a polycarbonate alloy excellent in environmental aspects can be expected.
Conventional PC / polyester alloys are excellent in heat resistance and chemical resistance, but they are poor in fluidity. To increase the fluidity of PC resins, alloys with styrene resins and addition of plasticizers are generally used. (For example, refer to Patent Document 1).
Further, a PC / polylactic acid alloy having a pearly luster and excellent fluidity and thermal / mechanical properties is known (for example, see Patent Document 2). This alloy is improved in high fluidity, flame retardancy, etc., impact resistance is low, durability such as moisture resistance and heat aging resistance is low, may cause problems in long-term use, Furthermore, the material recyclability was poor.

Furthermore, although PC resin has self-extinguishing properties, there are fields where higher flame retardancy is required in the electrical and electronic fields such as OA equipment, information / communication equipment, and home appliances. The improvement is achieved by the addition of various flame retardants.
As a method for improving the flame retardancy of PC resin, halogen flame retardants such as halogenated bisphenol A and halogenated polycarbonate oligomer have been used together with flame retardant aids such as antimony oxide from the viewpoint of flame retardant efficiency. However, in recent years, a flame retardant method using a flame retardant containing no halogen has been demanded from the market from the viewpoint of safety and environmental impact during disposal / incineration.
As the non-halogen flame retardant, a polycarbonate resin composition containing an organophosphorus flame retardant, especially an organophosphate compound, exhibits excellent flame retardancy and also acts as a plasticizer, and many methods have been proposed. ing.

Further, a flame retardant resin composition comprising a polycarbonate resin composition containing a polytetrafluoroethylene having a fibril-forming ability using a polycarbonate-polyorganosiloxane copolymer as a polycarbonate resin is also known (for example, patents). Reference 3). This composition is a composition exhibiting excellent flame retardancy in a specific range where the content of polyorganosiloxane is small.
In addition, a method using an organic alkali metal salt, an organic alkaline earth metal salt, a polyorganosiloxane, or the like is also known in order to improve flame retardancy without impairing transparency (see, for example, Patent Document 4). However, in any case, it is necessary to further improve the fluidity.
In order to improve the fluidity of the polycarbonate resin, a resin composition using a styrene resin or an aromatic polyester resin is known (for example, see Patent Document 5), but a fatty acid polyester, and further a polycarbonate-polyorganosiloxane. There is no description about the high-flow flame-retardant polycarbonate resin composition using a copolymer.

Japanese Examined Patent Publication No. 7-68445 JP-A-7-109413 JP-A-8-81620 JP-A-8-176425 JP 2003-147188 A

  The present invention has been made in view of the above circumstances, and has high impact properties, high fluidity, high heat resistance and high durability, is excellent in flame retardancy, and has little deterioration in properties even after long-term use. An object of the present invention is to provide a polycarbonate resin composition excellent in material recyclability and a molded body using the polycarbonate resin composition.

As a result of intensive studies to solve the above problems, the present inventors have determined that a predetermined proportion of polyorganosiloxane containing nitrogen-containing organic groups is added to a resin mixture comprising a specific proportion of an aromatic polycarbonate resin and polylactic acid. It was found that the above object can be achieved by the polycarbonate resin composition blended in (1). The present invention has been completed based on such findings.
That is, the present invention provides the following polycarbonate resin composition and molded article.
1. (A) 60 to 97% by mass of an aromatic polycarbonate resin and (B) 100 parts by mass of a resin mixture comprising 40 to 3% by mass of polylactic acid, and (C) 0.2 to 10 mass of a polyorganosiloxane containing a nitrogen-containing organic group. it a polycarbonate resin composition characterized containing parts, (C) a polyorganosiloxane represented by the following general formula containing a nitrogen-containing organic groups of component (1)

(In the formula, R ¹ is a monovalent organic group having 1 to 30 carbon atoms selected from an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and R ² is an organo group represented by R ¹ or —OR ^1. group, R ³ is an amino propyl group. plurality of R ^1, R ² is optionally be the same or different in each .n is an integer of 5 to 100.)
A polycarbonate resin composition which is a polyorganosiloxane having a structure having nitrogen-containing organic groups at both ends represented by the formula:
2. 2. The polycarbonate resin as described in 1 above, wherein the aromatic polycarbonate resin as component (A) is an aromatic polycarbonate-polyorganosiloxane copolymer or an aromatic polycarbonate resin containing an aromatic polycarbonate-polyorganosiloxane copolymer. Composition.
3. A molded article comprising the polycarbonate resin composition as described in 1 or 2 above.

  By blending polylactic acid, it becomes possible to increase the fluidity of the PC resin composition. By this increased fluidity, the moldability of the PC resin composition is improved and the impact strength is increased. Moreover, since moisture resistance improves by mix | blending polylactic acid, durability increases and it becomes a PC resin composition excellent in material recyclability. Furthermore, high flame retardance can be obtained by blending a polyorganosiloxane containing a nitrogen-containing organic group.

There is no restriction | limiting in particular as aromatic PC resin of (A) component which comprises the PC resin composition of this invention, A various thing is mentioned. Usually, an aromatic PC resin produced by a reaction between a dihydric phenol and a carbonate precursor can be used. That is, a product prepared by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method, that is, a reaction of a dihydric phenol and phosgene, a transesterification method of a dihydric phenol and diphenyl carbonate or the like is used. be able to. The aromatic PC resin is the main component of the resin composition of the present invention because it has better heat resistance, flame retardancy, and impact resistance than other thermoplastic resins.
Specifically, the aromatic PC resin as component (A) is represented by the general formula (2).

It is PC resin which has the terminal group represented by these. In the general formula (2), R ⁴ is an alkyl group having 1 to 35 carbon atoms, and may be linear or branched. The bond position may be any of the p-position, m-position and o-position, but the p-position is preferred. a represents an integer of 0 to 5. The viscosity average molecular weight of the aromatic PC resin is usually 10,000 to 40,000, and preferably 13,000 to 30,000, more preferably from the viewpoint of imparting heat resistance, flame retardancy and impact resistance. 15,000 to 24,000.
The viscosity average molecular weight (Mv) was determined by measuring the viscosity of the methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, and determining the intrinsic viscosity [η] from this, [η] = 1.23 × 10 ⁻ It is a value calculated by the equation of ⁵ Mv ^0.83 .

The aromatic polycarbonate having a terminal group represented by the general formula (2) can be easily produced by reacting a dihydric phenol with phosgene or a carbonate compound. That is, for example, in a solvent such as methylene chloride, by the reaction of a dihydric phenol and a carbonate precursor such as phosgene in the presence of a catalyst such as triethylamine and a specific end terminator, or between the dihydric phenol and diphenyl carbonate. It is produced by transesterification with such a carbonate precursor.
Here, as a dihydric phenol, following General formula (3)

The compound represented by these is mentioned. Wherein, R ⁵ and R ⁶ represents an alkyl group or a phenyl group having 1 to 6 carbon atoms and may be the same or different. Z ¹ is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylidene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group having 5 to 20 carbon atoms, or —SO ₂ —, -SO-, -S-, -O-, -CO- bond is shown. Preferably, it is an isopropylidene group. b and c are integers of 0 to 4, preferably 0.

Examples of the dihydric phenol represented by the general formula (3) include 4,4′-dihydroxydiphenyl; 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, Bis (4-hydroxyphenyl) alkanes such as 2,2-bis (4-hydroxyphenyl) propane; bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) oxide; bis (4-hydroxyphenyl) sulfide Bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ketone and the like. Of these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferable. These dihydric phenols may be used alone or in combination of two or more.
The dihydric phenol may be a homopolymer using one of the above dihydric phenols or a copolymer using two or more. Furthermore, the thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound together with the said bihydric phenol may be sufficient.

Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.
As the terminal terminator, a phenol compound in which a terminal group represented by the general formula (2) is formed, that is, a phenol compound represented by the following general formula (4) may be used.

(In the formula, R ⁴ represents an alkyl group having 1 to 35 carbon atoms, and a represents an integer of 0 to 5)
Examples of the phenol compound include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, docosylphenol, tetracosylphenol, hexacosylphenol, octacosy. Examples include ruphenol, triacontylphenol, dotriacontylphenol, tetratriacontylphenol, and p-tert-pentylphenol. These may be one kind or a mixture of two or more kinds. In these, the compound which does not contain a halogen atom from an environmental viewpoint is preferable. Further, these phenol compounds may be used in combination with other phenol compounds as necessary.
In addition, the aromatic polycarbonate manufactured by said method has the terminal group represented by the said General formula (2) substantially at the one terminal or both terminals of a molecule | numerator.

The aromatic PC resin as component (A) is an aromatic polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes abbreviated as “aromatic PC-POS copolymer”) or aromatic PC-POS. An aromatic PC resin containing a copolymer is preferable from the viewpoint of improving heat resistance, flame retardancy, and impact resistance. From this point of view, the aromatic PC-POS copolymer is preferably a PC-PDMS copolymer in which the polyorganosiloxane is polydimethylsiloxane (hereinafter sometimes abbreviated as PDMS), and the PDMS chain length (n ) Is more preferably 15 to 350, and an aromatic PC-PDMS copolymer having a PDMS chain length (n) of 30 to 150 is more preferable from the viewpoint of flame retardancy.
The polyorganosiloxane part (segment) in the aromatic PC-POS copolymer is preferably 0.2 to 10% by mass based on the aromatic PC-POS copolymer, and the components (A) and (B) The total amount is preferably 0.1 to 5% by mass.
The aromatic PC-POS copolymer has the following general formula (5)

(Wherein, R ⁷ represents an alkyl group having 1 to 35 carbon atoms, d is an integer of 0-5.)
For example, JP-A-50-29695, JP-A-3-292359, JP-A-4-202465, JP-A-8-81620, JP-A-8-302178. And a copolymer disclosed in JP-A-10-7897. The alkyl group having 1 to 35 carbon atoms represented by R ⁴ may be linear or branched. The bond position may be any of the p-position, m-position and o-position, but the p-position is preferred.
As the aromatic PC-POS copolymer, a polycarbonate part composed of a structural unit represented by the general formula (6) and a polyorganosiloxane part (segment) composed of a structural unit represented by the general formula (7) are preferably used. The copolymer which has in a molecule | numerator can be mentioned.

Here, R < ⁸ > and R < ⁹ > show a C1-C6 alkyl group or a phenyl group, and may be same or different. R ^{10 to} R ¹³ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and preferably a methyl group. R ^{10 to} R ¹³ may be the same or different. R ¹⁴ represents an aliphatic or aromatic divalent organic residue, preferably an o-allylphenol residue, a p-hydroxystyrene residue or an eugenol residue.
Z ² is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylidene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group having 5 to 20 carbon atoms, or —SO ₂ —, -SO-, -S-, -O-, -CO- bond is shown. Preferably, it is an isopropylidene group. e and f are integers of 0 to 4, preferably 0. m is an integer of 1 to 500, preferably 5 to 300, more preferably 15 to 200, and still more preferably 30 to 150.

  The aromatic PC-POS copolymer is prepared, for example, by a polycarbonate oligomer (hereinafter abbreviated as a PC oligomer) constituting a polycarbonate part produced in advance and an o-allyl at a terminal constituting a polyorganosiloxane part (segment). A polyorganosiloxane having a reactive group such as a phenol group, p-hydroxystyrene group or eugenol residue is dissolved in a solvent such as methylene chloride, chlorobenzene or chloroform, and a caustic aqueous solution of dihydric phenol is added as a catalyst. , Tertiary amines (triethylamine, etc.) and quaternary ammonium salts (trimethylbenzylammonium chloride, etc.)

(Wherein, R ⁷ represents an alkyl group having 1 to 35 carbon atoms, d is an integer of 0-5.)
It can manufacture by carrying out interfacial polycondensation reaction in presence of the general terminal stopper which consists of phenol compound represented by these. Examples of the phenol compound include the same compounds as those exemplified in the general formula (4).
The PC oligomer used for the production of the aromatic PC-POS copolymer can be easily obtained by reacting a dihydric phenol with a carbonate precursor such as phosgene or a carbonate compound in a solvent such as methylene chloride. Can be manufactured. Here, as a dihydric phenol, the thing similar to the exemplary compound of the said General formula (3) can be used, 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A) is especially preferable.
The PC oligomer is, for example, a reaction between a dihydric phenol and a carbonate precursor such as phosgene in a solvent such as methylene chloride, or a transesterification reaction between a dihydric phenol and a carbonate precursor such as diphenyl carbonate. Manufactured by.

Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.
The PC oligomer used for the production of the aromatic PC-POS copolymer may be a homopolymer using one kind of the above-mentioned dihydric phenol or a copolymer using two or more kinds. Furthermore, the thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound together with the said bihydric phenol may be sufficient.
In this case, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3 is used as a branching agent (polyfunctional aromatic compound). , 5-triisopropylbenzene, 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxylphenyl) ethyl] benzene, phloroglucin, Trimellitic acid, isatin bis (o-cresol) and the like can be used.

The aromatic PC-POS copolymer can be produced as described above. Generally, an aromatic polycarbonate is produced as a by-product, and is produced as an aromatic polycarbonate containing a polycarbonate-polyorganosiloxane copolymer.
The aromatic PC-POS copolymer produced by the above method has an aromatic end group represented by the general formula (5) on one or both of the molecules.

The (B) component polylactic acid used in the PC resin composition of the present invention is blended in order to obtain a molded article with good appearance by imparting high fluidity to the PC resin composition. The polylactic acid as component (B) is synthesized by ring-opening polymerization from a cyclic dimer of lactic acid, usually called lactide, and its production method is described in US Pat. No. 1,995,970, US Pat. No. 2,362. 511, U.S. Pat. No. 2,683,136, and the like.
In the case of producing polylactic acid by direct dehydration polycondensation without using ring-opening polymerization, lactic acid is preferably subjected to azeotropic dehydration condensation in the presence of an organic solvent, particularly a phenyl ether solvent, particularly preferably, Polymerization is performed by removing water from the solvent distilled by azeotropic distillation and returning the substantially anhydrous solvent to the reaction system, whereby polylactic acid having a polymerization degree suitable for the present invention is obtained.
As raw lactic acids, any of L- and D-lactic acid, a mixture thereof, or lactide which is a dimer of lactic acid can be used.
In the production of polylactic acid, an appropriate molecular weight regulator, a branching agent, other modifiers and the like can be blended. Moreover, lactic acid can be used individually or in mixture of 2 or more types, Furthermore, 2 or more types of obtained polylactic acid may be mixed and used.

As the polylactic acid of component (B) used in the present invention, natural polylactic acid is excellent in terms of environment (CO ₂ can be reduced), fluidity, thermal and mechanical properties. The polylactic acid preferably has a large molecule, and more preferably has a weight average molecular weight of 30,000 or more.
In the PC resin composition of the present invention, the content ratio of the aromatic PC resin as the component (A) and the polylactic acid as the component (B) needs to be in the range of 97: 3 to 60:40 by mass ratio. , Preferably in the range of 95: 5 to 60:40, more preferably in the range of 95: 5 to 70:30.
When the content ratio of the component (B) is 3% by mass or more, a blending effect is obtained, and when it is 40% by mass or less, the moisture resistance, impact resistance, and flame retardancy in the PC resin composition of the present invention are obtained. And heat resistance are improved.

Examples of the polyorganosiloxane containing a nitrogen-containing organic group (C) used in the PC resin composition of the present invention include the following general formula (1):

And a polyorganosiloxane having a structure having nitrogen-containing organic groups at both ends. In the general formula (1), R ¹ is a monovalent organic group having 1 to 30 carbon atoms selected from an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and R ² is R ¹ or —OR ¹ . The represented organooxy group, R ^3, is a monovalent organic group containing at least one nitrogen atom. A plurality of R ¹ , R ² and R ³ may be the same or different from each other. n shows the integer of 5-100.
The alkyl group represented by R ¹ has 1 to 30 carbon atoms, preferably 1 to 15 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, Examples include sec-butyl group, t-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, and various dodecyl groups. The cycloalkyl group represented by R ¹ has 3 to 30 carbon atoms, and examples thereof include a cyclopentyl group and a cyclohexyl group.
The aryl group represented by R ¹ has 6 to 30 carbon atoms, preferably 6 to 15 carbon atoms, such as phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, Examples thereof include isopropylphenyl group, naphthyl group, methylnaphthyl group and 2-hydroxyethoxyphenyl group.
The aralkyl group represented by R ¹ has 7 to 30 carbon atoms, preferably 7 to 15 carbon atoms. Examples of the aralkyl groups include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1- Phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, α-naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α -A naphthyl isopropyl group, (beta)-naphthyl methyl group, 1- (beta)-naphthyl ethyl group, 2- (beta)-naphthyl ethyl group, 1- (beta)-naphthyl isopropyl group, 2- (beta)-naphthyl isopropyl group, etc. are mentioned.

Represented by R ^2, specific examples of R ¹ in the organo group represented by R ¹ or -OR ¹ include the same ones as described above. Examples of the monovalent organic group containing at least one nitrogen atom represented by R ³ include amino group, aminomethyl group, aminoethyl group, aminopropyl group, N- (β-aminoethyl) iminopropyl group, aminophenoxymethyl. Group and the like.
As the polyorganosiloxane represented by the general formula (1), R ¹ is a methyl group, R ² is a methyl group and an ethoxy group, and R ³ is an aminopropyl group, and R ¹ is a methyl group and phenyl. And polyorganosiloxane in which R ² is a methyl group and a methoxy group, and R ³ is an aminopropyl group.
This (C) component has the effect | action which further improves the impact resistance and flame retardance of the PC resin composition obtained. (C) The compounding quantity of the polyorganosiloxane containing the nitrogen-containing organic group of a component needs to be 0.2-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. , Preferably it is 0.3-8 mass parts, More preferably, it is 2-6 mass parts. When the blending amount of component (C) is 0.2 parts by mass or more, impact resistance and flame retardancy are improved, and when the blending amount of component (C) is 10 parts by mass or less, the PC of the present invention. The heat resistance of the resin composition is good.

The PC resin composition of the present invention can be obtained by blending the above components (A), (B) and (C), and other components as necessary, and melt-kneading.
For this blending and kneading, a commonly used method, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a kneader, a multi screw extruder or the like is used. It can be done by a method.
In addition, the heating temperature at the time of melt-kneading is normally selected in the range of 220-260 degreeC.
This invention also provides the molded object which consists of said PC fat composition. The molding temperature of the PC resin composition of the present invention is usually selected in the range of 240 to 320 ° C.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Production Example 1 [PC-PDMS1; Production of PC-PDMS Copolymer]
(1) Production of PC oligomer 60 kg of bisphenol A was dissolved in 400 L of 5% by mass aqueous sodium hydroxide solution to prepare an aqueous sodium hydroxide solution of bisphenol A. Next, this sodium hydroxide aqueous solution of bisphenol A kept at room temperature was introduced at a flow rate of 138 L / hour and methylene chloride at a flow rate of 69 L / hour through a orifice reactor into a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m. In this, phosgene was co-flowed and blown at a flow rate of 10.7 kg / hour, and the reaction was continued for 3 hours. The tubular reactor used here was a double tube, and the discharge temperature of the reaction solution was maintained at 25 ° C. through the jacket portion through cooling water. The pH of the effluent was adjusted to 10-11.
The reaction solution thus obtained was allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase (220 L) was collected to obtain a PC oligomer (concentration 317 g / L). The degree of polymerization of the PC oligomer obtained here was 2 to 4, and the concentration of the chloroformate group was 0.7 mol / L.
(2) Production of reactive PDMS 1,483 g of octamethylcyclotetrasiloxane, 96 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% by mass sulfuric acid were mixed and stirred at room temperature for 17 hours. Thereafter, the oil phase was separated, 25 g of sodium bicarbonate was added, and the mixture was stirred for 1 hour.
After filtration, vacuum distillation was performed at 150 ° C. and 3 torr (400 Pa) to remove low-boiling substances to obtain an oil. To a mixture of 60 g 2-allylphenol and 0.0014 g platinum as platinum chloride-alcolate complex, 294 g of the oil obtained above was added at a temperature of 90 ° C. The mixture was stirred for 3 hours while maintaining the temperature at 90 to 115 ° C.
The product was extracted with methylene chloride and washed 3 times with 80 wt% aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulfate and heated to 115 ° C. in vacuo to remove the solvent. The terminal phenol PDMS obtained had 30 repeats of dimethylsilanooxy units as measured by NMR.

(3) Production of polycarbonate-polydimethylsiloxane bisphenol A polycarbonate resin (PC-PDMS copolymer) 182 g of reactive PDMS obtained in (2) above was dissolved in 2 L of methylene chloride, and PC obtained in (1) above. 10 L of oligomer was mixed. Thereto, 26 g of sodium hydroxide dissolved in 1 L of water and 5.7 ml of triethylamine were added, and the mixture was stirred at 500 rpm at room temperature for 1 hour to be reacted.
After completion of the reaction, to the above reaction system was added 600 L of bisphenol A dissolved in 5 L of a 5.2 mass% aqueous sodium hydroxide solution, 8 L of methylene chloride and 96 g of p-tert-butylphenol, and 2 at 500 rpm at room temperature. Stir for hours to react.
After the reaction, 5 L of methylene chloride is added, and further washed with 5 L of water, washed with 5 L of 0.03 mol / L aqueous sodium hydroxide, washed with 5 L of 0.2 mol / L hydrochloric acid, and washed twice with 5 L of water. The methylene chloride was finally removed to obtain a flaky PC-PDMS copolymer. The obtained PC-PDMS copolymer was vacuum-dried at 120 ° C. for 24 hours. The viscosity average molecular weight was 17,000, and the PDMS content was 4.0% by mass. The viscosity average molecular weight and PDPS content were determined by the following methods.

(A) Viscosity average molecular weight (Mv)
The viscosity of the methylene chloride solution at 20 ° C. was measured with an Ubbelohde viscometer, and the intrinsic viscosity [η] was determined from the viscosity.
[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83
(B) PDMS content
^It was determined based on the intensity ratio between the isopropyl methyl group peak of bisphenol A found at 1.7 ppm by ¹ H-NMR and the methyl group peak of dimethylsiloxane found at 0.2 ppm.

Production Example 2 [PC-PDMS2; Production of PC-PDMS Copolymer]
In Production Example 1 (2), except that the amount of 2-allylphenol used was 15 g and the amount of 1,1,3,3-tetramethyldisiloxane used was 37.6 g, Similarly, terminal phenol PDMS was obtained. The terminal phenol PDMS obtained had 120 repeats of dimethylsilanooxy units as measured by NMR.
Using this terminal phenol PDMS, a PC-PDMS copolymer was obtained in the same manner as in Production Example 1 (3), and the same measurement was performed. As a result, the viscosity average molecular weight was 17,000, and the PDMS content was 4. It was 0 mass%.

Production Example 3 [Production of polyorganosiloxane A: both terminal amino-modified PDMS]
Mixing 248 g (1 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 4440 g (15 mol) of octamethylcyclotetrasiloxane in a 5 liter glass flask equipped with a stirrer, reflux condenser and thermometer Then, 13 g of a 10% by mass methanol solution of tetramethylammonium hydroxide was added as an alkali catalyst, followed by stirring at 90 ° C. for 10 hours. The reaction product was heated to 150 ° C. and heated for 3 hours, and then a low boiling point product was removed under reduced pressure at 140 ° C., followed by filtration to obtain a colorless and transparent oil. The product had a viscosity of 100 mm ² / s (25 ° C.) and a refractive index of 1.4067 (25 ° C.). The obtained terminal amino-modified PDMS had a number of repeating dimethylsilanooxy units of about 60 as determined by amine equivalent measurement.
The viscosity measurement conditions were in accordance with JIS Z 8803. The refractive index was measured using an Abbe refractometer (manufactured by Atago Co., Ltd.). The amine equivalent was measured using an automatic titrator TS-980 (Hiranuma Sangyo Co., Ltd.).

Production Example 4 [Production of polyorganosiloxane B: side chain amino-modified PDMS]
In a 2 liter glass flask equipped with a stirrer, reflux condenser and thermometer, the following general formula (9)

(In the formula, n represents an integer of 3 to 8.)
As the alkali catalyst, 117 g of 3-aminopropylmethylsiloxane cyclic product represented by the following formula, 740 g (10 mol) of octamethylcyclotetrasiloxane and 32.4 g of 1,1,1,3,3,3-hexamethyldisiloxane were mixed. After adding 2.6 g of a 10% methanol solution of tetramethylammonium hydroxide, the mixture was stirred at 80 ° C. for 10 hours. The reaction product was heated to 150 ° C. and heated for 3 hours, and then a low boiling point product was removed under reduced pressure at 140 ° C., followed by filtration to obtain a colorless and transparent oil. This product had a viscosity of 70 mm ² / s (25 ° C.) and a refractive index of 1.4150 (25 ° C.). In the obtained side chain amino-modified PDMS, the number of repeating dimethylsilanooxy units was about 50 and the number of repeating 3-aminopropylmethylsilanooxy units was about 5 as measured by amine equivalent. The viscosity, refractive index, and amine equivalent were measured in the same manner as in Production Example 3.

Production Example 5 [Production of polyorganosiloxane C]
In a 2-liter glass flask equipped with a stirrer, reflux condenser, and thermometer, 356 g (1.6 mol) of 3-aminopropyltriethoxysilane and 1200 g (0.4 mol) of α, ω-dihydroxypolydimethylsiloxane were mixed. , And stirred at 115 ° C. for 4 hours. The reaction product was filtered at 110 ° C. under 4 kPa to remove low-boiling substances, and a colorless and transparent oil was obtained by filtration. The product had a viscosity of 64 mm ² / s (25 ° C.) and a refractive index of 1.4076 (25 ° C.). The obtained terminal amino PDMS had a number of repeating dimethylsilanooxy units of about 40 as determined by amine equivalent measurement. The viscosity, refractive index, and amine equivalent were measured in the same manner as in Production Example 3.

Production Example 6 [Production of polyorganosiloxane D]
In a 2-liter glass flask equipped with a stirrer, reflux condenser, and thermometer, 308 g (1.6 mol) of 3-aminopropylmethyldiethoxysilane and 1200 g (0.4 mol) of α, ω-dihydroxypolydimethylsiloxane were mixed. And stirred at 115 ° C. for 4 hours. The reaction product was filtered at 110 ° C. under 4 kPa to remove low-boiling substances, and a colorless and transparent oil was obtained by filtration. The product had a viscosity of 67 mm ² / s (25 ° C.) and a refractive index of 1.4074 (25 ° C.). The obtained terminal amino PDMS had a number of repeating dimethylsilanooxy units of about 40 as determined by amine equivalent measurement. The viscosity, refractive index, and amine equivalent were measured in the same manner as in Production Example 3.

Production Example 7 [Production of polyorganosiloxane E: both ends epoxy-modified PDMS]
62.7 g of allyl glycidyl ether and 375 g of toluene as a solvent were mixed in a 2 liter glass flask equipped with a stirrer, reflux condenser and thermometer, and 1% by mass of vinylsiloxane coordinated chloroplatinic acid as an addition reaction catalyst. After adding 0.23 g of the toluene solution, 737 g (1 mol) of α, ω-dihydrodimethylpolysiloxane (degree of polymerization 40) was added dropwise at 80 to 90 ° C. over 3 hours. After the reaction product was aged at 90 ° C. for 3 hours, it was confirmed by the infrared absorption spectrum that there was no absorption of Si—H, and low-boiling products were removed under reduced pressure at 100 ° C., followed by filtration to obtain a pale yellow transparent oil. It was. This product had a viscosity of 60 mm ² / s (25 ° C.) and a refractive index of 1.4110 (25 ° C.). The obtained terminal-epoxy-modified PDMS had a dimethylsilanooxy unit repeat number of about 40 as determined by epoxy equivalent measurement. The viscosity and refractive index were measured in the same manner as in Production Example 3. The epoxy equivalent was measured using an automatic titrator TS-980 (manufactured by Hiranuma Sangyo Co., Ltd.).

Examples 1-6 and Comparative Examples 1-5
Components (A) to (C) in the proportions shown in Table 1, and phosphorus antioxidants (Asahi Denka Co., product name PEP36) and phenolic antioxidants (Ciba Specialty Chemicals) as stabilizers , Trade name: Irganox 1076) is blended in an amount of 0.1 parts by mass with respect to a total of 100 parts by mass of components (A) to (C), and a vent type twin screw extruder (model name: TEM35, Toshiba Machine Co., Ltd.). And melt-kneaded at 260 ° C. and pelletized.
The obtained pellets were dried at 80 ° C. for 10 hours, and then injection molded at a molding temperature of 260 ° C. and a mold temperature of 80 ° C. to prepare test pieces. Each performance was evaluated by the following various evaluation tests using the obtained test pieces. The evaluation results are shown in Table 1.

The blending components and performance evaluation methods used are shown below.
[Ingredients]
(A) Component PC: Aromatic polycarbonate resin; Toughlon A1900 (made by Idemitsu Kosan Co., Ltd., viscosity average molecular weight = 19,500)
PC-PDMS1: Viscosity average molecular weight = 17,000, PDMS content = 4 mass%, PDMS chain length (n) = 30 (see Production Example 1)
PC-PDMS2: Viscosity average molecular weight = 17,000, PDMS content = 4 mass%, PDMS chain length (n) = 120 (see Production Example 2)
(B) Component polylactic acid 1: Lacia H-400 (Mitsui Chemicals, molecular weight MFR (190 ° C., 21.2 N) = 3)
Polylactic acid 2: Lacia H-100 (Mitsui Chemicals, molecular weight MFR (190 ° C., 21.2 N) = 8)
(C) Component silicone A: Amino silicone at both ends (see Production Example 3)
Silicone B: Side chain amino silicone (see Production Example 4)
Silicone C: Both-end amino silicone (see Production Example 5)
Silicone D: See Production Example 6 Silicone E: Both-end epoxy silicone (See Production Example 7)

[Performance evaluation method]
(1) IZOD (IZOD) Impact Strength Based on ASTM D256, a test piece having a thickness of 3.18 mm was used and measured at 23 ° C.
(2) Thermal strain temperature (HDT) (high load)
Based on JIS K 7191-1996, the load was measured at 1.83 MPa. This value is a measure of heat resistance, and although it depends on the purpose of use of the resin composition, it is usually preferably 100 ° C. or higher.
(3) Liquidity (SFL)
Measurement was performed at a molding temperature of 260 ° C., a mold temperature of 80 ° C., a wall thickness of 2 mm, a width of 10 mm, and an injection pressure of 7.85 MPa.
(4) Oxygen index (LOI)
It measured based on JISK7201.

  From Table 1, it can be seen that the PC resin compositions of Examples 1 to 6 have high impact resistance, high flame retardancy and high fluidity. Moreover, when the thing containing PC-PDMS is used as aromatic PC resin, impact resistance and a flame retardance will increase. On the other hand, it can be seen from the evaluation results of Comparative Examples 4 and 5 that the blending ratio of the aromatic PC resin and the polylactic acid is outside the range of claim 1, the fluidity and heat resistance are low. Moreover, it can be seen from the evaluation results of Comparative Examples 1 and 2 that the impact strength, flame retardancy, or heat resistance is low when the blending amount of the polyorganosiloxane is outside the range of claim 1.

  According to the present invention, it has high impact properties, high fluidity, high heat resistance and high durability, and is excellent in flame retardancy. An excellent PC resin composition can be obtained, and this PC resin composition can be used in electrical and electronic equipment such as OA equipment, information / communication equipment, and home appliances, in the automobile field, and in the construction field.

Claims (3)

(A) 60 to 97% by mass of an aromatic polycarbonate resin and (B) 100 parts by mass of a resin mixture comprising 40 to 3% by mass of polylactic acid, and (C) 0.2 to 10 mass of a polyorganosiloxane containing a nitrogen-containing organic group. A polyorganosiloxane containing a nitrogen-containing organic group as the component (C) is a polycarbonate resin composition characterized in that it comprises the following general formula (1):

(In the formula, R ¹ is a monovalent organic group having 1 to 30 carbon atoms selected from an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and R ² is an organo group represented by R ¹ or —OR ^1. group, R ³ is an amino propyl group. plurality of R ^1, R ² is optionally be the same or different in each .n is an integer of 5 to 100.)
A polycarbonate resin composition which is a polyorganosiloxane having a structure having nitrogen-containing organic groups at both ends represented by the formula:   The polycarbonate according to claim 1, wherein the aromatic polycarbonate resin as component (A) is an aromatic polycarbonate-polyorganosiloxane copolymer or an aromatic polycarbonate resin containing an aromatic polycarbonate-polyorganosiloxane copolymer. Resin composition.   The molded object which consists of a polycarbonate resin composition of Claim 1 or 2.