JPH06100684A - Production of polycarbonate-polyorganosiloxane copolymer - Google Patents

Abstract

PURPOSE:To obtain the copolymer which is used for a polycarbonate resin compsn. giving a molded article excellent in mechanical properties such as impact resistance and stiffness and in transparency. CONSTITUTION:The copolymer is produced by continuously mixing a polycarbonate oligomer with a polyorganosiloxane and reacting the mixture with a dihydric phenol in the presence of an alkaline compd., or by continuously mixing a polycarbonate oligomer with a polyorganosiloxane, reacting them in the presence of an alkaline compd. to give a polycarbonate-polyorganosiloxane co-oligomer, and reacting the resulting co-oligomer with a dihydric phenol in the presence of an alkaline compd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polycarbonate-polyorganosiloxane copolymer, and more specifically, it has excellent mechanical properties such as impact resistance and rigidity.
The present invention relates to a method for efficiently producing a polycarbonate-polyorganosiloxane copolymer used in a polycarbonate resin composition capable of obtaining a molded article having excellent transparency.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in mechanical strength, electrical characteristics and transparency, and are widely used as engineering plastics in various fields such as electric / electronic equipment fields and automobile fields. There is. As a polycarbonate resin having such characteristics, a glass fiber reinforced polycarbonate resin to which glass fiber is added in order to improve rigidity and dimensional stability is well known. However, the polycarbonate resin has a drawback that the transparency is significantly lowered by the addition of the glass fiber, and an unpleasant semi-transparent or hazy appearance is exhibited. This is due to the difference in the refractive index (n _D ) between the polycarbonate resin and the glass fiber. The refractive index of polycarbonate resin is about 1.585, and that of "E" glass widely used for glass fiber reinforced resin is about 1.545, which is a considerable difference.
As a method for improving this drawback, Japanese Patent Publication No. 62-133.
As disclosed in Japanese Patent Publication No. 8, ZrO ₂ and TiO ₂ which have a refractive index improving effect on SiO ₂ which is a main component of glass.
It is blended with a polycarbonate resin using a special glass fiber added with. However, the compounding of TiO ₂ causes a problem that the glass is colored brown. Further, adding ZrO ₂ or TiO ₂ to glass has a drawback that it becomes expensive. In the research group of the present inventors, a polycarbonate resin composition obtained by blending a polycarbonate resin and a glass fiber with a polycarbonate-polyorganosiloxane (for example, PDMS) copolymer having a refractive index lower than that of the polycarbonate resin has high transparency. We have developed a technology to obtain a significantly improved molded product. However, it has been found that the polycarbonate-polyorganosiloxane copolymer capable of greatly improving transparency has a problem that the resulting copolymer becomes cloudy when continuously produced.

In view of the above situation, the present inventor therefore continuously prepares a polycarbonate-polyorganosiloxane copolymer which is transparent and does not cloud the obtained copolymer. We have earnestly studied to develop a manufacturing method. As a result, when a polycarbonate-polyorganosiloxane copolymer is produced, by changing the flow of raw materials,
It was found that a copolymer having the desired properties can be obtained. The present invention has been completed based on such findings.

[0004]

That is, the present invention is
(A) Polycarbonate oligomer and (B) polyorganosiloxane are continuously mixed under the condition that an alkaline compound is not substantially present, and then (C) a dihydric phenol is reacted in the presence of the alkaline compound. The present invention provides a method for producing a characteristic polycarbonate-polyorganosiloxane copolymer. Further, in the present invention, (A) a polycarbonate oligomer and (B) a polyorganosiloxane are continuously mixed under the condition that substantially no alkaline compound is present, and then they are reacted in the presence of an alkaline compound to give a polycarbonate- A polyorganosiloxane copolymer oligomer is produced, and further,
The present invention also provides a method for producing a polycarbonate-polyorganosiloxane copolymer, which comprises reacting the polycarbonate-polyorganosiloxane copolymer oligomer with a dihydric phenol (C) in the presence of an alkaline compound.

In the present invention, the polycarbonate oligomer (PC oligomer) of the component (A) used for the production of the polycarbonate-polyorganosiloxane copolymer (PC-PDMS copolymer) is a solvent method, that is, methylene chloride or the like. In the presence of a known acid acceptor and a molecular weight modifier in a solvent, the general formula (II)

[0006]

[Chemical 2]

[In the formula, R ⁶ and R ⁷ are a hydrogen atom and a halogen atom (for example, chlorine, bromine, fluorine, iodine), respectively.
Or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, m and n are each an integer of 1 to 4, and m is 2 to 4; Is R ⁶
May be the same or different from each other,
When n is 2 to 4, R ⁷ may be the same or different. Z is a single bond and has 1 to 8 carbon atoms.
Alkylene group, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group or -SO ₂ of 5 to 15 carbon atoms -, - SO -, - S
-, -O-, -CO- bond or general formula (III)

[0008]

[Chemical 3]

The bond represented by ] It can manufacture by the reaction of the dihydric phenol and carbonate precursor like phosgene represented by these, or the transesterification reaction of the dihydric phenol and carbonate precursor like diphenyl carbonate. Here, there are various dihydric phenols represented by the general formula (II), but 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable. Further, a part or all of bisphenol A may be replaced with another dihydric phenol. As dihydric phenols other than bisphenol A, bis (4-hydroxyphenyl) alkanes other than bisphenol A, hydroquinone; 4,4 ′
-Dihydroxydiphenyl; bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide;
Bis (4-hydroxyphenyl) ether; Bis (4-
Examples thereof include compounds such as hydroxyphenyl) ketone or bis (3,5-dibromo-4-hydroxyphenyl) bropan; halogenated bisphenols such as bis (3,5-dichloro-4-hydroxyphenyl) bropan. In the present invention, the polycarbonate oligomer used for producing the PC-PDMS copolymer may be a homopolymer using one of these dihydric phenols, or a copolymer using two or more thereof. Good. Further, it may be a thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound in combination with the dihydric phenol.

Next, there are various polyorganosiloxanes as the component (B), but the general formula (I) is preferable.

[0011]

[Chemical 4]

The PDMS is represented by and is highly reactive.
Here, R ¹ , R ² , R ³ and R ⁴ are hydrogen,
It represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different. Further, in one molecule, k R ¹ and k R ² are
They may be the same or different. R ⁵ represents an aliphatic or aromatic organic residue, and X represents a hydroxyl group, a carboxyl group, an amino group, a phenolic hydroxyl group or an acid chloride. k is 1-10
It is an integer of 0, preferably 5 to 50. When k exceeds 100, the transparency of the obtained PC-PDMS copolymer decreases, which is not preferable. In the production of the PC-PDMS copolymer, the polyorganosiloxane of the component (B) is the above-mentioned P
The C oligomer is used in the reaction at a ratio of 0.3 to 100 (molar ratio), preferably 0.5 to 70.
When the PC oligomer is less than 0.3, the obtained PC-PDM
The decrease in the refractive index of the S copolymer is small. Further, when it exceeds 100, the molecular weight of the PC-PDMS copolymer is not improved.

In the method for producing a PC-PDMS copolymer according to the present invention, the above-mentioned PC oligomer of component (A) and (B) are used.
It is characterized in that the component PDMS is continuously mixed under the condition that substantially no alkaline compound is present. That is, in the production method of the present invention, first, P of the component (A) is
The C oligomer and PDMS as the component (B) are continuously mixed in an organic solvent (for example, methylene chloride) in a mixer under the condition that substantially no alkaline compound is present. Here, the mixer is not particularly limited as long as it can mix fluids, and may be a vertical type or a horizontal type, and may be a dynamic mixer or a static mixer. It may also be an orifice or a centrifugal pump. Specific examples of the dynamic mixer include a multi-line mixer [manufactured by Satake Chemical Industry Co., Ltd.], a Komatsu Ruzer Disintegrator [manufactured by Komatsu Zenoa Co., Ltd.], a pipeline homomixer [Special Machine Industry ( Co., Ltd.] and the like. Specific examples of the static mixer include a Kenix type static mixer, a sulzer type static mixer, and a Toray type static mixer.

The mixture of the PC oligomer of the component (A) and the PDMS of the component (B), which are continuously mixed in this mixer, is then fed to the reactor, in the presence of the alkaline compound and the catalyst (C). The reaction product of the PC-PDMS copolymer can be obtained by reacting with the dihydric phenol as the component). Alternatively, the PC oligomer of the component (A) and the P of the component (B), which are continuously mixed in this mixer,
The mixture with DMS is then fed to the reactor and reacted in the presence of alkaline compound and catalyst to give PC-PD.
Form an MS copolymer oligomer. Furthermore, this P
The reaction product of the PC-PDMS copolymer can be obtained by reacting the C-PDMS copolymer oligomer with the dihydric phenol as the component (C) in the presence of an alkaline compound and a catalyst. Here, as the dihydric phenol as the component (C), the same one as in the production of the PC oligomer can be used. This PC oligomer and PD
The reaction product of the PC-PDMS copolymer obtained by the reaction with MS has an excess of PC oligomer in a molar amount. Therefore, the PC-PDMS copolymer oligomer and the PC oligomer in which the PC oligomer is reacted with both ends of PDMS. It is a mixture of. Here, the reactor is not particularly limited as long as it can stir the fluid, and may be a vertical type or a horizontal type. For example, there is a pipeline homomixer [made by Tokushu Kika Kogyo Co., Ltd.]. The reaction temperature in this reactor is 0 to 60 ° C, preferably 10 to 50 ° C. The reaction residence time may be 1 second or longer.

The above-mentioned PC-PDMS copolymer or P
Examples of the alkaline compound used to obtain the C-PDMS copolymer oligomer include, for example, NaOH and KOH.
And so on. This alkaline compound is PDMS
1 to 20, preferably 1.1 in molar ratio with respect to the terminal groups of
-10 is added. If the alkaline compound is less than 1, P
It is not preferable because the reaction between the C oligomer and PDMS does not proceed completely. On the other hand, when the amount of the alkaline compound exceeds 20, decomposition of the chloroformate group of the PC oligomer increases, and the molecular weight of the resulting PC-PDMS copolymer is not improved, which is not preferable.

As the catalyst, a tertiary amine or a quaternary ammonium salt can be used. Specifically, examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine and the like. Further, as the quaternary ammonium salt, for example,
Trimethylbenzylammonium chloride, triethylammonium chloride and the like can be mentioned. The catalyst is added in a molar ratio of 1.0 × 10 ^{−4 to} 5.0 × 10 ⁻² , preferably, to the chloroformate group of the PC oligomer.
It is 5.0 × 10 ^{−4 to} 1.0 × 10 ⁻² . Addition amount is 1.0 x 1
When it is less than 0 ^-4 , the reaction progresses slowly, and it is 5.0 × 10 ^-2.
If it exceeds, the effect is not seen for the amount added, and it is not necessary to add more than this. In addition, as a terminal blocker, for example, p-tert-butylphenol (PT
BP), p-tert-octylphenol, p-cumylphenol, phenol, tribromophenol and the like can be used.

PC-obtained by the manufacturing method of the present invention
The PDMS copolymer has the general formula (IV)

[0018]

[Chemical 5]

[In the formula, R ⁶ , R ⁷ , Z, m and n are the same as described above. And a polycarbonate unit having a degree of polymerization of 3 to 100, having a repeating unit having a structure represented by
General formula (V)

[0020]

[Chemical 6]

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
X and k are the same as above. ), Which is composed of a polyorganosiloxane portion having a repeating unit represented by the formula (1), and has very excellent transparency. The degree of polymerization of the polyorganosiloxane part is preferably 100 or less, more preferably 50 or less. If the degree of polymerization exceeds 100,
The transparency of the copolymer is lowered, which is not preferable. PC above
The -PDMS copolymer is a block copolymer composed of a polycarbonate part having a repeating unit represented by the general formula (IV) and a polyorganosiloxane part having a repeating unit represented by the general formula (V). And viscosity average molecular weight of 10,000 to 40,000, preferably 15,000.
It is from 00 to 35,000. The ratio of the polycarbonate part to the polyorganosiloxane part in this PC-PDMS copolymer varies depending on the required transparency,
It cannot be uniquely determined. Usually, the polycarbonate part is selected in the range of 50 to 99.9% by weight, preferably 60 to 99.5% by weight, and the polyorganosiloxane part is selected in the range of 50 to 0.1% by weight, preferably 40 to 0.5% by weight.

In order to obtain a molded article using the PC-PDMS copolymer excellent in transparency obtained by the production method of the present invention, first, (I) PC-PDMS copolymer, (II)
A polycarbonate resin composition containing glass fiber and (III) polycarbonate resin as main components is prepared. That is, the polycarbonate resin composition is usually (I)
PC-PDMS copolymer 10 to 95% by weight, preferably 10 to 90% by weight, (II) glass 5 to 60% by weight, preferably 10 to 50% by weight and (III) polycarbonate resin 0 to 85% by weight, preferably Is 0 to 80% by weight. Here, the (I) PC-PDMS copolymer is (III) when a copolymer having a high proportion of a polycarbonate part is used.
The amount of the polycarbonate resin blended can be reduced, and in some cases it may not be necessary to blend the polycarbonate resin as the component (III). In this resin composition, if the compounding ratio of the (II) glass is less than 5% by weight, the dimensional stability is lowered, which is not preferable. On the other hand, if it exceeds 60% by weight, it is difficult or impossible to knead the resin, which is not preferable. As the glass (II) used in the preparation of this polycarbonate resin composition, various kinds or forms can be applied. For example, glass fibers, glass beads, glass flakes, glass powder and the like can be used, and these may be used alone or in combination of two or more kinds. Among these, the glass fibers widely used for resin reinforcement may be any of alkali-containing glass, low-alkali glass and non-alkali glass. The fiber length is 0.1 to 8 mm, preferably 0.3 to 6 mm, and the fiber diameter is 3 to 30 μm, preferably 5 to 25 μm. The form of the glass fiber is not particularly limited, and various forms such as roving, milled fiber, chopped strand, etc. can be mentioned. These glass fibers may be used alone or in combination of two or more kinds. Further, these glass materials are surface-treated with a silane coupling agent such as aminosilane-based, epoxysilane-based, vinylsilane-based, methacrylsilane-based, a chromium complex compound, a boron compound or the like in order to enhance the affinity with the resin. It may be

Next, the polycarbonate resin composition is mixed with the above-mentioned components (I), (II) and (III) and various optional components used as necessary, and kneaded. The compounding and kneading are methods commonly used, for example, ribbon blender, Henschel mixer, Banbury mixer,
It can be carried out by a method using a drum tumbler, a single-screw extruder, a twin-screw extruder, a co-kneader, a multi-screw extruder or the like. The heating temperature for kneading is usually selected in the range of 250 to 300 ° C. The polycarbonate resin composition thus obtained,
Various known molding methods, such as injection molding, blow molding,
By applying extrusion molding, compression molding, calendar molding, rotational molding, etc., it is possible to manufacture molded articles in the automotive field such as glass for automobiles and sunroofs, and molded articles in the field of home appliances. In addition, various additives, other synthetic resins, elastomers, and the like can be added to the resin composition, if necessary. For example, various additives include antioxidants such as hindered phenol-based, phosphite-based, phosphate-based, and amine-based antioxidants, ultraviolet absorbers such as benzotriazole-based and benzophenone-based antioxidants, and hindered amine-based light-absorbing agents. Examples include stabilizers, external lubricants such as aliphatic carboxylic acid ester-based and paraffin-based lubricants, commonly used flame retardants, release agents, antistatic agents, and colorants.

[0024]

The present invention will be further described in detail with reference to production examples, examples and comparative examples. Production Example 1 [Production of Polycarbonate (PC) Oligomer] 400
60 kg of bisphenol A (BPA) was dissolved in liter of 5% sodium hydroxide aqueous solution to prepare an aqueous solution of bisphenol A sodium hydroxide. Then, an aqueous sodium hydroxide solution of bisphenol A kept at room temperature at a flow rate of 138 liters / hour, and methylene chloride at a flow rate of 69 liters / hour, an inner diameter of 10 mm and a pipe length of 10 m.
Was introduced into the tubular reactor of No. 2 through an orifice plate, and phosgene was co-currently injected into the reactor at a flow rate of 10.7 kg / hour,
The reaction was continued for 3 hours. The tubular reactor used here was a double tube, and cooling water was passed through the jacket to keep the discharge temperature of the reaction solution at 25 ° C. The pH of the discharged liquid was adjusted to 10-11. By leaving the reaction solution thus obtained, the aqueous phase is separated and removed, and the methylene chloride phase (220 liters) is collected.
170 liters of methylene chloride was further added thereto, and the mixture was sufficiently stirred to obtain a PC oligomer (concentration: 317 g / liter). The degree of polymerization of the PC oligomer obtained here was 3 to 4, and the concentration of the chloroformate group was 0.7N.

Production Example 2-1 [Synthesis of Reactive Polydimethylsiloxane A (PDMS-A)] 1483 g of octamethylcyclotetrasiloxane, 96 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86%. Sulfuric acid was mixed and stirred at room temperature for 17 hours.
Then, the oil phase was separated, 25 g of sodium hydrogen carbonate was added, and the mixture was stirred for 1 hour. After filtration, 150 ℃, 3to
Vacuum distillation was performed at rr to remove low-boiling substances. To a mixture of 60 g of 2-allylphenol and 0.0014 g of platinum as platinum chloride-alcoholate complex was added 294 g of the oil obtained above at a temperature of 90 ° C. 90 this mixture
The mixture was stirred for 3 hours while maintaining the temperature at 115 ° C. The product was extracted with methylene chloride and 3% with 80% aqueous methanol.
It was washed twice to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulphate and dried in vacuum at 115
The solvent was distilled off to a temperature of ° C. The terminal phenol PDMS-A thus obtained had a repeating number of dimethylsilanooxy units of 30 as measured by NMR.

Production Example 2-2 (Synthesis of Reactive PDMS-B) In Production Example 2-1,
Example 1 was repeated except that the amount of 1,1,3,3-tetramethyldisiloxane was changed to 18.1 g. The obtained terminal phenol PDMS-B had a repeating number of dimethylsilanooxy units of 150 as measured by NMR.

Example 1 The PC oligomer obtained in Production Example 1 and the reactive PDMS obtained in Production Example 2-1 were reacted according to the flow shown in FIG. That is, in the above reaction, a 5% by weight solution of PC oligomer and reactive PDMS-A in methylene chloride, 1% by weight triethylamine (TE
A) Aqueous solution and 25 wt% sodium hydroxide (NaO
H) Aqueous solutions were used respectively. Each flow rate is PC
Oligomer: 0.23 l / h, reactive PDMS-
A: 4.3 liters / hour, TEA: 0.36 liters / hour, NOH: 0.23 liters / hour. Pipeline homomixer [made by Tokushu Kika Kogyo Co., Ltd., 2SL type: internal volume 0.3 liter, diameter of first turbine blade 42.5 mm, diameter of second first turbine blade 48]
mm], the mixer is 500 rpm, and the reactor is 300
It was rotated at 0 rpm. The main pipe (PC oligomer line) used had an inner diameter of 16 mm. TE
A was charged 60 cm from the mixer, and NaOH was charged 80 cm from the mixer. And the temperature of the reactor was 25-30 degreeC. The resulting reaction product (PC-PD
(Containing MS copolymer oligomer) was allowed to stand and separated, and 330 cc of the organic phase was transferred to a 1-liter batch type reactor, 120 cc of methylene chloride and p-tert-butylphenol 2.
2 g was added and stirred to homogenize. An alkaline aqueous solution of bisphenol A (bisphenol A: 19 g, sodium hydroxide: 11 g, water: 130 cc) was added to this, and 50
The reaction was carried out at 0 rpm for 1 hour. After the reaction, the mixture was transferred to a 7-liter washing tank, 400 cc of methylene chloride and 400 cc of water were added, and the organic phase and the aqueous phase were separated. After the separation, the organic phase was washed with alkali (0.01 N NaOH) and water, and then methylene chloride was removed to obtain PC-PDMS copolymer flakes. Pellet the obtained flakes at 280 ° C.,
A haze was measured by injection-molding a square plate having a thickness of 3 mm at 280 ° C. The haze of the obtained molded product was 2 (%), which was extremely excellent in transparency. The haze is measured by J
According to IS K 7105.

Example 2 Example 2 was carried out in the same manner as in Example 1 except that a Sulzer type static mixer (the number of elements: 3, SMV type) was used as the mixer. The haze of the obtained molded product was 2 (%), which was extremely excellent in transparency. Example 3 In Example 1, instead of the mixer, an orifice (diameter 2.
5 mm) was used, and the same procedure as in Example 1 was performed.
The haze of the obtained molded product was 3 (%), which was extremely excellent in transparency.

Comparative Example 1 The procedure of Example 1 was repeated, except that the reactive PDMS-B obtained in Production Example 2-2 was used as PDMS. The haze of the obtained molded product is 95.
(%), The transparency was inferior to that of the example. Comparative Example 2 In Example 1, the mixer was not used, and the piping (inner diameter 1
6 mm) was used and charged into the reactor in the same manner as in Example 1. The haze of the obtained molded product is 3
It was 6 (%) and was inferior in transparency as compared with the examples. The viscosity average molecular weights of the PC-PDMS copolymers obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were 20,000.
0, the PDMS content was 4.0% by weight.

Application Example 1 Pellets of the PC-PDMS copolymer obtained in Example 1 and a polycarbonate resin [Taflon A2200, manufactured by Idemitsu Petrochemical Co., Ltd.] were blended at a ratio of 5: 4 to obtain glass as glass. Fiber [Asahi Fiber Glass Co., Ltd.
Manufactured by ECR Glass], and pellets were prepared at 300 ° C. using a 30 mm vented extruder so that the glass content would be 30% by weight. The glass was supplied from the downstream side of the hopper supply position of the raw material resin of the extruder. The pellets obtained were press-molded at 300 ° C. to a thickness of 3 mm and the haze was measured. The haze of the obtained molded product is 11
(%) Was excellent in transparency.

Application Example 2 The haze was measured in the same manner as in Application Example 1 except that only the polycarbonate resin was used as the resin in Application Example 1. The haze of the obtained molded product is 41 (%).
The transparency is inferior to that of the application example 1, and the PC according to the present invention
-The difference due to the PDMS copolymer is remarkable.

[0032]

As described above, the PC-PDMS copolymer produced by the production method of the present invention is extremely excellent in transparency. Therefore, the polycarbonate resin composition containing the PC-PDMS copolymer according to the present invention can be effectively used as a raw material for various molded products that are widely used in the fields of electric / electronic devices and automobiles.

[Brief description of drawings]

FIG. 1 is a diagram showing a flow of an example of a method for producing a polycarbonate-polyorganosiloxane copolymer of the present invention.

FIG. 2 is a diagram showing a flow of another example of the method for producing a polycarbonate-polyorganosiloxane copolymer of the present invention.

FIG. 3 is a diagram showing a part of a raw material flow in Example 1.

Claims (3)

[Claims] 1. A polycarbonate oligomer (A) and a polyorganosiloxane (B) are continuously mixed under the condition that substantially no alkaline compound is present, and then,
A method for producing a polycarbonate-polyorganosiloxane copolymer, which comprises reacting (C) a dihydric phenol in the presence of an alkaline compound. 2. A polycarbonate oligomer (A) and a polyorganosiloxane (B) are continuously mixed under the condition that substantially no alkaline compound is present, and then,
A polycarbonate-polyorganosiloxane copolymer oligomer is produced by reacting in the presence of an alkaline compound, and further, the polycarbonate-polyorganosiloxane copolymer oligomer is reacted with the (C) dihydric phenol in the presence of an alkaline compound. A method for producing a polycarbonate-polyorganosiloxane copolymer, comprising: 3. The polyorganosiloxane of component (B) has the general formula (I): ^{(R 1, R 2, R} 3 and R ⁴ are each hydrogen, an alkyl group or a phenyl group having 1 to 6 carbon atoms, or may be different even for the same. In addition, R ⁵
Represents an organic residue containing an aliphatic or aromatic group, and X represents a hydroxyl group, a carboxyl group, an amino group, a phenolic hydroxyl group or an acid chloride. k is an integer of 1 to 100. The method for producing a polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein