JP6589248B2 - Polyorganosiloxane, polycarbonate-polyorganosiloxane copolymer and method for producing the same - Google Patents

Description

  The present invention relates to a polyorganosiloxane, a polycarbonate-polyorganosiloxane copolymer capable of obtaining a polycarbonate molded product with less yellowness without impairing transparency and low-temperature impact resistance, and a method for producing the same.

Polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes abbreviated as “PC-POS”) has excellent properties such as high impact resistance, chemical resistance, and flame retardancy. It is expected to be widely used in various fields such as equipment field and automobile field. Especially for mobile phones, smartphones, mobile PCs, tablets, portable terminals, etc., lighting covers, building materials, digital cameras, video cameras, etc. that require visibility, police shields, helmet visors, sports Use for other daily necessities such as protective equipment is spreading. In addition to normal conditions, such as room temperature, these are assumed to be used under low temperature, such as a cold region, or outdoors.
Usually, as a typical polycarbonate, a homopolycarbonate using 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is generally used as a dihydric phenol as a raw material. In order to improve the physical properties of this homopolycarbonate such as flame retardancy and impact resistance, a polycarbonate-polyorganosiloxane copolymer using polyorganosiloxane as a copolymerization monomer is known. It is known that a polycarbonate-polyorganosiloxane copolymer is superior in flame retardancy and impact resistance as compared to a homopolycarbonate such as bisphenol A (Patent Document 1).
Patent Document 2 discloses a polycarbonate-polyorganosiloxane copolymer with improved transparency, and evaluates the total light transmittance, haze value, and the like.
Patent Document 3 discloses a polycarbonate-polyorganosiloxane copolymer with improved color tone. Patent Document 3 teaches that by reducing the content of a specific component in a polycarbonate-polyorganosiloxane copolymer, the difference in color tone due to residence time at the time of injection molding is small as well as excellent thermal stability. ing.

JP 2012-246430 A JP 2011-46911 A Special table 2011-122048 gazette

However, in the above patent documents and the like, there is no mention of the yellowish color of the polycarbonate-polyorganosiloxane copolymer itself. Even if it is excellent in transparency, if the yellowness of the polycarbonate-polyorganosiloxane copolymer itself has not been reduced, for example, lighting covers, instrument panels that require good visibility, helmet visors, police shields, etc. It becomes a problem in use.
An object of the present invention is to provide a polycarbonate-polyorganosiloxane copolymer having excellent transparency and low yellowness without deteriorating mechanical properties.

The present inventors have found that the above-mentioned problems can be achieved by controlling the molecular weight distribution of the polyorganosiloxane used in the polycarbonate-polyorganosiloxane copolymer.
That is, this invention relates to the following 1-11.
1. Obtained from measurement by gel permeation chromatography using polystyrene as a conversion standard, the horizontal axis is a logarithmic value log (M) of molecular weight M, and the vertical axis is a derivative of concentration fraction w by logarithmic value log (M) of molecular weight. In the differential molecular weight distribution curve of dw / dlog (M), the integrated value of dw / dlog (M) in the range of 2.5 ≦ log (M) ≦ 3.1 is the entire range of log (M) The polyorganosiloxane is 0 to 10% based on the integrated value of dw / dlog (M).
2. 2. The polyorganosiloxane according to 1, wherein in the differential molecular weight distribution curve, the value of dw / dlog (M) is maximum within a range of 3.3 ≦ log (M) ≦ 3.9.
3. The polyorganosiloxane according to 1 or 2, having an average chain length of 20 to 50.
4). The polyorganosiloxane according to any one of 1 to 3, wherein the polyorganosiloxane is a polyorganosiloxane represented by the following general formula (1) or (2).

[Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Y ^{is, -R 5 O -, - R} 5 COO -, - R 5 NH -, - R 5 NHR 6 -, - COO -, - S -, - R 5 COO-R 7 -O-, or -R ⁵ O—R ⁸ —O—, wherein R ⁵ represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, an arylene group, or a diarylene group. R ⁶ represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R ⁷ represents a diarylene group. R ⁸ represents a linear, branched or cyclic alkylene group, or a diarylene group. Z represents a hydrogen atom or a halogen atom. β represents a divalent group derived from a diisocyanate compound or a divalent group derived from dicarboxylic acid or a halide of dicarboxylic acid. The sum of p and q is n, and n indicates an average number of repetitions of 20-50. ]
A process for producing a polycarbonate-polyorganosiloxane copolymer using the polyorganosiloxane according to any one of 5.1 to 4 as a raw material.
6). Polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate block (A) comprising a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (B) comprising a repeating unit represented by the following general formula (II) Coalesce,
The horizontal axis is the logarithmic value log (M) of the molecular weight M, and the vertical axis is the concentration fraction w obtained from the measurement by gel permeation chromatography using the polystyrene of the polyorganosiloxane block (B) as a conversion standard. In the differential molecular weight distribution curve which is dw / dlog (M) differentiated by the logarithmic value log (M), the value obtained by integrating the dw / dlog (M) value in the range of 2.5 ≦ log (M) ≦ 3.1 Is a polycarbonate-polyorganosiloxane copolymer in which dw / dlog (M) value is 0 to 10% over the entire range of log (M).

[In formula, R < ⁹ > and R < ¹⁰ > shows a halogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group each independently. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, a carbon An arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O— or —CO—; a and b each independently represent an integer of 0 to 4.
R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The average repeating number n of 20 to 50 indicates the total number of siloxane repeating units in the polyorganosiloxane block. ]
7). The polycarbonate according to 6, wherein in the differential molecular weight distribution curve of the polyorganosiloxane block (B), the value of dw / dlog (M) is maximum in the range of 3.3 ≦ log (M) ≦ 3.9. Polyorganosiloxane copolymer.
8). The polycarbonate-polyorganosiloxane copolymer according to 6 or 7, wherein the polyorganosiloxane block (B) has an average chain length of 20 to 50.
9. The polycarbonate-polyorganosiloxane copolymer according to any one of 6 to 8, wherein the content of the polyorganosiloxane block (B) in the polycarbonate-polyorganosiloxane copolymer is 0.5 to 20% by mass.
10. The polycarbonate-polyorganosiloxane copolymer according to any one of 6 to 9, which has a viscosity average molecular weight of 12,000 to 40,000.
A molded article formed by molding the polycarbonate-polyorganosiloxane copolymer according to any one of 11.6 to 10.

  According to the present invention, by controlling the molecular weight distribution of the polyorganosiloxane and controlling the chain length distribution, the polycarbonate-polyorganosiloxane copolymer having excellent transparency and low yellowness is obtained without reducing the mechanical strength. Combines can be obtained.

The graph which shows the differential molecular weight distribution curve of the polyorganosiloxane of Example 1 and Comparative Example 1.

  The polyorganosiloxane of the present invention is obtained by measurement by gel permeation chromatography using polystyrene as a conversion standard, the horizontal axis is a logarithmic value log (M) of molecular weight M, and the vertical axis is concentration fraction w of molecular weight. In the differential molecular weight distribution curve which is dw / dlog (M) differentiated by logarithmic value log (M), the value obtained by integrating dw / dlog (M) value in the range of 2.5 ≦ log (M) ≦ 3.1 is , Log (M) is 0 to 10% of the integrated value of dw / dlog (M) value in the entire range.

  In the present invention, in the differential molecular weight distribution curve, a value obtained by integrating dw / dlog (M) values in the range of 2.5 ≦ log (M) ≦ 3.1 is dw / M in the entire range of log (M). It is 0-10% with respect to the value which integrated dlog (M) value, Preferably it is 0-9%. When the said ratio exceeds 10%, it exists in the tendency for the yellowishness of the copolymer of polyorganosiloxane and a polycarbonate to increase. Here, the value obtained by integrating the dw / dlog (M) value in the range of 2.5 ≦ log (M) ≦ 3.1, and the value obtained by integrating the dw / dlog (M) value in the entire range of log (M). The ratio with respect to the molecular weight distribution of polyorganosiloxane indicates the ratio at which a component having a log (M) of 2.5 to 3.1 is present relative to the whole polyorganosiloxane.

  The GPC apparatus for obtaining the molecular weight / molecular weight distribution measurement value of polyorganosiloxane is not particularly limited, and is generally a commercially available high-temperature GPC apparatus such as a high-temperature GPC with a built-in differential refractometer (RI) manufactured by Tosoh Corporation. It is possible to use a measuring instrument “HLC-8200”. Specifically, as a GPC column, a column obtained by connecting “TSK-GEL G4000HXL” and “TSK-GEL G2000HXL” manufactured by Tosoh Corporation is used. The column temperature is set to 40 ° C., tetrahydrofuran (THF) is used as the eluent, and measurement is performed at a flow rate of 1.0 ml / min. Standard polystyrene made by Tosoh Corporation is used for preparing the calibration curve. The logarithmic value of the molecular weight thus obtained is referred to as logarithmic molecular weight (log (M)).

A time curve (generally referred to as an elution curve) of an intensity distribution detected by a differential refraction (RI) detector of a GPC apparatus is converted into a molecular weight using a calibration curve obtained from a substance having a known molecular weight. Here, since the RI detection intensity is proportional to the component concentration, the intensity area when the total area of the elution curve is 100% is obtained, and the concentration fraction of each elution time is obtained. The integrated molecular weight distribution curve can be obtained by sequentially integrating the concentration fractions and plotting the logarithmic value of the molecular weight (log (M)) on the horizontal axis and the integrated value of the concentration fraction (w) on the vertical axis.
Subsequently, the differential value of the curve in the logarithmic value of each molecular weight (that is, the slope of the integral molecular weight curve) is obtained, the logarithmic value of the molecular weight (log (M)) is plotted on the horizontal axis, and the differential value (dw / dlog ( M)) can be plotted to obtain a differential molecular weight distribution curve. Therefore, the differential molecular weight distribution means a value obtained by differentiating the concentration fraction (w) by the logarithmic value of the molecular weight (log (M)), that is, “dw / dlog (M)”. From this differential molecular weight distribution curve, the differential molecular weight distribution dw / dlog (M) at a specific log (M) can be read. In addition, also about the polyorganosiloxane compound which mix | blended several polyorganosiloxane, after measuring a polyorganosiloxane compound by GPC method, a differential molecular weight distribution curve can be obtained with the same method.

  In another embodiment of the present invention, the polyorganosiloxane may have a maximum value when the value of dw / dlog (M) is 3.3 ≦ log (M) ≦ 3.9. The maximum value of the differential molecular weight distribution dw / dlog (M) refers to the peak top in the differential molecular weight distribution curve. If the log (M) when the value of dw / dlog (M) takes the maximum value in the differential molecular weight distribution curve is less than 3.3, the low-temperature impact resistance of the copolymer of polyorganosiloxane and polycarbonate is inferior. As a result, when it exceeds 3.9, the transparency of the copolymer tends to decrease.

  The average chain length of the polyorganosiloxane is preferably 20 to 50, more preferably 30 to 45, and still more preferably 35 to 45. The average chain length is calculated by nuclear magnetic resonance (NMR) measurement. If the average chain length is 20 or more, the impact resistance at low temperature of the copolymer of polyorganosiloxane and polycarbonate can be sufficiently obtained. If the average chain length is 50 or less, the copolymer of polyorganosiloxane and polycarbonate is excellent in transparency.

  As polyorganosiloxane which has the said characteristic, what is shown to the following general formula (1) and (2) can be mentioned, for example.

[Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Y ^{is, -R 5 O -, - R} 5 COO -, - R 5 NH -, - R 5 NHR 6 -, - COO -, - S -, - R 5 COO-R 7 -O-, or -R ⁵ O—R ⁸ —O— is shown. R ⁵ represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, an arylene group, or a diarylene group. R ⁶ represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R ⁷ represents a diarylene group. R ⁸ represents a linear, branched or cyclic alkylene group, or a diarylene group. Z represents a hydrogen atom or a halogen atom. β represents a divalent group derived from a diisocyanate compound or a divalent group derived from dicarboxylic acid or a halide of dicarboxylic acid. The sum of p and q is n, and n indicates an average number of repetitions of 20-50. ]

Examples of the halogen atom independently represented by R ^{1 to} R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group independently represented by R ^{1 to} R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups (“various” means linear and all branched chains. And the same applies hereinafter), various pentyl groups, and various hexyl groups. As an alkoxy group which R < ¹ > -R < ⁴ > shows each independently, the case where an alkyl group site | part is the said alkyl group is mentioned. Examples of the aryl group independently represented by R ^{1 to} R ⁴ include a phenyl group and a naphthyl group.
R ^{1 to} R ⁴ are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
As the polyorganosiloxane represented by the general formulas (1) and (2), those in which R ^{1 to} R ⁴ are all methyl groups are preferable.

Y ^{indicated, -R 5 O -, - R} 5 COO -, - R 5 NH -, - R 5 NHR 6 -, - R 5 COO-R 7 -O-, or -R ⁵ O-R ⁸ -O Examples of the linear or branched alkylene group represented by R ^{5 in} — include alkylene groups having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and cyclic alkylene groups having 5 to 15 carbon atoms, preferably A C5-C10 cycloalkylene group is mentioned.

The aryl-substituted alkylene group represented by R ⁵ may have a substituent such as an alkoxy group or an alkyl group on the aromatic ring. Specific examples of the structure include, for example, the following general formula (3) or ( The structure of 4) can be shown. In addition, when it has an aryl substituted alkylene group, the alkylene group is couple | bonded with Si.

(C represents a positive integer and is usually an integer of 1 to 6)

The diarylene group represented by R ⁵ , R ⁷ and R ⁸ is a group in which two arylene groups are linked directly or via a divalent organic group. Specifically, —Ar ¹ —W— It is a group having a structure represented by Ar ² —. Here, Ar < ¹ > and Ar < ² > show an arylene group, W is a single bond or a C1-C8 alkylene group, a C2-C8 alkylidene group, a C5-C15 cycloalkylene group, carbon number 5-15 cycloalkylidene group, fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, aryl alkylidene group having 7 to 15 carbon atoms, -S -, - SO -, - SO 2 -, - O- Or -CO- is shown.
Examples of the alkylene group represented by W include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, and the like, and an alkylene group having 1 to 5 carbon atoms is preferable. Examples of the alkylidene group represented by W include an ethylidene group and an isopropylidene group. Examples of the cycloalkylene group represented by W include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group, and a cycloalkylene group having 5 to 10 carbon atoms is preferable. Examples of the cycloalkylidene group represented by W include a cyclohexylidene group, 3,5,5-trimethylcyclohexylidene group, 2-adamantylidene group and the like, and a cycloalkylidene group having 5 to 10 carbon atoms is preferable. A cycloalkylidene group having 5 to 8 carbon atoms is more preferable. Examples of the aryl moiety of the arylalkylene group represented by W include aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. Examples of the aryl moiety of the arylalkylidene group represented by W include aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.
Examples of the arylene group represented by R ⁵ , Ar ^1, and Ar ² include arylene groups having 6 to 14 ring carbon atoms such as a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. These arylene groups may have an arbitrary substituent such as an alkoxy group or an alkyl group.

The alkyl group represented by R ⁶ is linear or branched having 1 to 8, preferably 1 to 5 carbon atoms. Examples of the alkenyl group include straight chain or branched chain groups having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a phenylmethyl group and a phenylethyl group.
Linear chain R ⁸ represents, branched or cyclic alkylene group are the same as R ^5.
Y is preferably —R ⁵ O—, and R ⁵ is an aryl-substituted alkylene group, particularly a residue of a phenol compound having an alkyl group, and is derived from an organic residue derived from allylphenol or eugenol. The organic residue is more preferable. At this time, it is preferable that Z is a hydrogen atom.
In addition, about p and q in General formula (2), it is preferable that it is p = q, ie, p = n / 2, q = n / 2.
Β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid. For example, in the following general formulas (5-1) to (5-5) And a divalent group represented.

  Examples of the polyorganosiloxane represented by the general formula (1) include compounds represented by the following general formulas (1-1) to (1-11).

In the general formulas (1-1) to (1-11), R ^{1 to} R ⁴ , n and R ⁶ are as defined above, and preferred ones are also the same. c shows a positive integer and is an integer of 1-6 normally.
Among these, the phenol-modified polyorganosiloxane represented by the general formula (1-1) is preferable from the viewpoint of ease of polymerization. In terms of availability, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, which is one of the compounds represented by the general formula (1-2), Α, ω-bis [3- (4-hydroxy-3-methoxyphenyl) propyl] polydimethylsiloxane which is one of the compounds represented by the general formula (1-3) is preferable.

  The method for producing the crude polyorganosiloxane used in the present invention is not particularly limited. For example, according to the method described in JP-A-11-217390, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize α, ω-dihydrogenorganopentasiloxane, Phenol compounds having an unsaturated group in the α, ω-dihydrogenorganopentasiloxane in the presence of a hydrosilylation catalyst (for example, 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.), etc. A crude polyorganosiloxane can be obtained by addition reaction. Further, according to the method described in Japanese Patent No. 2662310, octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of sulfuric acid (acidic catalyst), and the obtained α, ω-dihydrogenorgano is obtained. Similarly to the above, a crude polyorganosiloxane can be obtained by subjecting polysiloxane to an addition reaction with a phenol compound having an unsaturated group in the presence of a hydrosilylation reaction catalyst. The α, ω-dihydrogenorganopolysiloxane can be used by appropriately adjusting its chain length n depending on the polymerization conditions, or a commercially available α, ω-dihydrogenorganopolysiloxane may be used. .

  Examples of the hydrosilylation reaction catalyst include transition metal catalysts. Among them, platinum catalysts are preferably used from the viewpoint of reaction rate and selectivity. Specific examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, a complex of platinum and a vinyl group-containing siloxane, platinum-supported silica, platinum-supported activated carbon, and the like.

By bringing the crude polyorganosiloxane into contact with the adsorbent, the transition metal derived from the transition metal catalyst used as the hydrosilylation reaction catalyst contained in the crude polyorganosiloxane is adsorbed on the adsorbent and removed. It is preferable to do.
As the adsorbent, for example, one having an average pore diameter of 1000 mm or less can be used. If the average pore diameter is 1000 mm or less, the transition metal in the crude polyorganosiloxane can be efficiently removed. From such a viewpoint, the average pore diameter of the adsorbent is preferably 500 mm or less, more preferably 200 mm or less, still more preferably 150 mm or less, and still more preferably 100 mm or less. From the same viewpoint, the adsorbent is preferably a porous adsorbent.

  The adsorbent is not particularly limited as long as it has the above average pore diameter. For example, activated clay, acidic clay, activated carbon, synthetic zeolite, natural zeolite, activated alumina, silica, silica-magnesia-based adsorbent, diatomaceous earth. Cellulose and the like can be used, and it is preferably at least one selected from the group consisting of activated clay, acidic clay, activated carbon, synthetic zeolite, natural zeolite, activated alumina, silica and silica-magnesia-based adsorbent.

After the transition metal contained in the crude polyorganosiloxane is adsorbed on the adsorbent, the adsorbent can be separated from the polyorganosiloxane by any separation means. Examples of means for separating the adsorbent from the polyorganosiloxane include a filter and centrifugal separation. When a filter is used, a filter such as a membrane filter, a sintered metal filter, or a glass fiber filter can be used, but it is particularly preferable to use a membrane filter.
From the viewpoint of separating the adsorbent from the polyorganosiloxane after adsorption of the transition metal, the average particle size of the adsorbent is usually 1 μm to 4 mm, preferably 1 to 100 μm.

  When the adsorbent is used in the present invention, the amount used is not particularly limited. The porous adsorbent is preferably used in an amount in the range of 1 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the crude polyorganosiloxane.

  If the crude polyorganosiloxane to be treated is not in a liquid state due to its high molecular weight, it may be heated to a temperature at which the polyorganosiloxane is in a liquid state when adsorbing with the adsorbent and separating the adsorbent. Good. Alternatively, it may be carried out by dissolving in a solvent such as methylene chloride or hexane.

  A polyorganosiloxane having a desired molecular weight distribution can be obtained, for example, by adjusting the molecular weight distribution by blending a plurality of polyorganosiloxanes. After blending a plurality of α, ω-dihydrogenorganopolysiloxanes, a crude polyorganosiloxane having a desired molecular weight distribution is obtained by addition reaction of a phenol compound having an unsaturated group in the presence of a hydrosilylation reaction catalyst. You can also get Further, after blending a plurality of crude polyorganosiloxanes, purification such as removal of the hydrosilylation reaction catalyst may be performed. A plurality of polyorganosiloxanes after purification may be blended. Moreover, it can also adjust suitably with the polymerization conditions at the time of polyorganosiloxane manufacture. Moreover, it can also obtain by fractionating only a part from existing polyorganosiloxane by means of various separations.

  In still another embodiment of the present invention, a method for producing a polycarbonate-polyorganosiloxane (hereinafter sometimes abbreviated as PC-POS) copolymer is provided, and the production method uses the above-mentioned polyorganosiloxane as a raw material. It is used as.

  As a method for producing the PC-POS copolymer, a known production method such as an interfacial polymerization method (phosgene method), a pyridine method, or a transesterification method can be used. Especially in the case of the interfacial polymerization method, the separation process between the organic phase containing the PC-POS copolymer and the aqueous phase containing unreacted substances, catalyst residues, etc. becomes easy, and each washing by alkali washing, acid washing and pure water washing Separation of the organic phase containing the PC-POS copolymer and the aqueous phase in the process becomes easy, and the PC-POS copolymer can be obtained efficiently.

There is no particular limitation on the method for producing the PC-POS copolymer, and it can be produced by referring to a known method for producing a PC-POS copolymer, for example, the method described in JP 2010-241943 A. .
Specifically, an aromatic polycarbonate oligomer produced in advance and the above polyorganosiloxane are dissolved in a water-insoluble organic solvent (such as methylene chloride), and an aqueous alkaline compound solution of dihydric phenol (such as bisphenol A) (water). Sodium oxide aqueous solution, etc.), and a tertiary amine (triethylamine, etc.) or a quaternary ammonium salt (trimethylbenzylammonium chloride, etc.) as a polymerization catalyst, and a terminal terminator (monovalent phenol such as pt-butylphenol) In the presence of an interfacial polycondensation reaction. The PC-POS copolymer can also be produced by copolymerizing polyorganosiloxane, dihydric phenol, phosgene, carbonate ester or chloroformate.

As described above, the raw material polyorganosiloxane is obtained by measurement by gel permeation chromatography using polystyrene as a conversion standard. The horizontal axis is a logarithmic value log (M) of molecular weight M, and the vertical axis is a concentration fraction w. In the differential molecular weight distribution curve dw / dlog (M) obtained by differentiating the logarithm of logarithm of the molecular weight log (M), the dw / dlog (M) value is integrated in the range of 2.5 ≦ log (M) ≦ 3.1. A polyorganosiloxane having a value of 0 to 10% with respect to a value obtained by integrating dw / dlog (M) values in the entire range of log (M) is used.
Further, the raw material polyorganosiloxane can take the maximum value in the range of dw / dlog (M) 3.3 ≦ log (M) ≦ 3.9, the average chain length, and the specific polyorganosiloxane. The general formulas, specific examples and production methods are as described above.

The polycarbonate oligomer can be produced by reacting a dihydric phenol with a carbonate precursor such as phosgene or triphosgene in an organic solvent such as methylene chloride, chlorobenzene, or chloroform. In addition, when manufacturing a polycarbonate oligomer using a transesterification method, it can also manufacture by reaction with carbonate precursor like dihydric phenol and diphenyl carbonate.
As the dihydric phenol, it is preferable to use a dihydric phenol represented by the following general formula (a).

[In formula, R < ⁹ > and R < ¹⁰ > shows a halogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group each independently. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, a carbon An arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O— or —CO—; a and b each independently represent an integer of 0 to 4. ]

In the general formula (a), examples of the halogen atom independently represented by R ⁹ and R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group independently represented by R ⁹ and R ¹⁰ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. Examples of the alkoxy group independently represented by R ⁹ and R ¹⁰ include a case where the alkyl group moiety is the alkyl group.
Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, and the like, and an alkylene group having 1 to 6 carbon atoms is preferable. Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group, and a cycloalkylene group having 5 to 10 carbon atoms is preferable. Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, 3,5,5-trimethylcyclohexylidene group, 2-adamantylidene group and the like, and a cycloalkylidene group having 5 to 10 carbon atoms is preferable. A cycloalkylidene group having 5 to 8 carbon atoms is more preferable. Examples of the aryl moiety of the arylalkylene group represented by X include aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.

a and b each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1.
Among them, a and b are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or a and b are 0 and X is an alkylene group having 3 carbon atoms, particularly an isopropylidene group. Some are preferred.

Examples of the dihydric phenol represented by the general formula (a) include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis ( Bis (hydroxyphenyl) alkanes such as 4-hydroxyphenyl) ethane and 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) And cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, and bis (4-hydroxyphenyl) ketone. It is done. These dihydric phenols may be used individually by 1 type, and 2 or more types may be mixed and used for them.
Among these, bis (hydroxyphenyl) alkane dihydric phenol is preferable, and bisphenol A is more preferable. When bisphenol A is used as the dihydric phenol, in the general formula (a), X is an isopropylidene group and a PC-POS copolymer in which a = b = 0 is obtained.

  Examples of dihydric phenols other than bisphenol A include bis (hydroxyaryl) alkanes, bis (hydroxyaryl) cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, and dihydroxy. Examples include diphenyls, dihydroxydiarylfluorenes, dihydroxydiaryladamantanes and the like. These dihydric phenols may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  Examples of bis (hydroxyaryl) alkanes include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, and 2,2- Bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxy Phenyl) naphthylmethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy) -3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-chloropheny) ) Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane.

  Examples of bis (hydroxyaryl) cycloalkanes include 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) norbornane, 1,1-bis (4-hydroxyphenyl) cyclododecane and the like. Examples of dihydroxyaryl ethers include 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether.

  Examples of dihydroxydiaryl sulfides include 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide. Examples of dihydroxydiaryl sulfoxides include 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, and the like. Examples of the dihydroxydiaryl sulfones include 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.

  Examples of dihydroxydiphenyls include 4,4'-dihydroxydiphenyl. Examples of dihydroxydiarylfluorenes include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Examples of the dihydroxydiaryladamantanes include 1,3-bis (4-hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane, 1,3-bis (4-hydroxyphenyl) -5,7- Examples thereof include dimethyladamantane.

  As other dihydric phenols, for example, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) -9-anthrone, 1,5 -Bis (4-hydroxyphenylthio) -2,3-dioxapentane and the like.

In the process for producing the PC-POS copolymer, a molecular weight modifier (terminal stopper) can be used to adjust the molecular weight of the obtained PC-POS copolymer. Examples of the molecular weight regulator include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol and p-tert-amylphenol. Mention may be made of monohydric phenols. These monohydric phenols may be used individually by 1 type, and may be used in combination of 2 or more type.
By using the above-mentioned molecular weight modifier and the like, the viscosity average molecular weight of PC-POS can be appropriately produced according to the intended use and product.

  After the above interfacial polycondensation reaction, the mixture is allowed to stand to separate into an aqueous phase and an organic solvent phase [separation step], and the organic solvent phase is washed (preferably washed in the order of basic aqueous solution, acidic aqueous solution, and water) [washing Step], the PC-POS copolymer can be obtained by concentrating [concentration step] and drying [drying step] the obtained organic phase.

The present invention relates to a polycarbonate-polycarbonate containing a polycarbonate block (A) comprising a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (B) comprising a repeating unit represented by the following general formula (II). An organosiloxane copolymer,
The horizontal axis is the logarithmic value log (M) of the molecular weight M, and the vertical axis is the concentration fraction w obtained from the measurement by gel permeation chromatography using the polystyrene of the polyorganosiloxane block (B) as a conversion standard. In the differential molecular weight distribution curve which is dw / dlog (M) differentiated by the logarithmic value log (M), the value obtained by integrating the dw / dlog (M) value in the range of 2.5 ≦ log (M) ≦ 3.1 Relates to a polycarbonate-polyorganosiloxane copolymer, which is 0 to 10% with respect to a value obtained by integrating dw / dlog (M) values in the entire range of log (M).

In the general formula (I), R ⁹ , R ¹⁰ , X, a and b are as described above, and preferred ranges are also the same. R ¹ and R ² in the general formula (II) are also as described above, and preferred ranges are also the same.

  The polyorganosiloxane block in the PC-POS copolymer of the present invention has a value obtained by integrating dw / dlog (M) value in the range of 2.5 ≦ log (M) ≦ 3.1 in the differential molecular weight distribution curve. , Log (M), 0 to 10%, preferably 0 to 9% of the integrated value of dw / dlog (M) over the entire range. If the ratio exceeds 10%, the yellowness of the polyorganosiloxane tends to increase, and therefore the yellowness of the PC-POS copolymer tends to increase as a whole.

  The differential molecular weight distribution curve of the polyorganosiloxane block in the PC-POS copolymer is obtained by decomposing the PC-POS copolymer by using a strong alkaline aqueous solution such as a sodium hydroxide methanol solution. After extracting the organosiloxane, it can be confirmed by the above-described measurement by gel permeation chromatography using polystyrene as a conversion standard. As the GPC apparatus for obtaining the molecular weight / molecular weight distribution measurement value of the polyorganosiloxane, the above-described apparatus can be used.

  The polyorganosiloxane block in the PC-POS copolymer of the present invention can also take a maximum value when the value of dw / dlog (M) is in the range of 3.3 ≦ log (M) ≦ 3.9. When the log (M) when the value of dw / dlog (M) takes the maximum value in the differential molecular weight distribution curve is less than 3.3, the PC-POS copolymer is inferior in low-temperature impact resistance. If it exceeds 9, the transparency of the PC-POS copolymer tends to decrease.

  The average chain length n of the polyorganosiloxane block (II) in the PC-POS copolymer of the present invention is preferably 20 to 50, more preferably 30 to 45, and still more preferably 35 to 45. The average chain length is calculated by nuclear magnetic resonance (NMR) measurement. If the average chain length n is 20 or more, sufficient impact resistance at low temperatures can be obtained. Moreover, if average chain length n is 50 or less, the copolymer excellent in transparency can be obtained.

In the present invention, the content of the polyorganosiloxane block (B) represented by the general formula (II) in the PC-POS copolymer is preferably 0.5 to 20% by mass, more preferably 0.5 to 10% by mass. The content of the polyorganosiloxane block (B) in the PC-POS copolymer is a value calculated by nuclear magnetic resonance (NMR) measurement.
When the content of the polyorganosiloxane block (B) is less than 0.5% by mass, the impact resistance at low temperatures (about −20 ° C.) is decreased and the Izod impact strength tends to be decreased. Absent. Moreover, when content of a polyorganosiloxane block (B) exceeds 20 mass%, the impact resistance at normal temperature (about 23 degreeC) will fall.

The viscosity average molecular weight of the PC-POS copolymer of the present invention is usually in the range of about 12,000 to 40,000, preferably about 13,000 to 30,000. When the viscosity average molecular weight is less than 12,000, the strength of the molded product produced using the PC-POS copolymer of the present invention is not sufficient. On the other hand, if the viscosity average molecular weight exceeds 40,000, the viscosity of the copolymer increases, so that it is necessary to increase the temperature during injection molding or extrusion molding, and the transparency tends to decrease due to thermal degradation.
Although it is possible to lower the viscosity of the PC-POS copolymer by raising the molding temperature, in that case, the molding cycle becomes longer and less economical, and if the temperature is raised too much, the heat of the PC-POS copolymer Transparency tends to decrease due to deterioration.
The viscosity average molecular weight (Mv) is a value calculated from Schnell's formula ([η] = 1.23 × 10 ⁻⁵ × Mv ^0.83 ) by measuring the intrinsic viscosity [η] of the methylene chloride solution at 20 ° C. is there.

  In the PC-POS copolymer of the present invention, various known additives can be blended in the polycarbonate resin composition as desired, and these include reinforcing materials, stabilizers, antioxidants, UV absorption. Agents, antistatic agents, lubricants, mold release agents, dyes, pigments, and other flame retardants.

The PC-POS copolymer of the present invention can be made into a PC resin composition by blending and kneading known additives as necessary.
The above blending and kneading are usually performed using, 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. It can be done by a method.
The heating temperature for kneading is usually selected in the range of 250 to 320 ° C.

The present invention also relates to a molded body formed by molding the above-described PC-POS copolymer.
For molding the obtained PC resin composition, various conventionally known molding methods such as injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, etc. However, it is preferable to perform injection molding at a mold temperature of 60 ° C. or higher, preferably 80 to 120 ° C.
Under the present circumstances, the resin temperature in injection molding is about 280-360 degreeC normally, Preferably it is 280-330 degreeC.
The molded body of the present invention includes a mobile phone, a smartphone, a mobile personal computer, a tablet, a portable terminal and other casings, a lighting cover, a building material, a digital camera, a video camera and other electronic equipment casings that require visibility, and a police shield, It can be used in other daily necessities such as helmet visors and sports equipment.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these examples. In addition, the characteristic value in each example and the evaluation result were calculated | required according to the following procedures.

(1) Gel permeation chromatography (GPC)
The GPC measurement of the polyorganosiloxane was performed under the following conditions.
Test equipment: TOSOH HLC 8220
Measurement conditions: TOSOH TSK-GEL GHXL-L, G4000HXL, G2000HXL
Solvent: tetrahydrofuran (THF)
Column temperature: 40 ° C
Flow rate: 1.0 ml / min Detector: RI
Injection concentration: 0.2 w / v%
Injection volume: 0.1ml
Standard polystyrene made by Tosoh Corporation was used for the production of the calibration curve.
The molecular weight distribution of polyorganosiloxane in polycarbonate-polydimethylsiloxane (PC-PDMS) was measured as follows. The obtained PC-PDMS copolymer flakes (3.9 g) were added to methylene chloride to form a 10% by mass solution, and the flakes were completely dissolved. While stirring with a magnetic stirrer, 30 ml of a mixed aqueous solution of 48 mass% sodium hydroxide aqueous solution and methanol 1: 9 (volume ratio) was added and stirred for 3 hours. Thereafter, 30 ml of methylene chloride was added, and the precipitated crystals (main component: bisphenol A) were filtered with fold filter paper, and the crystals were washed with methylene chloride. The methylene chloride solution in the filtrate was washed twice with 15% by volume of 0.03 mol / L NaOH aqueous solution, then with 15% by volume of 0.2N HCl, and then with 15% by volume of pure water. The obtained methylene chloride solution was dried with a dryer, and the resulting viscous liquid (main component: PDMS) was measured by GPC to confirm that the molecular weight distribution was the same as that of the polyorganosiloxane used. .

  The differential molecular weight distribution curve can be obtained by the following method. First, a time curve (elution curve) of the intensity distribution detected by the RI detector was used as a molecular weight distribution curve with respect to a logarithmic value of the molecular weight (log (M)) using a calibration curve. Next, after obtaining an integral molecular weight distribution curve with respect to log (M) when the total area of the distribution curve is 100%, the integral molecular weight distribution curve is differentiated with log (M) to obtain log (M). A differential molecular weight distribution curve can be obtained. In addition, a series of operations until obtaining the differential molecular weight distribution curve can be usually performed using analysis software built in the GPC measurement apparatus.

(2) Polydimethylsiloxane content It was calculated by the integral value ratio of methyl groups of polydimethylsiloxane by NMR measurement.

(3) Viscosity average molecular weight of polycarbonate-polyorganosiloxane copolymer Viscosity average molecular weight (Mv) was determined by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer. Was calculated by the following formula (Schnell formula).
[Η] = 1.23 × 10 ⁻⁵ × Mv ^0.83

<Polycarbonate oligomer>
As the polycarbonate oligomer, the concentration was 318 g / L, the chloroformate group concentration was 0.75 mol / L, the weight average molecular weight (Mw) was 3,100, and the end group molar fraction determined from NMR was pt-butylphenol (PTBP): A methylene chloride solution of a polycarbonate oligomer of OH: chloroformate (CF) = 3.3: 7.7: 89.0 was used as a raw material.
The weight average molecular weight (Mw) is GPC [column: TOSOH TSK-GEL MULTIPORE HXL-M (2) + Shodex KF801 (1)] using tetrahydrofuran as a developing solvent, temperature 40 ° C., flow rate 1.0 ml / min. , Detector: RI], and measured as a standard polystyrene equivalent molecular weight (weight average molecular weight: Mw).

Example 1
In a 50 L tank reactor equipped with a baffle plate, paddle type stirring blade and cooling jacket, 15 L of the above polycarbonate oligomer solution of raw material, 8.3 L of methylene chloride, [average chain length n = 36; log (M) 2.5 The value obtained by integrating the dw / dlog (M) value in the range of ˜3.1 is compared to the value obtained by integrating the dw / dlog (M) value in the entire range of log (M) (hereinafter, log in the examples). (M) may be referred to as a ratio of 2.5 to 3.1) 7.6%; allylphenol terminal-modified poly having a log (M) of 3.6] with a maximum value of dw / dlog (M) Charge 393 g of dimethylsiloxane (PDMS) and 5.8 mL of triethylamine, add 1496 g of a 6.4% by mass aqueous sodium hydroxide solution with stirring, and add polycarbonate oligomer and allylphenol for 10 minutes. The reaction was conducted in Le terminal-modified PDMS.
To this polymerization solution, a methylene chloride solution of pt-butylphenol (PTBP) (70 g of PTBP dissolved in 2.0 L of methylene chloride), an aqueous solution of sodium hydroxide of BPA (648 g of NaOH and 2.0 g of sodium dithionite) A solution prepared by dissolving 1099 g of BPA in an aqueous solution dissolved in 9.5 L of water) was added, and the polymerization reaction was carried out for 50 minutes.
For dilution, 10 L of methylene chloride was added and stirred for 10 minutes, and then the organic phase was separated into an organic phase containing polycarbonate and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.
The methylene chloride solution of PC-PDMS thus obtained was washed successively with 15% by volume of 0.03 mol / L NaOH aqueous solution and 0.2N hydrochloric acid, and then the electric conductivity in the aqueous phase after washing. Washing with pure water was repeated until the value became 1 mS / m or less.
The methylene chloride solution of polycarbonate obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 120 ° C. under reduced pressure. The amount of PDMS was 6.0% by mass, the viscosity number measured according to ISO 1628-4 (1999) was 46.9, and the viscosity average molecular weight Mv = 17400.
100 parts by mass of the obtained PC-PDMS copolymer flakes and 0.1 part by mass of IRGAFOS168 (trade name: manufactured by BASF) as an antioxidant are mixed and supplied to a vent type single screw extruder, and the resin temperature Melt kneading was performed at 280 ° C. to obtain a pellet sample for evaluation. After this pellet sample for evaluation was dried at 120 ° C. for 8 hours, using an injection molding machine, a test piece for injection molding and performing each test at a molding resin temperature of 280 ° C. and a mold temperature of 80 ° C. The following tests were made.
Moreover, it confirmed that it was the same molecular weight distribution as used PDMS by GPC measurement of PDMS in PC-PDMS.

(1) Tensile properties: breaking strength, breaking elongation Using the test piece having a thickness of 3.2 mm obtained in Example 1, the breaking strength and breaking elongation were measured under conditions of 50 mm / min in accordance with ASTM D638. did. It shows that a tensile characteristic is so favorable that a numerical value is large.
(2) Flexural properties: flexural strength, flexural modulus Using the test piece having a wall thickness of 4.0 mm obtained in Example 1, the flexural strength and flexural elasticity under the condition of 2 mm / min according to ISO178. The rate was measured. It shows that a bending characteristic is so favorable that a numerical value is large.
(3) Deflection temperature under load (HDT)
Using a test piece having a thickness of 3.2 mm obtained in Example 1, measurement was performed at a load of 1.83 MPa in accordance with ASTM D648.
(4) Total light transmittance and haze value For a test piece having a thickness of 2 mm, the total light transmittance was measured three times based on ISO13468, and the haze value was measured three times based on ISO14782, and the average was obtained for each. It was. The results are shown in Table 1.
(5) Measurement of YI value Using a spectrophotometer "U-4100" (manufactured by Hitachi High-Technologies Corporation), a YI value was measured for a test piece having a thickness of 2 mm under the conditions of a C light source and a 2-degree visual field.
(6) Izod impact strength Using test pieces with a thickness of 3.2 mm (about 1/8 inch) produced by an injection molding machine, in accordance with ASTM standard D-256, at measurement temperatures of 23 ° C. and −20 ° C. The notched Izod impact strength was measured. The results are shown in Table 1.
Moreover, also about Examples 2-3 mentioned later, the test piece was similarly created using the flakes of the PC-PDMS copolymer obtained in each Example, and it measured about said (1)-(5). The results are shown together in Table 1.

Example 2
The allylphenol-end-modified PDMS used in Example 1 is [average chain length n = 40; log (M) 2.5 to 3.1 is 7.2%; dw / dlog (M) is the maximum value. This was performed in the same manner as in Example 1 except that the allylphenol-terminated PDMS having a log (M) of 3.6] was changed. The PDMS amount of the obtained flakes was 6.0% by mass, the viscosity number measured according to ISO 1628-4 (1999) was 46.2, and the viscosity average molecular weight Mv = 17100. The results are shown in Table 1.

Comparative Example 1
In the allylphenol terminal-modified PDMS used in Example 1, the average chain length n = 37, the ratio of log (M) 2.5 to 3.1 is 14.8%, and dw / dlog (M) takes the maximum value. The same procedure as in Example 1 was conducted except that the log (M) was changed to an allylphenol-end-modified PDMS having a log (M) of 3.6. The PDMS amount of the obtained flakes was 6.0% by mass, the viscosity number measured according to ISO 1628-4 (1999) was 47.4, and the viscosity average molecular weight was 17700. Moreover, the test piece was created similarly to Example 1 using the obtained PC-PDMS copolymer flakes, and (1) to (5) were measured in the same manner as in Example 1. The results are shown together in Table 1. Moreover, the test piece was created similarly to Example 1 using the obtained PC-PDMS copolymer flake also about the comparative example 2 mentioned later, and the measurement about (1)-(5) was performed. The results are shown together in Table 1.

Comparative Example 2
The average chain length n = 40, the ratio of log (M) 2.5 to 3.1 is 14.6%, and dw / dlog (M) takes the maximum value for the allylphenol-terminated PDMS used in Comparative Example 1. The same procedure as in Comparative Example 1 was conducted except that the log (M) was changed to an allylphenol-end-modified PDMS with 3.7. The PDMS amount of the obtained flakes was 6.0% by mass, the viscosity number measured according to ISO 1628-4 (1999) was 47.3, and the viscosity average molecular weight was 17,600.

As is clear from the table, in Examples 1 to 3 using PDMS in which the ratio of components having a log (M) of 2.5 to 3.1 in the molecular weight distribution of PDMS is 10% or less of the entire PDMS, An effect of excellent transparency and low yellowness (YI) can be obtained without deteriorating mechanical properties. On the other hand, in Comparative Examples 1 and 2 in which the proportion of the component having a log (M) of 2.5 to 3.1 exceeds 10% of the whole PDMS, the yellowness (YI) is significantly higher than the YI value of the examples. It is high and it turns out that yellowishness is not improved.
FIG. 1 is a graph showing differential distribution curves obtained in Example 1 and Comparative Example 1, and is a value obtained by integrating dw / dlog (M) values in a range of 2.5 ≦ log (M) ≦ 3.1. Is in the range of 2.5 ≦ log (M) ≦ 3.1 in the first embodiment in which dw / dlog (M) value is 0 to 10% with respect to the integrated value of dw / dlog (M) in the entire range of log (M) The curve rises sharply, whereas the integrated value of dw / dlog (M) in the range of 2.5 ≦ log (M) ≦ 3.1 is dw / d in the entire range of log (M). In Comparative Example 1, which exceeds 10% of the value obtained by integrating the dlog (M) value, it can be seen that the rise of the curve in the range of 2.5 ≦ log (M) ≦ 3.1 is gradual.

  According to the present invention, the molecular weight distribution of the polyorganosiloxane in the polycarbonate-polyorganosiloxane copolymer is controlled, and the chain length distribution is controlled, thereby reducing the mechanical strength and improving the transparency. A polycarbonate-polyorganosiloxane copolymer with little taste can be obtained.

Claims (6)

  Obtained from measurement by gel permeation chromatography using polystyrene as a conversion standard, the horizontal axis is a logarithmic value log (M) of molecular weight M, and the vertical axis is a derivative of concentration fraction w by logarithmic value log (M) of molecular weight. In the differential molecular weight distribution curve of dw / dlog (M), the integrated value of dw / dlog (M) in the range of 2.5 ≦ log (M) ≦ 3.1 is the entire range of log (M) A process for producing a polycarbonate-polyorganosiloxane copolymer using, as a raw material, a polyorganosiloxane that is 0 to 10% with respect to a value obtained by integrating dw / dlog (M) values.   The polycarbonate-poly of claim 1, wherein in the differential molecular weight distribution curve of the raw material polyorganosiloxane, the value of dw / dlog (M) is maximum in the range of 3.3≤log (M) ≤3.9. A method for producing an organosiloxane copolymer. The method for producing a polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein the polyorganosiloxane has a structure represented by the following general formula (1) or (2).

[Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Y ^{is, -R 5 O -, - R} 5 COO -, - R 5 NH -, - R 5 NHR 6 -, - COO -, - S -, - R 5 COO-R 7 -O-, or -R ⁵ O—R ⁸ —O— is shown. R ⁵ represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, an arylene group, or a diarylene group. R ⁶ represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R ⁷ represents a diarylene group. R ⁸ represents a linear, branched or cyclic alkylene group, or a diarylene group. Z represents a hydrogen atom or a halogen atom. β represents a divalent group derived from a diisocyanate compound or a divalent group derived from dicarboxylic acid or a halide of dicarboxylic acid. The sum of p and q is n, and n indicates the average number of repetitions. ]   The manufacturing method of the polycarbonate polyorganosiloxane copolymer as described in any one of Claims 1-3 which has the process of making the said polyorganosiloxane and a polycarbonate oligomer react in an organic solvent.   The manufacturing method of the polycarbonate polyorganosiloxane copolymer of Claim 4 which has the process of further adding dihydric phenol.   The manufacturing method of the polycarbonate polyorganosiloxane copolymer as described in any one of Claims 1-5 whose viscosity average molecular weights of the obtained polycarbonate polyorganosiloxane copolymer are 12,000-40,000.