JP2012246390A - Polycarbonate-polydiorganosiloxane copolymer resin, and method for producing the same - Google Patents

Abstract

Disclosed is a polycarbonate-polydiorganosiloxane copolymer resin excellent in impact resistance, heat resistance and appearance, and a method for producing the same.
A polycarbonate-polydiorganosiloxane copolymer resin having a specific structure, the amount of n-hexane extracted component, and the ratio of the amount of carbonated hydroxyaryl residues and the amount of unreacted hydroxyaryl residues in the hydroxyaryl-terminated polydiorganosiloxane. Is a polycarbonate-polydiorganosiloxane copolymer resin having a specific range.
[Selection figure] None

Description

  The present invention relates to a polycarbonate-polydiorganosiloxane copolymer resin excellent in impact resistance, heat resistance and appearance, and a method for producing the same.

  Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, etc., and are therefore widely used in electrical, mechanical, automotive, medical applications and the like. However, development of a polycarbonate resin with further excellent performance is desired as the application expands. For example, for large thin-walled molded products that require flame resistance, such as copiers and printer housings, further thinning is desired. Impact resistance, fluidity, and heat resistance are higher than polycarbonate resin. There is a demand for resin materials with an excellent total balance. It is known that polycarbonate-polydiorganosiloxane copolymer resins are more excellent in flame retardancy, impact resistance and fluidity than polycarbonate resins, and are promising as resin materials that can solve the above problems.

  Patent Document 1 discloses a polycarbonate-polydiorganosiloxane copolymer resin excellent in impact resistance. Although such a copolymer resin is excellent in impact resistance, the heat resistance is greatly reduced as compared with polycarbonate, and further, there is a problem that the appearance is poor because pearly luster is generated in the molded product.

  Patent Document 2 discloses an average domain size of 20 to 45 nm in a matrix of a polycarbonate polymer obtained by mixing a first polycarbonate-polydiorganosiloxane copolymer resin and a second polycarbonate-polydiorganosiloxane copolymer resin. A resin composition in which a polydiorganosiloxane domain is embedded has been proposed. This resin composition is disclosed to have impact resistance and certain translucency. More specifically, the resin composition has translucency (defined as having a light transmission of about 25 to about 85% and a haze of less than about 104) in combination with a visual effect additive. It is disclosed that an aesthetic visual effect can be obtained, and that the impact resistance and flame retardancy are excellent, and the weld line visibility is low. However, there is no mention of the relationship between the aggregate structure of the polydiorganosiloxane domain and the heat resistance.

  Patent Document 3 discloses a polycarbonate-polydiorganosiloxane copolymer resin having an average polydiorganosiloxane domain size of 5 to 40 nm, a normalized dispersion of 40% or less, and a total light transmittance of 88% or more. . This polycarbonate-polydiorganosiloxane copolymer resin has a problem of low impact resistance at low temperatures, although it has excellent transparency due to the formation of a specific agglomerated structure and good appearance of a molded product.

WO91 / 00885 Publication JP-T-2006-523243 JP 2011-46911 A

  An object of the present invention is to provide a polycarbonate-polydiorganosiloxane copolymer resin excellent in impact resistance, heat resistance and appearance, and a method for producing the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors are a polycarbonate-polydiorganosiloxane copolymer resin having a specific structure, the amount of n-hexane extracted component, and the carbonate formation of hydroxyaryl-terminated polydiorganosiloxane. The polycarbonate-polydiorganosiloxane copolymer resin in which the ratio of the amount of hydroxyaryl residues to the amount of unreacted hydroxyaryl residues is in a specific range expresses significantly higher impact resistance and heat resistance, and further, the appearance of the molded product is good. As a result of further investigation based on this finding, the present invention has been completed. According to the present invention, the above problem is solved by the following configuration.

(Configuration 1)
It consists of a polycarbonate block represented by the following formula [1] and a polydiorganosiloxane block represented by the following formula [3], the n-hexane extract component is 0.4 to 2.5 wt%, and n-hexane. A polycarbonate-polydiorganosiloxane copolymer in which the amount C of carbonated hydroxyaryl residue of the hydroxyaryl-terminated polydiorganosiloxane contained in the extraction component and the amount of unreacted hydroxyaryl residue H of the hydroxyaryl-terminated polydiorganosiloxane satisfy the following formula: Polymerized resin.
1 ≦ C / H ≦ 50

［上記式［１］において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数３〜１４のアリール基、炭素原子数３〜１４のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ｅ及びｆは夫々１〜４の整数であり、Ｗは単結合もしくは下記式［２］で表される基からなる群より選ばれる少なくとも一つの基である。

[In the above formula [1], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 20 carbon atoms. A cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 3 to 14 carbon atoms, an aryloxy group having 3 to 14 carbon atoms, and the number of carbon atoms It represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following formula [2].

（上記式［２］においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１〜１８のアルキル基、炭素原子数３〜１４のアリール基及び炭素原子数７〜２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数３〜１４のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｇは１〜１０の整数、ｈは４〜７の整数である。）］

(In the above formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a carbon atom. Represents a group selected from the group consisting of an aryl group having 3 to 14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. An alkyl group, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 3 to 3 carbon atoms. 14 aryl groups, aryloxy groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, nitro groups, aldehyde groups, cyano groups and carbon atoms Represents a group selected from the group consisting of a boxyl group, and when there are plural groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7).

（上記式［３］において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは６０〜３００の自然数である。ＸはＣ_２〜Ｃ_８の二価脂肪族基である。）

(In the above formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms, or R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. And q is 0 or a natural number, and p + q is a natural number of 60 to 300. X is a C _{2 to} C ₈ divalent aliphatic group.)

(Configuration 2)
2. The polycarbonate-polydiorganosiloxane according to 1 above, wherein the polycarbonate-polydiorganosiloxane has an aggregate structure in which a polydiorganosiloxane domain is dispersed in a matrix of a polycarbonate polymer, the average size of the polydiorganosiloxane domain is 10 to 30 nm, and the normalized dispersion is 20% or more. Copolymer resin.

(Configuration 3)
2. A molded article comprising the polycarbonate-polydiorganosiloxane copolymer resin as described in 1 above.

(Configuration 4)
(A) By reacting dihydric phenol (I) represented by the formula [4] with phosgene in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution, chloroformate of dihydric phenol (I) and Preparing a mixed solution of chloroformate compounds comprising carbonate oligomers of dihydric phenol (I) having a terminal chloroformate group
(B) While stirring the mixed solution of step (A), the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the formula [5] is added,
(C) Polycarbonate characterized by adding a tertiary amine catalyst and interfacial polycondensation at the same time or after making the mixed solution of step (B) into a highly emulsified state having a viscosity of 1,000 cp or more -Production method of polydiorganosiloxane copolymer resin.

（式中、Ｒ^１、Ｒ^２、ｅ、ｆ及びＷは前記と同じである。）

(Wherein R ¹ , R ² , e, f and W are the same as described above.)

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、ｐ、ｑ及びＸは前記と同じである。）

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , p, q and X are the same as above).

(Configuration 5)
5. The polycarbonate-polydiorganosiloxane copolymer resin as described in 1 above, which is produced by the production method as described in 4 above.

  The molded product made of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention exhibits extremely high impact resistance and heat resistance and has a good appearance, so that the industrial effect exerted by the molded product is tremendous.

It is a graph of the small angle X-ray scattering profile and analysis result in the thickness 1.0mm part of the three-stage plate measured in Example 1, (a) is a graph of a measurement scattering profile (measurement data), (b) is then It is a graph of the analyzed particle size distribution. It is a graph of the small angle X-ray scattering profile and analysis result in the thickness of 1.0 mm part of the three-stage plate measured in Comparative Example 3, (a) is a graph of the measured scattering profile (measurement data), (b) is then It is a graph of the analyzed particle size distribution. 2 is a ¹ H-NMR spectrum of an n-hexane extract component of a copolymer resin produced in Example 2. FIG. 2 is a ¹ H-NMR spectrum of an n-hexane extract component of a copolymer resin produced in Comparative Example 2.

Details of the present invention will be described below.
(Polycarbonate-polydiorganosiloxane copolymer resin)
The polycarbonate-polydiorganosiloxane copolymer resin of the present invention comprises a dihydric phenol (I) represented by the general formula [4] and a hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula [5]. Produced by interfacial polycondensation reaction. Examples of the dihydric phenol (I) represented by the general formula [4] include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropyl) Phenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 Bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4′- Dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl Ether, 4,4′-sulfonyldiphenol, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 2,2′-dimethyl-4,4′-sulfonyldiphenol, 4,4 '-Dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'- Dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydroxyphenyl) cyclohexa 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1,3-adamantane) And diyl) diphenol and 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane.

  Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-biphenyl. (4-hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

  As the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula [5], for example, the following compound [6] is preferably used.

  The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol. It is easily produced by hydrosilylation reaction at the end of a polydiorganosiloxane chain having a polymerization degree of Of these, (2-allylphenol) -terminated polydiorganosiloxane, (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane and (2-methoxy-) are particularly preferred. 4-Allylphenol) -terminated polydimethylsiloxane is preferred.

  In order to achieve high impact resistance, heat resistance, and appearance characteristics, the degree of diorganosiloxane polymerization (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is 60 to 300. The degree of diorganosiloxane polymerization (p + q) is preferably 80 to 250, more preferably 90 to 200, and particularly preferably 100 to 148. Above the lower limit of such a suitable range, the impact resistance particularly at low temperatures is excellent, and the heat resistance is also excellent. Below the upper limit of this preferred range, the heat resistance is excellent. Further, within such a preferable range, it is easy to adjust the average size and the normalized dispersion of the polydiorganosiloxane domain to a preferable range.

The polydiorganosiloxane content in the total weight of the copolymer resin is preferably 0.1 to 20% by weight. The polydiorganosiloxane component content is more preferably 0.5 to 15% by weight, still more preferably 1 to 10% by weight. Above the lower limit of the preferable range, the impact resistance at low temperature is excellent, and below the upper limit of the preferable range, the impact resistance at normal temperature does not decrease, and pearly luster and weld lines are generated on the surface of the molded product. No appearance and excellent appearance. Such diorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by ¹ H-NMR measurement.

  In this invention, hydroxyaryl terminal polydiorganosiloxane (II) may use only 1 type, and may use 2 or more types. Further, within a range not hindering the production method of the present invention, other comonomer other than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) is 10% by weight or less based on the total weight of the copolymer resin. It can also be used in combination in the range.

(The amount of n-hexane extracted component and C / H value in polycarbonate-polydiorganosiloxane copolymer resin)
In the present invention, the n-hexane extract component is an extract component obtained by treating a polycarbonate-polydiorganosiloxane copolymer resin by the method described in the Examples, and is a compound (general formula [7] shown below). An unreacted product of a hydroxyaryl-terminated polydiorganosiloxane (II) represented by the formula, a phosgene condensate of a hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula [8], and a hydroxyaryl terminal represented by the general formula [9] And polydiorganosiloxane (II) dihydric phenol (I) condensate, dihydric phenol (I) low molecular weight oligomer).

  The weight ratio of the n-hexane extracted component is 0.4 to 2.5 wt% with respect to the total amount of the resin. The n-hexane extract component weight ratio is preferably 1.0 to 2.3 wt% with respect to the total amount of the resin. Since a low molecular weight oligomer component is also extracted as the n-hexane extraction component, the lower limit is substantially 0.4 wt%. When the n-hexane extract component weight ratio is larger than 2.5 wt%, it is not preferable because appearance defects of molded products such as pearl luster and weld lines occur.

The polycarbonate-polydiorganosiloxane copolymer resin of the present invention has a carbonated hydroxyaryl residue amount C of hydroxyaryl-terminated polydiorganosiloxane and an unreacted hydroxyaryl residue of hydroxyaryl-terminated polydiorganosiloxane contained in the n-hexane extract component. The amount H satisfies the following formula (A).
1 ≦ C / H ≦ 50 (A)

  When the hydroxyaryl-terminated polydiorganosiloxane (II) is condensed with phosgene and dihydric phenol (I), the hydroxyaryl terminal of the hydroxyaryl-terminated polydiorganosiloxane (II) becomes a carbonated hydroxyaryl residue carbonated. On the other hand, when the hydroxyaryl-terminated polydiorganosiloxane (II) is not condensed with phosgene and dihydric phenol (I), the hydroxyaryl terminal of the hydroxyaryl-terminated polydiorganosiloxane (II) remains as an unreacted hydroxyaryl residue. The general formula of the carbonated hydroxyaryl residue is shown in Formula [10], and the general formula of the unreacted hydroxyaryl residue is shown in Formula [11].

（上記式［１０］、式［１１］において、Ｘ、Ｙは原子、若しくは連続する分子鎖である。）

(In the above formula [10] and formula [11], X and Y are atoms or a continuous molecular chain.)

The relative ratio of the carbonated hydroxyaryl residue amount C of the hydroxyaryl-terminated polydiorganosiloxane contained in the n-hexane extract component to the unreacted hydroxyaryl residue amount H of the hydroxyaryl-terminated polydiorganosiloxane is determined by the ratio of the n-hexane extract component. Calculated by ¹ H-NMR measurement. Tetrachloroethane (5.95 ppm) was used as an internal standard, and the signal derived from the carbonated hydroxyaryl residue of the hydroxyaryl-terminated polydiorganosiloxane (2.73 ppm-2.63 ppm) and the unreacted hydroxyaryl-terminated polydiorganosiloxane C / H is calculated from the integration ratio of signals derived from hydroxyaryl residues (2.68 ppm-2.58 ppm).

  The C / H value is 1 or more, preferably 2 or more, more preferably 3 or more. The C / H value is 50 or less, preferably 40 or less, and more preferably 35 or less. If the C / H value is in a suitable range, occurrence of appearance defects of molded products such as pearl luster and weld lines is suppressed.

(Average size and normalized dispersion of polydiorganosiloxane domain in polycarbonate-polydiorganosiloxane copolymer resin)
The average domain size and the normalized dispersion of the polydiorganosiloxane domain of the thermoplastic resin composition molded article in the present invention are evaluated by a small angle X-ray scattering method (SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering / diffraction generated in a small-angle region where the scattering angle (2θ) is less than 10 °. In this small-angle X-ray scattering method, if there is a region of about 1 to 100 nm in which the electron density is different in a substance, the X-ray diffuse scattering is measured by the difference in the electron density. The particle diameter of the measurement object is obtained based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 ° is measured, the small-angle X-ray scattering profile is measured, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. Assuming that there is a particle size, a simulation is performed using a commercially available analysis software from the temporary particle size and the temporary particle size distribution model to obtain the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size and particle size distribution of the polydiorganosiloxane domain dispersed in the polycarbonate polymer matrix, which cannot be accurately measured by observation with a transmission electron microscope, is accurate, simple, and reproducible. It can be measured well.

  The average domain size means the number average of individual domain sizes. Normalized dispersion means a parameter in which the spread of the particle size distribution is normalized by the average size. Specifically, it is a value obtained by normalizing the dispersion of the polydiorganosiloxane domain size with the average domain size, and is represented by the following formula (1).

上記式（１）において、σはポリジオルガノシロキサンドメインサイズの標準偏差、Ｄ_ａｖは平均ドメインサイズである。

In the above formula (1), σ is the standard deviation of the polydiorganosiloxane domain size, and D _av is the average domain size.

  The terms “average domain size” and “normalized dispersion” used in connection with the present invention are measurements obtained by measuring by a small-angle X-ray scattering method using a molded article having a thickness of 1.0 mm formed by injection molding. Indicates the value. Specifically, a three-stage plate formed by injection molding (width 50 mm, length 90 mm, thickness is 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), 1.0 mm (length) from the gate side. 25 mm) and the average arithmetic roughness (Ra) of the surface is 0.03 μm), the average size and particle size of the polydiorganosiloxane domain at the intersection of 5 mm from the end of 1.0 mm thickness and 5 mm from the side. The distribution (normalized dispersion) is measured by the small angle X-ray scattering method.

  In the present invention, the polydiorganosiloxane domain means a domain mainly composed of polydiorganosiloxane dispersed in a polycarbonate matrix, and may contain other components. As described above, the polydiorganosiloxane domain is not necessarily composed of a single component because the structure is formed by phase separation from the polycarbonate polycarbonate.

  In the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, the average size of the polydiorganosiloxane domain is preferably in the range of 10 to 30 nm. The average size is more preferably 12 to 26 nm, still more preferably 14 to 22 nm, and particularly preferably 15 to 19 nm. Above the lower limit of this range, the impact resistance at low temperatures is exceptionally high and the heat resistance is also excellent. Below the upper limit of this range, pearl luster and weld lines are not generated on the surface of the molded product, and the appearance is excellent.

  In the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, the normalized dispersion of the polydiorganosiloxane domain is preferably 20 to 50%. Such normalized dispersion is more preferably 22 to 45%, still more preferably 24 to 40%, and particularly preferably 26 to 38%. Even if the average size of the polydiorganosiloxane domain is in a suitable range, if it is smaller than the lower limit of such a suitable range, good impact strength is not exhibited, and if it is larger than the upper limit of such a suitable range, molding such as pearly luster Product appearance defects are likely to occur. By having such an appropriate average domain size and its normalized dispersion, a polycarbonate-polydiorganosiloxane copolymer resin having an excellent balance of low-temperature impact resistance, heat resistance, and molded article appearance can be obtained.

(Total light transmittance)
The polycarbonate-polydiorganosiloxane copolymer resin of the present invention preferably has a total light transmittance of 88% or less in a molded product having a thickness of 2.0 mm formed by injection molding. The total light transmittance is more preferably 85% or less, still more preferably 82% or less, and particularly preferably 80% or less. Further, in a molded product having a thickness of 2.0 mm made of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, the haze is preferably 2 to 80%. Such haze is more preferably 3 to 75%, and still more preferably 4 to 70%.

(Viscosity average molecular weight of polycarbonate-polydiorganosiloxane copolymer resin)
The viscosity-average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin is preferably in the range of 5.0 × 10 ^{3 to} 5.0 × 10 ⁴ . The viscosity average molecular weight is more preferably 1.0 × 10 ^{4 to} 4.0 × 10 ⁴ , further preferably 1.5 × 10 ^{4 to} 3.5 × 10 ⁴ , and particularly preferably 1.7 × 10 ⁴ to 2. .5 × 10 ⁴ . When the viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin is less than 5.0 × 10 ³ , practical mechanical strength is difficult to obtain in many fields, and when it exceeds 5.0 × 10 ⁴ , the melt viscosity is It is high and generally requires a high molding temperature, so it tends to cause problems such as thermal degradation of the resin.

(Production method)
(Step of producing a chloroformate compound from dihydric phenol (I))
In one embodiment of the present invention, the polycarbonate-polydiorganosiloxane copolymer resin can be produced as follows. That is, first, in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution, the reaction of divalent phenol (I) with a chloroformate-forming compound such as phosgene or divalent phenol (I) chloroformate. To prepare a mixed solution of a chloroformate compound containing a dihydric phenol (I) chloroformate and / or a carbonate oligomer of a dihydric phenol (I) having a terminal chloroformate group. As the chloroformate-forming compound, phosgene is preferred.

  In producing the chloroformate compound from the dihydric phenol (I), the entire amount of the dihydric phenol (I) may be converted to the chloroformate compound at one time, or a part of the divalent phenol (I) may be used as a post-added monomer at the subsequent interface weight. You may add as a reaction raw material to a condensation reaction. The post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.

  The method for this chloroformate compound formation reaction is not particularly limited, but usually a method of carrying out in a solvent in the presence of an acid binder is preferred. Furthermore, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added, and it is preferable to add them.

  As the chloroformate-forming compound, phosgene is preferred. Moreover, when using the phosgene which is a suitable chloroformate formation compound, the method of blowing gasified phosgene into a reaction system can be employ | adopted suitably. The use ratio of the chloroformate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 1 mole of phosgene per mole of dihydric phenol (I) or a slight excess thereof. More specifically, it is preferable to use 1 to 1.4 mol, more preferably 1 to 1.3 mol, and particularly preferably 1 to 1.2 mol of phosgene per mol of dihydric phenol (I). Below this lower limit of the preferred range, unreacted hydroxyaryl-terminated polydiorganosiloxane (II) is likely to be generated, and above the upper limit of the preferred range, the amount of n-hexane extractable component increases. As a result, molded product appearance defects such as pearl luster and weld lines occur, which is not preferable.

  Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Is used.

  The use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, 2 equivalents or slightly more than 2 equivalents per mole of dihydric phenol (I) used for forming the chloroformate compound of dihydric phenol (I) (usually 1 mole corresponds to 2 equivalents). It is preferable to use an acid binder.

  As said solvent, what is necessary is just to use a solvent inert to various reaction, such as what is used for manufacture of a well-known polycarbonate, individually or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used. The concentration of the dihydric phenol (I) is preferably 400 g / L or less, more preferably 300 g / L or less, and still more preferably 250 g / L or less.

  The molar ratio of the organic solvent insoluble in water is preferably 8 moles or more, more preferably 10 moles or more, still more preferably 12 moles or more, particularly preferably 14 moles or more, per mole of dihydric phenol (I). The upper limit is not particularly limited, but 50 mol or less is sufficient from the viewpoint of the size of the apparatus and the production cost. By setting the molar ratio of the organic solvent to the dihydric phenol (I) within such a range, it becomes easier to control the average size and normalized dispersion of the polydiorganosiloxane domain to appropriate values.

The pressure in the formation reaction of the chloroformate compound is not particularly limited and may be any of normal pressure, pressurization, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50 ° C, and in many cases, heat is generated with the reaction, so it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours.
As the pH range in the formation reaction of the chloroformate compound, known interfacial reaction conditions can be used, and the pH is usually adjusted to 10 or more.

  In the present invention, after preparing a mixed solution of the chloroformate of the dihydric phenol (I) and the chloroformate compound containing the carbonate oligomer of the dihydric phenol (I) having a terminal chloroformate group in this way, While stirring the mixed solution, the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula [5] is added, and the hydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound are subjected to interfacial polycondensation. Thus, a polycarbonate-polydiorganosiloxane copolymer resin is obtained.

  In order to improve the uniform dispersibility, it is desirable that the hydroxyaryl-terminated polydiorganosiloxane (II) is mixed with a solvent and put into a mixed solution containing a terminal chloroformate compound in a solution state. The concentration of the solution is desirably diluted within a range that does not inhibit the reaction, preferably in the range of 1 to 50 wt%, more preferably in the range of 5 to 40 wt%, particularly preferably in the range of 10 to 30 wt%. is there. Such a solvent is not particularly limited, but is preferably the same as the solvent used for the above-mentioned reaction for producing the chloroformate compound, and particularly preferably methylene chloride.

  In performing the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Used. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the dihydric phenol (I) as described above is added as a post-added monomer to this reaction stage, It is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles of monovalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

  In such a polycondensation reaction, a terminal terminator or a molecular weight regulator is usually used. Examples of the terminal terminator include compounds having a monohydric phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols, aliphatic carboxylic acids Examples include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, alkyl ether phenol and the like. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, based on 100 mol of all dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. is there.

  In the interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II), a tertiary amine catalyst is added at the same time as or after the above liquid mixture is brought into a highly emulsified state. By interfacial polycondensation.

(Process of polycondensation reaction by high emulsification)
Arbitrary methods are employ | adopted as a method of making a reaction mixture into a highly emulsified state. For example, a method using a homomixer, a tank with a stirring blade, a static mixer or the like can be mentioned, and a method using a homomixer is particularly preferable because the emulsion droplets can be miniaturized. In addition, it is preferable to adjust the temperature of the reaction mixture to 25 to 35 ° C. at the time of high emulsification because the polycondensation reaction after high emulsification easily proceeds and purification after completion of the reaction becomes easy.

  The emulsion viscosity in the highly emulsified state is preferably 1,000 cp or more. More preferably, it is 1,500 cp or more, More preferably, it is 2,000 cp or more. The upper limit of the emulsion viscosity is practically 20,000 cp or less. Above the preferable lower limit of the emulsion viscosity, the interfacial polycondensation reaction proceeds efficiently because the interfacial area is large due to the miniaturization of the emulsified droplets, and the amount of unreacted hydroxyaryl residues in the hydroxyaryl-terminated polydiorganosiloxane (II) Is extremely low. That is, most of the hydroxyaryl residue of the hydroxyaryl-terminated polydiorganosiloxane (II) is a carbonated hydroxyaryl residue condensed via a carbonate bond. That is, unreacted or hydroxyaryl-terminated polydiorganosiloxane in which only one terminal is a carbonated hydroxyaryl residue is substantially lost. Thereby, since a suitable aggregate structure is formed, a polycarbonate-polydiorganosiloxane copolymer resin having excellent appearance without generating pearl luster on the surface of the molded article is provided. The viscosity of the emulsion gradually increases with the progress of the polymerization reaction without adding a tertiary amine catalyst, and may exceed 5,000 cp depending on the reaction conditions.

  The interfacial polycondensation reaction is performed by adding a tertiary amine catalyst while vigorously stirring the reaction mixture in a highly emulsified state. Stirring can be carried out by using a device such as a static mixer, an orifice mixer, a colloid mill, a flow jet mixer, an ultrasonic wave, as well as a method by rotating a stirring blade. By adding a tertiary amine catalyst, the viscosity of the emulsion gradually increases, and depending on the reaction conditions, the viscosity exceeds 5,000 cp.

As the tertiary amine catalyst, triethylamine is particularly preferably used.
If desired, phase transfer catalysts including quaternary ammonium salts can be used. The phase transfer catalyst has a function of transferring the water-soluble reactant into the organic phase across the interface, and a homogeneous reaction can occur rapidly in the organic phase. Therefore, in a reaction involving a water-soluble nucleophile, if a phase transfer catalyst is added, the nucleophile migrates as an ion pair into the organic phase, where it reacts with an organic reagent (phosgene). The cycle is completed by the cation catalyst moving back into the aqueous phase. Phase transfer catalysts are generally well known in the art, as are their production methods, and quaternary salts and quaternary resins centered on nitrogen, phosphorus, arsenic, bismuth, antimony, etc .; amine salts, ammonium salts, crowns Examples include ether, polyether, cryptand, phosphonium salt, arsonium salt, antimonium salt, bismasonium salt, α-phosphoryl sulfoxide, sulfone, sulfide and the like.

  The reaction time of such a polymerization reaction needs to be relatively long in order to prevent the generation of unreacted monomers. The upper limit is preferably 30 minutes or longer, more preferably 50 minutes or longer, and the upper limit is preferably 2 hours or shorter, more preferably 1.5 hours or shorter from the viewpoint of production efficiency.

  The polycarbonate-polydiorganosiloxane copolymer resin of the present invention can be made into a branched polycarbonate copolymer resin by using a branching agent in combination with the above dihydric phenol compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

Even if the branched polycarbonate copolymer resin is produced by the interfacial polycondensation reaction after the completion of the production reaction, the branched solution may contain a branching agent in the mixed solution during the production reaction of the chloroformate compound. It may be a method in which an agent is added. The proportion of the carbonate constituent unit derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, in the total amount of carbonate constituent units constituting the copolymer resin. Especially preferably, it is 0.05-1.0 mol%. Such a branched structure amount can be calculated by ¹ H-NMR measurement.

  The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure, but can usually be suitably performed at normal pressure or about the pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but it is usually performed in 0.5 to 10 hours.

In some cases, the obtained polycarbonate copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η _SP / C] can also be obtained as a polycarbonate copolymer resin.
The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purity) after various post-treatments such as a known separation and purification method.

(Molding)
The polycarbonate-polydiorganosiloxane copolymer resin of the present invention can be pelletized by melt kneading using an extruder such as a single screw extruder or a twin screw extruder. In producing such pellets, various flame retardants, reinforcing fillers, and additives that can be blended with the polycarbonate resin can also be blended.

  The polycarbonate-polydiorganosiloxane copolymer resin of the present invention is usually formed into various molded articles by injection molding of the pellets produced as described above. Furthermore, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without going through pellets.

  In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Further, the polycarbonate-polydiorganosiloxane copolymer resin of the present invention can be used in the form of various modified extrusion molded products, sheets, films, and the like by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the thermoplastic resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

Thereby, a molded article having excellent impact resistance, heat resistance and appearance is provided.
Furthermore, various surface treatments can be performed on the molded article made of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary polycarbonate resin is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation).

  The present invention will be described in more detail below with reference to examples, but these do not limit the present invention. Unless otherwise specified, parts in the examples are parts by weight, and% is% by weight. The evaluation was performed according to the following method.

(1) Viscosity average molecular weight (Mv)
Using a Ostwald viscometer, a specific viscosity (η _SP ) calculated by the following formula was determined from a solution of 0.7 g of a polycarbonate-polydiorganosiloxane copolymer resin dissolved in 100 ml of methylene chloride at 20 ° C.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight Mv was calculated from the obtained specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

(2) Polydiorganosiloxane component content Using JNM-AL400 manufactured by JEOL Ltd., the ¹ H-NMR spectrum of the polycarbonate-polydiorganosiloxane copolymer resin was measured, and the integral ratio of the peak derived from dihydric phenol (I) And the integration ratio of peaks derived from hydroxyaryl-terminated polydiorganosiloxane (II).

(3) Emulsion viscosity Based on JIS K7117-1, it measured using the rotor of M2 using the Toki Sangyo Co., Ltd. TVB type | mold viscosity meter (TVB-10M). The viscosity was measured at a time when the rotor was sufficiently rotated at 23 ° C. and the stress (viscosity) became constant. The measurement was performed at a rotor rotational speed of 6 rpm.

(4) Average size of polydiorganosiloxane domain and standardized dispersion After pellets were dried with hot air at 120 ° C. for 5 hours, molding temperature was 280 using an injection molding machine (manufactured by Nippon Steel Works, JSW J-75EIII). ℃, mold temperature 80 ℃, molding cycle 50 seconds width 50mm, length 90mm, thickness 3.0mm (length 20mm), 2.0mm (length 45mm), 1.0mm (length) from the gate side 25 mm), and a three-stage plate having an arithmetic average roughness (Ra) of 0.03 μm was formed.
The average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domain at the intersection of 5 mm from the end of 1.0 mm part thickness of this three-stage plate and 5 mm from the side part was measured with an X-ray diffractometer (Corporation). Measurement was performed using RINT-TTRII manufactured by Rigaku Corporation. The X-ray source was a CuKα characteristic X-ray (wavelength 0.1541841 nm), a tube voltage of 50 kV, and a tube current of 300 mA. The small angle scattering optical system was Slit: 1st 0.03 mm, HS 10 mm, SS 0.2 mm, and RS 0.1 mm. The measurement was performed by an asymmetric scanning method (2θ scanning) with an FT of 0.01 ° step, 4 sec / step, and a scanning range of 0.06-3 °. For the analysis of curve fitting, small angle scattering analysis software NANO-Solver (Ver. 3.3) manufactured by Rigaku Corporation was used. The analysis is an aggregate structure in which spherical domains of polydiorganosiloxane are dispersed in a polycarbonate polymer matrix, and assuming that there is a variation in particle size distribution, the density of the polycarbonate matrix is 1.2 g / cm ³ and the polydiorganosiloxane domain is The density was 1.1 g / cm ^3, and an isolated particle model that did not consider the interparticle interaction (interparticle interference) was used.

(5) Relative ratio (C / H) of the amount C of carbonated hydroxyaryl residue of the hydroxyaryl-terminated polydiorganosiloxane of the n-hexane extract component and the amount of unreacted hydroxyaryl residue H of the hydroxyaryl-terminated polydiorganosiloxane
In 30 ml of methylene chloride, 3.0 g of a polycarbonate-polydiorganosiloxane copolymer resin was dissolved, and 50 ml of acetone and 200 ml of n-hexane were added dropwise with stirring. The solution was concentrated with an evaporator until the solution volume became 100 ml, the precipitate was filtered, and the filtrate was collected. The precipitate was transferred to a beaker, 200 ml of hexane was added, stirred and rinsed, the precipitate was filtered, and the filtrate was collected. The filtrates were mixed, concentrated with an evaporator, and dried to measure the weight of the extracted components. Using JNM-AL400 manufactured by JEOL Ltd., the ¹ H-NMR spectrum of the extracted component was measured (deuterated solvent: chloroform, 20 ° C.). Tetrachloroethane (5.95 ppm) was used as an internal standard, and the signal derived from the carbonated hydroxyaryl residue of the hydroxyaryl-terminated polydiorganosiloxane (2.73 ppm-2.63 ppm) and the unreacted hydroxyaryl-terminated polydiorganosiloxane C / H was calculated from the integration ratio of signals derived from hydroxyaryl residues (2.68 ppm-2.58 ppm).

(6) Impact resistance evaluation (Charpy impact strength with notch)
The notched Charpy impact strength of the test piece cooled to −30 ° C. according to ISO 179 was measured. Test specimen thickness 4 mm.

(7) Heat resistance evaluation (deflection temperature under load)
Based on ISO75-1 and 2, the deflection temperature under load was measured. Load: 1.80 MPa.

(8) Appearance evaluation of molded product The surface of the three-stage plate prepared in (3) was visually observed. The case where the pearly luster exhibited a remarkably uneven color tone was rated as x, and the case where a uniform color tone was exhibited as ◯.

The hydroxyaryl-terminated polydiorganosiloxane used in Examples and Comparative Examples is as follows.
(II) -1: X-22-1822E manufactured by Shin-Etsu Chemical Co., Ltd.
(II) -2: X-22-1966 manufactured by Shin-Etsu Chemical Co., Ltd.
(II) -3: X-22-1061 manufactured by Shin-Etsu Chemical Co., Ltd.
(II) -4: X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd.

Examples 1-4, Comparative Examples 1-2
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 9.25 parts of ion-exchanged water and 1.83 parts of a 48% aqueous sodium hydroxide solution, and the dihydric phenol (I) represented by the formula [4] 2.95 parts of 2,2-bis (4-hydroxyphenyl) propane and 0.004 part of hydrosulfite were added and dissolved in 10 minutes, then 7.28 parts of methylene chloride was added, and the mixture was stirred at 15 to 25 ° C. The phosgene A part was blown in after 70 minutes. After phosgene blowing, 0.35 part of 48% aqueous sodium hydroxide, B part of methylene chloride, and methylene chloride solution of p-tert-butylphenol (PTBP) (0.055 part of PTBP dissolved in 0.50 part of methylene chloride) ) And added as a solution in which (II) -1 is dissolved in E part and 0.2 part of methylene chloride as the dihydric phenol (II) represented by the formula [5], and stirred for 10 minutes as an emulsified state by low-speed stirring. Continued. Using a homomixer (manufactured by TOKUSHU KIKA KOGYO CO. LTD, TK HOMO MIXER MARKII) for 30 seconds at 2,000 rpm, 30 seconds at 4,000 rpm, and 1 minute at 8,000 rpm for high emulsification Then, 0.002 part of triethylamine was added with stirring, and the mixture was further stirred at 28 to 33 ° C. for 50 minutes to complete the reaction. The emulsion viscosity in the highly emulsified state immediately after the homomixer treatment was Vcp. After completion of the reaction, 10.0 parts of methylene chloride was added to the product and mixed, and then stirring was stopped. The aqueous phase and the organic phase were separated to obtain a polycarbonate resin solution. This resin solution was washed with pure water and then with 0.2 mol / L hydrochloric acid, and washing with pure water was repeated until the conductivity of the aqueous phase was almost the same as that of ion-exchanged water. The washed resin solution was put into a kneader filled with warm water, and methylene chloride was evaporated while stirring to obtain a polycarbonate-polydiorganosiloxane copolymer resin granule. After dehydration, it was dried at 120 ° C. for 12 hours using a hot air circulating dryer. The dried powder was extracted with n-hexane, and C / H of the n-hexane extract component was measured. Tris (2,4-di-tert-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals Co., Ltd .: Irgaphos 168) was mixed with the dried powder to 300 ppm, and then a vented twin screw extruder (Technobel). Pellets were obtained by melt-kneading with KZW15-25MG manufactured by K.K. Extrusion conditions were a discharge rate of 2.5 kg / h, a screw rotation speed of 250 rpm, and an extrusion temperature of 260 ° C. from the first supply port to the die part. Using the obtained pellets, an injection molded product was prepared, and the average size of the polydiorganosiloxane domain and the normalized dispersion of the polydiorganosiloxane domain size were measured to evaluate the appearance of the molded product, heat resistance, and impact resistance.

  Types of hydroxyaryl-terminated polydiorganosiloxane (II) used in Examples 1-4 and Comparative Examples 1-2, diorganosiloxane polymerization degree, polydiorganosiloxane component content, phosgene amount A, methylene chloride amount B Table 1 shows the values, the value of the dihydric phenol (II) amount E, and the value of the emulsion viscosity V during high emulsification.

Comparative Example 3
The same procedure as in Example 2 was performed except that 0.06 part of triethylamine was added in a stirred state without performing the homomixer treatment.

Comparative Example 4
Linear aromatic polycarbonate resin synthesized by interfacial polycondensation from bisphenol A and p-tert-butylphenol as a terminator and phosgene (manufactured by Teijin Chemicals Ltd .: Panlite L-1225L (trade name), viscosity average) Molecular weight 19,900)
Viscosity average molecular weight, C / H value, average size of polydiorganosiloxane domain, normalized dispersion of polydiorganosiloxane domain size and molding of polycarbonate-polydiorganosiloxane copolymer resins of Examples 1-4 and Comparative Examples 1-4 Table 1 shows product appearance evaluation results, heat resistance evaluation results, and impact resistance evaluation results.

  As is apparent from the results in Table 1, the polycarbonate-polydiorganosiloxane copolymer resin of the present invention is excellent in impact resistance and heat resistance, and has a good appearance with no pearly luster. That is, the polycarbonate-polydiorganosiloxane copolymer resin of the present invention exhibits outstanding impact resistance as compared with the aromatic polycarbonate resin, and suppresses a decrease in heat resistance due to the introduction of the polydiorganosiloxane component. Overcoming appearance defects.

  A molded article made of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention exhibits excellent impact resistance and heat resistance, and has a good appearance of the molded article. Utilizing these characteristics, it can be used for a wide range of applications. As a specific example, it can be widely used in the electric / electronic equipment field and the automobile field. More specifically, various housing molded products such as electrical and electronic equipment casings, battery housings, lens barrels, memory cards, speaker cones, disk cartridges, surface light emitters, mechanical parts for micromachines, molded products with hinges, or molded for hinges Goods etc. are illustrated.

Claims (5)

It consists of a polycarbonate block represented by the following formula [1] and a polydiorganosiloxane block represented by the following formula [3], the n-hexane extract component is 0.4 to 2.5 wt%, and n-hexane. A polycarbonate-polydiorganosiloxane copolymer in which the amount C of carbonated hydroxyaryl residue of the hydroxyaryl-terminated polydiorganosiloxane contained in the extraction component and the amount of unreacted hydroxyaryl residue H of the hydroxyaryl-terminated polydiorganosiloxane satisfy the following formula: Polymerized resin.
1 ≦ C / H ≦ 50

[In the above formula [1], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 20 carbon atoms. A cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 3 to 14 carbon atoms, an aryloxy group having 3 to 14 carbon atoms, and the number of carbon atoms It represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following formula [2].

(In the above formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a carbon atom. Represents a group selected from the group consisting of an aryl group having 3 to 14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. An alkyl group, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 3 to 3 carbon atoms. 14 aryl groups, aryloxy groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, nitro groups, aldehyde groups, cyano groups and carbon atoms Represents a group selected from the group consisting of a boxyl group, and when there are plural groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7).

(In the above formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms, or R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. And q is 0 or a natural number, and p + q is a natural number of 60 to 300. X is a C _{2 to} C ₈ divalent aliphatic group.)   The polycarbonate-polydiorgano according to claim 1, which has an aggregate structure in which polydiorganosiloxane domains are dispersed in a matrix of polycarbonate polymer, the average size of the polydiorganosiloxane domains is 10 to 30 nm, and the normalized dispersion is 20% or more. Siloxane copolymer resin.   A molded article comprising the polycarbonate-polydiorganosiloxane copolymer resin according to claim 1. (A) By reacting dihydric phenol (I) represented by the formula [4] with phosgene in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution, chloroformate of dihydric phenol (I) and Preparing a mixed solution of chloroformate compounds comprising carbonate oligomers of dihydric phenol (I) having a terminal chloroformate group
(B) While stirring the mixed solution of step (A), the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the formula [5] is added,
(C) Polycarbonate characterized by adding a tertiary amine catalyst and interfacial polycondensation at the same time or after making the mixed solution of step (B) into a highly emulsified state having a viscosity of 1,000 cp or more -Production method of polydiorganosiloxane copolymer resin.

(Wherein R ¹ , R ² , e, f and W are the same as described above.)

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , p, q and X are the same as above).   The polycarbonate-polydiorganosiloxane copolymer resin of Claim 1 manufactured by the manufacturing method of Claim 4.

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