Polycarbonate-organosiloxane copolymer and resin compositions comprising the copolymer

Abstract

This invention relates to a polycarbonate-polyorganosiloxane copolymer, which is manufactured using a diol monomer (a1) and a polyorganosiloxane (a2) satisfying the following conditions. The copolymer has a polyorganosiloxane block (A-1) containing specific repeating units and a polycarbonate block (A-2) containing specific repeating units. The mixture obtained by contacting the diol monomer (a1), the polyorganosiloxane (a2), the diester, and the alkaline catalyst in the same proportion as in the manufacture of the polycarbonate-polyorganosiloxane copolymer at 100-250°C for 0.5-5 hours has a haze value of 30 or less as measured according to ISO 14782:1999 at 23°C and an optical path length of 10 mm.

Description

[Technical Field]

[0001] This invention relates to a polycarbonate-polyorganosiloxane copolymer and a resin composition comprising the copolymer. [Previous Technology]

[0002] Polycarbonate resin is an engineering plastic with excellent transparency and mechanical properties, as well as very high impact resistance. It is known that polycarbonate-organosiloxane copolymers, formed by copolymerizing polycarbonate and polysiloxane, maintain high transparency while exhibiting excellent low-temperature impact resistance and chemical resistance. Generally, known methods for manufacturing polycarbonate resin include: a method in which aromatic dihydroxy compounds react directly with phosgene (interfacial polycondensation); or a method in which aromatic dihydroxy compounds undergo transesterification with diester carbonate in a molten state (melt polymerization).

[0003] To manufacture polycarbonate-organosiloxane copolymers, interfacial polymerization is generally employed. For example, it is known that diaryl glycol compounds such as bisphenols can be reacted with phosgene in the presence of an organic solvent to generate polycarbonate oligomers with reactive chloroformate groups. Simultaneously with the generation of these polycarbonate oligomers, or sequentially, the polycarbonate oligomers, bisphenols, and polysiloxanes with hydroxyl-containing aryl groups at both ends are contacted in a dichloromethane / water medium to manufacture the copolymer (Patent Document 1). Generally, during polymerization, identical raw material components may combine to form self-coupled compounds, or some raw materials may not participate in the polymerization reaction, resulting in unreacted raw material components. These components exist in the polymer but are not uniformly incorporated into the polymer backbone, thus significantly reducing the polymer's transparency and mechanical properties. The aforementioned interfacial polymerization method rarely encounters this problem, yielding polycarbonate-organosiloxane copolymers with excellent transparency and mechanical properties.

[0004] On the other hand, interfacial polymerization requires the use of phosgene, which is highly toxic, as the carbonate source. Furthermore, the polymerization system requires dichloromethane, which has a significant environmental impact, as a solvent, and removing dichloromethane requires large-scale degassing equipment and a large amount of energy, making it economically disadvantageous. To avoid these problems, research is underway on manufacturing methods other than interfacial polymerization, such as melt polymerization, to produce polycarbonate-polyorganosiloxane copolymers.

[0005] According to Patent Document 2, a polycarbonate-organosiloxane copolymer is manufactured by melt polymerization using a bisphenol compound, an aromatic carbonate diester, a silanol-terminated polysiloxane, and a catalyst. Patent Document 3 discloses a method for manufacturing block copolymerized silicate carbonates in the presence of a carbonate-terminated polyorganosiloxane, a dihydroxy aromatic compound, a diaryl carbonate, and a carbonate transesterification catalyst. Patent Document 4 discloses a method for manufacturing a polysiloxane / polycarbonate block cocondensation product, comprising the following steps: reacting a hydroxyaryloxy-terminated dimethylsiloxane with an oligocarbonate having a specific weight average molecular weight and a specific terminal ratio (OH-terminated and aryl-terminated groups) in a molten state in the presence of a catalyst.

[0006] Patent Document 5 discloses a method for manufacturing a poly(organosiloxane) / polycarbonate block copolymer, which involves melt polymerization of a poly(organosiloxane) containing a poly(organosiloxane) component with a specific terminal structure, a Si-free bisphenol, and a diaryl carbonate in the presence of a specific catalyst. Patent Document 6 discloses a method for manufacturing modified polycarbonate resin by solid-state polymerization, which, according to Patent Document 6, uses a polysiloxane compound as a starting material. Patent Documents 7-9 disclose a method for obtaining a polysiloxane-polycarbonate block cocondensate by transesterification. [Prior Art Documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2015-189953 [Patent Document 2] US Patent No. 5,227,449 [Patent Document 3] Japanese Patent Application Publication No. Hei 8-311206 [Patent Document 4] Japanese Patent Application Publication No. Hei 10-251408 [Patent Document 5] Japanese Patent Application Publication No. 2008-248262 [Patent Document 6] Japanese Patent Application Publication No. 2008-513594 [Patent Document 7] Japanese Patent Application Publication No. 2017-505841 [Patent Document 8] Japanese Patent Application Publication No. 2016-532734 [Patent Document 9] Japanese Patent Application Publication No. 2016-532733 [Summary of the Invention]

[0008] [The problem the invention aims to solve]

[0009] Patent documents 2-7 disclose a method for manufacturing polycarbonate-polyorganosiloxane copolymers using melt polymerization, but this method is insufficient in terms of obtaining polycarbonate-polyorganosiloxane copolymers with good transparency and mechanical properties. Patent document 2 does not provide any indication of the transparency of polymers obtained using silanol-terminated siloxanes, and it is known that silanol-terminated dimethylsiloxanes tend to induce intramolecular condensation with lower molecular weights. Cyclic siloxanes generated by intramolecular condensation may remain in the obtained polycarbonate-polysiloxane copolymer, which may not only adversely affect its transparency and mechanical properties, but also cause adverse effects such as relay contact failure in applications in the electrical and electronic fields.

[0010] Although Patent Document 3 indicates an increase in the amount of polydimethylsiloxane incorporated into the polymer backbone, it does not provide any indication regarding the transparency of the resulting polymer. Furthermore, the appearance of carbonate-terminated polysiloxane in the molten state, along with other raw materials, is described as "milky white." This suggests that the carbonate-terminated polysiloxane separates from the other raw materials, and components generated by self-coupling or unreacted carbonate-terminated polysiloxane remain in the polymer. These components significantly reduce the transparency and mechanical properties of the polycarbonate-polysiloxane copolymer. In Patent Document 3, even in a manufacturing example where a large amount of siloxane is incorporated into the polymer backbone, an alkali metal catalyst (sodium hydroxide) with a mole number 10 × 10⁻⁶ relative to bisphenol A is used. When an excess amount of catalyst is used, the increase in the amount of residual catalyst component will induce hydrolysis of the polycarbonate chain. Therefore, it is speculated that the obtained polymer does not have the heat resistance or weather resistance to withstand practical conditions.

[0011] In the method disclosed in Patent Document 4, the appearance of the obtained polymer is described as "white". Therefore, it can be said that the uniformity of the polymer when the siloxane is polymerized with other raw materials is not sufficient, and there is room for improvement in its transparency or mechanical properties.

[0012] It is believed that the copolymer disclosed in Patent Document 5 has a larger domain structure, which would have an adverse effect on transparency. In Patent Document 6, the transparency of polycarbonate resin is described in general terms, but it has not been confirmed that the polycarbonate-polyorganosiloxane copolymer has high transparency. In Patent Documents 7 to 9, copolymers with polysiloxane blocks having the same structure are manufactured by transesterification (melt polymerization), but as described in Patent Document 8, the obtained resin is an opaque white powder.

[0013] Currently, although attempts have been made to obtain polycarbonate-organosiloxane copolymers using methods other than interfacial polymerization, an effective method for obtaining polycarbonate-organosiloxane copolymers with high transparency has not yet been found. The objective of this invention is to obtain polycarbonate-organosiloxane copolymers with high transparency using methods other than interfacial polymerization. [Technical Means for Solving the Problem]

[0014] Through repeated and diligent research, the inventors discovered that highly transparent polycarbonate-polyorganosiloxane copolymers can be obtained by methods other than interfacial polymerization. The polycarbonate-polyorganosiloxane copolymer of this invention has a specific structure. That is, this invention relates to the following:

[0015] [1] A polycarbonate-polyorganosiloxane copolymer, which is manufactured using a diol monomer (a1) and a polyorganosiloxane (a2) satisfying the following conditions, and having: a polyorganosiloxane block (A-1) comprising repeating units represented by the following general formula (1); and a polycarbonate block (A-2) comprising repeating units represented by the following general formula (2); The mixture obtained by contacting the diol monomer (a1), the polyorganosiloxane (a2), the diester and the alkaline catalyst in the same amount ratio as when manufacturing the above-mentioned polycarbonate-polyorganosiloxane copolymer at 100 to 250°C for 0.5 to 5 hours has a haze value of 30 or less as measured according to ISO 14782:1999 under the conditions of 23°C and an optical path length of 10 mm. [Chem. 1] [In the formula, R1 and R2 may be the same or different, and independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 12 carbon atoms, or an alkylaryl group with 1 to 10 carbon atoms in the alkyl group; a represents an integer from 2 to 500; R10 represents a divalent aliphatic hydrocarbon group with 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group with 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms, and may be substituted by substituents; the above-mentioned divalent aliphatic hydrocarbon group, the above-mentioned divalent alicyclic hydrocarbon group, or the above-mentioned divalent aromatic hydrocarbon group may contain at least one heteroatom selected from oxygen atom, nitrogen atom, and sulfur atom, and at least one halogen atom selected from fluorine atom, chlorine atom, bromine atom, and iodine atom; y represents an integer from 10 to 500] [2] The polycarbonate-polyorganosiloxane copolymer described in [1] above further includes the structural unit represented by the following general formula (3). [Chemical 2] In the formula, R3 and R4 may be the same or different, and independently represent hydrogen atom, halogen atom, alkyl with 1 to 10 carbon atoms, alkoxy with 1 to 10 carbon atoms, aryl with 6 to 12 carbon atoms or alkylaryl with 1 to 10 carbon atoms in the alkyl part; R6 represents aryl with 6 to 20 carbon atoms, alkyl with 1 to 10 carbon atoms or alkylaryl with 1 to 10 carbon atoms in the alkyl part, and may include -O-, -COO-, -CO-, -S-, -NH-, -NR111 - As a functional group; R8 can be the same or different, and can independently represent an aryl group with 6 to 20 carbon atoms, an alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, or an alkylaryl group with 1 to 10 carbon atoms in the alkyl group, and can include -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R111 represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms; z represents 0 or 1; b represents an integer from 0 to 200]

[0016] [3] The polycarbonate-polyorganosiloxane copolymer described in [1] or [2] above, wherein the polyorganosiloxane block (A-1) comprises the structure represented by the following general formula (I). [Chemical 3] In the formula, R1 to R4 may be the same or different, and independently represent hydrogen atom, halogen atom, alkyl with 1 to 10 carbons, alkoxy with 1 to 10 carbons, aryl with 6 to 12 carbons or alkylaryl with 1 to 10 carbons in the alkyl part; R5 and R6 may be the same or different, and independently represent aryl with 6 to 20 carbons, alkyl with 1 to 10 carbons or alkylaryl with 1 to 10 carbons in the alkyl part, and may contain -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R7 and R8 may be the same or different, and independently represent an aryl group with 6 to 20 carbon atoms, an alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, or an alkylaryl group with 1 to 10 carbon atoms in the alkyl group, and may include -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R111 represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms; z and z1 independently represent 0 or 1; a represents an integer from 2 to 500, and b and b1 independently represent an integer from 0 to 200. [4] The polycarbonate-polyorganosiloxane copolymer described in any of [1] to [3] above, wherein the diol monomer (a1) is selected from at least one compound from the group consisting of aromatic dihydroxy compounds represented by the following general formula (111) and aliphatic dihydroxy compounds represented by the following general formula (112).[Chemical Formula 4] [In the formula, R55 and R56 independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, respectively; X represents a single bond, an alkyl group having 1 to 8 carbon atoms, an alkylene group having 2 to 8 carbon atoms, an alkylene group having 5 to 15 carbon atoms, an alkylene group having 5 to 15 carbon atoms, an alkylene group having 5 to 15 carbon atoms, a alkylene group having 7 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-; s and t independently represent integers from 0 to 4; R100 represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, and may contain a branched structure or a cyclic structure; R100 may contain at least one heteroatom selected from oxygen, nitrogen, and sulfur atoms, and at least one halogen atom selected from fluorine, chlorine, bromine, and iodine atoms] [5] The polycarbonate-polyorganosiloxane copolymer described in any of [1] to [4] above, wherein the diol monomer (a1) is an aromatic bisphenol selected from 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-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 1,1-bis(4-hydroxyphenyl)cyclododecene, or is an aliphatic diol selected from isosorbide, cyclohexane-1,4-diethanol, tricyclodecane-diethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol and 1,4-butanediol.

[0017] [6] The polycarbonate-polyorganosiloxane copolymer described in any one of [1] to [5] above, wherein the polycarbonate block (A-2) has one or more of the repeating units selected from the group represented by the following general formulas (ai) to (av). [5] [7] The polycarbonate-polyorganosiloxane copolymer described in any one of [1] to [6] above, wherein in the above general formula (1) or general formula (I), a is an integer of 2 to 300. [8] The polycarbonate-polyorganosiloxane copolymer described in any one of [1] to [7] above, wherein the polyorganosiloxane block (A-1) having the structural unit represented by the above general formula (1) includes at least one of the group represented by the structural units represented by the following general formulas (1-1) to (1-3). [Chem. 6][In the formula, R1~R8, z, z1, a, b, b1 are as described above; 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]

[0018] [9] As described in any of [1] to [8] above, the polycarbonate-polyorganosiloxane copolymer, wherein R1 and R2 in the above general formula (1), or R1 to R4 in general formula (1) and general formula (3) all represent methyl.

[10] As described in any of [2] to [9] above, the polycarbonate-polyorganosiloxane copolymer, wherein in the above general formula (3), R6 is trimethylene (-(CH2)3-).

[11] As described in any of [2] to

[10] above, the polycarbonate-polyorganosiloxane copolymer, wherein in the above general formula (3), R8 is selected from any structure of the group consisting of dialethylene (-(CH2)2-), methyl-substituted dialethylene (-CH2CHMe-), trimethylene (-(CH2)3-), and tetramethylene (-(CH2)4-).

[12] The polycarbonate-polyorganosiloxane copolymer described in any one of [1] to

[11] above, wherein the content of the polyorganosiloxane block represented by general formula (1) or general formula (I) in the polycarbonate-polyorganosiloxane copolymer is 0.1% by mass or more and 60% by mass or less.

[13] The polycarbonate-polyorganosiloxane copolymer described in any one of [1] to

[12] above has a viscosity average molecular weight (Mv) of 5,000 or more and 50,000 or less.

[14] The polycarbonate-polyorganosiloxane copolymer described in any one of [1] to

[13] above, wherein the haze value of the 1 mm thick plate obtained by molding the polycarbonate-polyorganosiloxane copolymer is 40 or less as measured according to ISO 14782:1999.

[0019]

[15] The polycarbonate-organosiloxane copolymer described in any one of [1] to

[14] above is obtained by melt polymerization.

[16] The polycarbonate-organosiloxane copolymer described in any one of [1] to

[15] above, wherein the carbonate diester is selected from at least one compound of diaryl carbonate, dialkyl carbonate and alkylaryl carbonate.

[17] The polycarbonate-organosiloxane copolymer described in any one of [1] to

[16] above, wherein the alkaline catalyst is selected from at least one of the group consisting of alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, aryl-containing quaternary phosphonium salts and metal compounds.

[18] A polycarbonate resin composition comprising the polycarbonate-organosiloxane copolymer described in any one of [1] to

[17] above.

[19] The polycarbonate resin composition described in

[18] above further comprises an inorganic filler.

[20] The polycarbonate resin composition described in

[19] above comprises 1 to 150 parts by weight of the aforementioned inorganic filler relative to 100 parts by weight of the aforementioned polycarbonate-polyorganosiloxane copolymer.

[21] The polycarbonate resin composition described in

[19] or

[20] above, wherein the aforementioned inorganic filler is glass fiber or carbon fiber.

[22] A molded article comprising the polycarbonate resin composition described in any one of

[18] to

[21] above. [Effects of the Invention]

[0020] According to the present invention, a polycarbonate-polyorganosiloxane copolymer with high transparency can be obtained by means other than interfacial polymerization.

Implementation Method

[0021] Hereinafter, the polycarbonate-polyorganosiloxane copolymer and the polycarbonate resin composition comprising the copolymer of the present invention will be described in detail. In this specification, preferred specifications may be used arbitrarily, and combinations thereof may be preferred. In this specification, the designation "XX to YY" means "XX or more and YY or less".

[0022] <Polycarbonate-Polyorganosiloxane Copolymer> The polycarbonate-polyorganosiloxane copolymer of the present invention is characterized by having: a polyorganosiloxane block (A-1) comprising repeating units represented by the following general formula (1); and a polycarbonate block (A-2) comprising repeating units represented by the following general formula (2); and the polycarbonate-polyorganosiloxane copolymer is manufactured using a diol monomer (a1) and a polyorganosiloxane (a2) that satisfy the following conditions: the mixture obtained by contacting the above-mentioned diol monomer (a1), the above-mentioned polyorganosiloxane (a2), diester and alkaline catalyst at 100 to 250°C for 0.5 to 5 hours has a haze value of 30 or less as measured according to ISO 14782:1999 under the conditions of 23°C and an optical path length of 10 mm. [Chem. 7] [In the formula, R1 and R2 may be the same or different, and independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 12 carbon atoms, or an alkylaryl group with 1 to 10 carbon atoms in the alkyl group; a represents an integer from 2 to 500; R10 represents a divalent aliphatic hydrocarbon group with 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group with 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms, and may be substituted by substituents; the above-mentioned divalent aliphatic hydrocarbon group, the above-mentioned divalent alicyclic hydrocarbon group, or the above-mentioned divalent aromatic hydrocarbon group may contain at least one heteroatom selected from oxygen atom, nitrogen atom, and sulfur atom, and at least one halogen atom selected from fluorine atom, chlorine atom, bromine atom, and iodine atom; y represents an integer from 10 to 500]

[0023] The haze value mentioned above was measured at 23°C using a haze measuring device according to ISO 14782:1999, in a glass tank with an optical path length of 10 mm filled with the above mixture. The inventors have discovered that if the haze value of the raw material mixture after heat treatment of the polycarbonate-organosiloxane copolymer is outside the above range, the transparency of the obtained polycarbonate-organosiloxane copolymer decreases. Furthermore, it has been found that in this invention, by using diol monomers and polyorganosiloxanes with a haze value of 30 or less in the heat-treated raw material mixture as raw materials, a polycarbonate-organosiloxane copolymer with high transparency can ultimately be obtained. That is, after obtaining the raw material for manufacturing the polycarbonate-organosiloxane copolymer, a portion of the raw material is taken to obtain the above mixture, and the haze value of the mixture is measured. When the haze value of the mixture meets the above-mentioned necessary conditions, the raw material is used to manufacture the polycarbonate-organosiloxane copolymer. The obtained polycarbonate-organosiloxane copolymer exhibits high transparency. By using raw material mixtures with a haze value of 30 or less, measured under the above conditions—in other words, raw materials with good compatibility—a homogeneous system was polymerized. As a result, the reactivity rate of the organosiloxanes increased, exhibiting an effect of incorporating the organosiloxanes into the polycarbonate-organosiloxane copolymer with higher randomness; therefore, it is presumed that the transparency of the obtained polycarbonate-organosiloxane copolymer is improved. The desired haze value of the raw material mixture can be obtained, for example, by introducing substituents with high affinity for the hydroxyl groups of the glycol monomers, i.e., substituents with repeating chain structures containing polar functional groups, to the ends of the organosiloxanes. These substituents with repeating chain structures contact the glycol monomers more frequently than substituents without repeating chain structures; therefore, it is presumed that they are strongly compatible with the glycol monomers. Therefore, it is speculated that introducing the aforementioned substituents with repeating chains to the end of polyorganosiloxanes can improve the affinity between polyorganosiloxanes and diol monomers more than introducing substituents with repeating chain structures to the end.

[0024] The polycarbonate-polyorganosiloxane copolymer of the present invention is required to satisfy the following conditions: the mixture obtained by contacting the glycol monomer (a1), polyorganosiloxane (a2), diester, and alkaline catalyst at 100-250°C for 0.5-5 hours has a haze value measured at 23°C and an optical path length of 10 mm, preferably 20 or less, more preferably 10 or less, further preferably 5 or less, and further preferably 1 or less. The mixture used to measure the haze value needs to be obtained by contacting at 100-250°C for 0.5-5 hours. The temperature conditions used to obtain the mixture are preferably 150-250°C, more preferably 180-250°C, and the contact time is preferably 0.7-4 hours, more preferably 0.7-2 hours. When the temperature conditions and contact time used to obtain the mixture are within the above-mentioned range, and the mixture obtained under these conditions has the haze value specified in this invention, it is possible to obtain a polycarbonate-polyorganosiloxane copolymer with higher transparency.

[0025] <Diol Monomer (a1)> The diol monomer (a1) described above is not particularly limited as long as it has the structure represented by the following general formula (a1). Aromatic dihydroxy compounds or aliphatic dihydroxy compounds can be used as the diol monomer (a1). [Chemical 8]

[0026] In the above general formula (a1), R10 represents a divalent aliphatic hydrocarbon group with 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group with 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms, which may be substituted by substituents. The divalent aliphatic hydrocarbon group, divalent alicyclic hydrocarbon group, or divalent aromatic hydrocarbon group may contain at least one heteroatom selected from oxygen atom, nitrogen atom, and sulfur atom, and at least one halogen atom selected from fluorine atom, chlorine atom, bromine atom, and iodine atom.

[0027] Examples of divalent aliphatic hydrocarbon groups with 2 to 40 carbon atoms include: ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-heptadecyl, n-octadecyl, etc. Examples of divalent alicyclic hydrocarbon groups with 3 to 40 carbon atoms include: cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclotetradecyl, adamantyl, bicycloheptyl, bicyclodecyl, tricyclodecyl, etc.

[0028] Various divalent aromatic hydrocarbon groups with 6 to 20 carbon atoms can be listed, especially those derived from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)cycloalkanes, bis(4-hydroxyphenyl)oxides, bis(4-hydroxyphenyl)sulfides, bis(4-hydroxyphenyl) sulfides, bis(4-hydroxyphenyl) sulfides, bis(4-hydroxyphenyl) sulfides, and bis(4-hydroxyphenyl) ketones. In addition, divalent aromatic hydrocarbon groups derived from hydroquinone, resorcinol, and catechol can also be listed. These can be used individually or in combination of two or more.

[0029] Specifically, as the diol monomer (a1) mentioned above, at least one compound selected from the group consisting of aromatic dihydroxy compounds represented by the following general formula (111) and aliphatic dihydroxy compounds represented by the following general formula (112) can be cited. [Chem. 9] [In the formula, R55 and R56 independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, respectively; X represents a single bond, an alkyl group having 1 to 8 carbon atoms, an alkylene group having 2 to 8 carbon atoms, an alkylene group having 5 to 15 carbon atoms, an alkylene group having 5 to 15 carbon atoms, an alkylene group having 5 to 15 carbon atoms, a alkylene group having 7 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-; s and t independently represent integers from 0 to 4; R100 represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, and may contain a branched structure or a cyclic structure; R100 may contain at least one heteroatom selected from oxygen, nitrogen, and sulfur atoms, and at least one halogen atom selected from fluorine, chlorine, bromine, and iodine atoms]

[0030] Aromatic dihydroxy compounds represented by general formula (111) will be described in detail. In the above general formula (111), examples of halogen atoms independently represented by R55 and R56 include: fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of alkyl groups independently represented by R55 and R56 include: methyl, ethyl, n-propyl, isopropyl, various butyl groups (the term "various" refers to straight-chain and all branched groups, the same below), various pentyl groups, and various hexyl groups. Examples of alkoxy groups independently represented by R55 and R56 include those with the above-mentioned alkyl groups at the alkyl site.

[0031] Examples of the alkyl group represented by X include methylene, ethyl, trimethylene, tetramethylene, hexamethylene, etc., preferably alkyl groups having 1 to 5 carbon atoms. Examples of the alkylene group represented by X include ethylene, isopropylene, etc. Examples of the cycloalkyl group represented by X include cyclopentadiyl or cyclohexadiyl, cyclooctadiyl, etc., preferably cycloalkyl groups having 5 to 10 carbon atoms. Examples of the aryl group represented by X include phenyl, naphthyl, biphenyl, etc. Examples of the cycloalkylene group represented by X include cyclohexylene, 3,5,5-trimethylcyclohexylene, 2-adamantylene, etc., preferably cycloalkylene groups having 5 to 10 carbon atoms, more preferably cycloalkylene groups having 5 to 8 carbon atoms. Examples of the aryl group represented by X include phenyl, naphthyl, biphenyl, anthracene, etc., forming an aryl group having 6 to 14 carbon atoms. Examples of aryl groups that form aryl groups with 6 to 14 carbon atoms include phenyl, naphthyl, biphenyl, and anthracene.

[0032] s and t each independently represent an integer from 0 to 4, preferably from 0 to 2, and more preferably 0 or 1. Preferably, s and t are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or s and t are 0 and X is an alkylene group, especially an isopropylene group.

[0033] The aliphatic dihydroxy compound represented by general formula (112) is described in detail. Specifically, the divalent aliphatic hydrocarbon group represented by R100 with 2 to 40 carbons is preferably an alkyl group with 2 to 18 carbons, more preferably 2 to 10 carbons, and even more preferably 3 to 6 carbons; it is preferably an alkyl group with 4 to 20 carbons, more preferably 5 to 20 carbons; or it is a divalent oxygen- or nitrogen-containing saturated heterocyclic group with 4 to 20 carbons, more preferably 5 to 20 carbons.

[0034] Examples of alkyl groups having 2 to 18 carbon atoms include: ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-heptadecyl, n-octadecyl, etc. Examples of cycloalkyl groups having 4 to 20 carbon atoms include: cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclotetradecyl, adamantyl, bicyclohepyl, bicyclodecyl, tricyclodecyl, etc. Regarding divalent oxygen- or nitrogen-containing heterocyclic groups, examples of cycloalkyl groups containing oxygen or nitrogen atoms in their skeletons include those described above.

[0035] Examples of aliphatic dihydroxy compounds include, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 2,2-dimethylpropane-1,3-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, octaethylene glycol, dipropylene glycol, N-methyldiethanolamine, terephthalic acid, and other dihydroxy compounds having a chain aliphatic hydrocarbon group; 1,2-cyclohexanediol, 1,3- Cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, 1,4-cyclohexanediethanol, 2,6-decahydronaphthalenediol, 1,5-decahydronaphthalenediol, 2,3-decahydronaphthalenediol, 2,6-decahydronaphthalenediethanol, 1,5-decahydronaphthalenediethanol, 2,3-decahydronaphthalenediethanol, 2,3-norvalinediol, 2,5-norvalinediol, 2,3-norvalinediethanol, 2,2-bis(4-hydroxycyclohexyl)-propane, 1,3-adamantanediol, Dihydroxy compounds with alicyclic hydrocarbon groups, such as 1,3-adamantanediethanol and tricyclodecanediethanol; condensed polycyclic ether diols such as isosorbide; 3,9-bis(2-hydroxyethyl)-2,4,8,10-tetraoxellaspiro[5.5]undecane; 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxellaspiro[5.5]undecane; 3,9-bis(2-hydroxy-1,1-diethylethyl)-2,4,8,10-tetraoxellaspiro[5.5]undecane; 3,9-bis(2- Heterocyclic spirocyclic compounds such as cyclic ether diols such as hydroxy-1,1-dipropylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane and 1,4-dehydrated erythritol; cyclic acetal diols such as 2-(5-ethyl-5-hydroxymethyl-1,3-dialkyl-2-yl)-2-methylpropane-1-ol; N-heterocyclic diols such as 3,4-pyrrolidinediol, 3,4-dimethylpiperidinediol, N-ethyl-3,4-piperidinediol, and N-ethyl-3,5-piperidinediol; and S-heterocyclic diols such as deoxythiofructose.

[0036] As an aliphatic dihydroxy compound, particularly preferably, an aliphatic diol selected from isosorbide, cyclohexane-1,4-diethanol, tricyclodecane-diethanol, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol and 1,4-butanediol.

[0037] Aromatic bisphenol compounds can be cited as examples of aromatic dihydroxy compounds. Aromatic bisphenols selected from compounds represented by the following general formulas are particularly preferred examples. [Chemical 10]

[0038] Specifically, it is preferable to use: bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol C (2,2-bis(4-hydroxy-3-methylphenyl)propane), bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane), bisphenol 3MZ (1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane), bisphenol HTG (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), and bisphenol-CDE (1,1-bis(4-hydroxyphenyl)cyclododecene). Among them, if an aliphatic diol is used as the diol monomer (a1), the mixture obtained by contacting the diol monomer (a1), the above-mentioned polyorganosiloxane (a2), the above-mentioned carbonate compound and alkaline catalyst at 100-250°C for 0.5-5 hours has a lower haze value measured according to ISO 14782:1999 under the conditions of 23°C and an optical path length of 10 mm, and the total light transmittance of the finally obtained polycarbonate-polyorganosiloxane copolymer is improved, which is better.

[0039] <Polyorganosiloxane (a2)> Polyorganosiloxane (a2) preferably has the structure represented by the following general formula (a2-0). [Chemical 11] [In the formula, R1 to R4 may be the same or different, and independently represent hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, or alkylaryl groups having 1 to 10 carbon atoms in the alkyl group; R5 and R6 may be the same or different, and independently represent aryl groups having 6 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or alkylaryl groups having 1 to 10 carbon atoms in the alkyl group, and may include -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R111 represents alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 10 carbon atoms; a represents an integer from 2 to 500; R40' represents a divalent aliphatic hydrocarbon group with 2 to 380 carbon atoms, a divalent alicyclic hydrocarbon group with 3 to 380 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 380 carbon atoms, which may be substituted with substituents; the aforementioned divalent aliphatic hydrocarbon group, the aforementioned divalent alicyclic hydrocarbon group, or the aforementioned divalent aromatic hydrocarbon group may contain at least one heteroatom selected from oxygen, nitrogen, and sulfur atoms, and at least one halogen atom selected from fluorine, chlorine, bromine, and iodine atoms; R40" represents a divalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group with 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms, which may be substituted with substituents; e and u represent 0 or 1]

[0040] When R5 and R6 are alkyl groups, the number of carbon atoms is preferably 1 to 5.

[0041] As R40', it is preferred to include the following repeating chain structure, which is formed by linking at least two hydrocarbon groups including at least one hydrocarbon group selected from divalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, divalent alicyclic hydrocarbon group with 3 to 20 carbon atoms, or divalent aromatic hydrocarbon group with 6 to 20 carbon atoms, and at least one heteroatom selected from the group consisting of oxygen atom, nitrogen atom and sulfur atom. The structure comprises at least one hydrocarbon group selected from divalent aliphatic hydrocarbon groups with 1 to 20 carbon atoms, divalent alicyclic hydrocarbon groups with 3 to 20 carbon atoms, or divalent aromatic hydrocarbon groups with 6 to 20 carbon atoms, and at least one heteroatom selected from the group consisting of oxygen, nitrogen, and sulfur atoms. Preferably, it comprises at least one structure selected from the group consisting of -OH, -O-, -(C=O)-, -O(C=O)-, -O(C=O)O-, -NH2, -NRH, -NR-, -NR-(C=O)-, -N=CR-, -SH, -S-, -SS-, and -(S=O)-. R represents a hydrogen atom, a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms, which may be substituted with substituents. Examples of repeating chain structures include polyethers, polyacetals, polylactones, polyacrylates, polyesters, polycarbonates, polyketides, polysulfides, polyurethanes, polyamides, or polyimides. Preferably, at least one is selected from the group consisting of polyethers, polyacrylates, and polycarbonates, with polyethers being the most preferred. As a polyether, polyalkylene ethers are preferred, including polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol. These structures are preferred from the viewpoint of improving affinity with the glycol monomer (a1) and promoting uniform polymerization.

[0042] The polyorganosiloxane (a2) is preferably a structure having any one of the structures represented by the following general formulas (a2-1) to (a2-3). [Chemical 12] [In the formula, R1 to R4 may be the same or different, and each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 1 to 10 carbon atoms in the alkyl group; R5 and R6 may be the same or different, and each independently represents an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkylaryl group having 1 to 10 carbon atoms in the alkyl group, and may contain -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R7 and R8 may be the same or different, and each independently represents a hydrogen atom, a halogen atom ....] The structure represents an aryl group with 6 to 20 carbon atoms, an alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, or an alkylaryl group with 1 to 10 carbon atoms in the alkyl group, and may include -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R111 represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms; 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; z and z1 independently represent 0 or 1, respectively; a represents an integer from 2 to 500, and b and b1 independently represent integers from 0 to 200, respectively. The above structure is preferred from the viewpoint of improving affinity with the diol monomer (a1) and promoting uniform polymerization.

[0043] In the above general formulas (a2-0) and (a2-1) to (a2-3), examples of halogen atoms represented by R1 to R4 include: fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of alkyl groups with 1 to 10 carbon atoms represented by R1 to R4 include: methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. Examples of alkoxy groups represented by R1 to R4 include those with the alkyl group described above. Examples of aryl groups represented by R1 to R4 include: phenyl, naphthyl, etc. Examples of alkylaryl groups represented by R1 to R4 include those with the alkyl group described above and the aryl group described above. R1 to R4 are preferably hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, aryl groups with 6 to 12 carbon atoms, or aralkyl groups with 1 to 10 carbon atoms, and are more preferably methyl.

[0044] Examples of aryl groups with 6 to 20 carbon atoms represented by R5 and R6 in the above general formulas (a2-0) and (a2-1) to (a2-3) include: aryl groups with 1 to 10 carbon atoms, such as aryl groups with 1 to 20 carbon atoms, such as: methylene, diallyl, trimethylene, methyl-substituted diallyl, tetramethylene (tetramethylene may have a branched structure), etc. Examples of alkylaryl groups represented by R5 and R6 include cases where the alkyl part is the above-mentioned alkyl group and the aryl part is the above-mentioned aryl group. R5 and R6 are preferably alkyl groups with 1 to 10 carbon atoms, more preferably diallyl, methyl-substituted diallyl or trimethylene. It is especially preferred that R6 in the formula is trimethylene (-(CH2)3-).

[0045] Examples of aryl groups with 6 to 20 carbon atoms represented by R7 and R8 in the above general formulas (a2-1) to (a2-3) include: arylphenyl, arylnaphthyl, etc. Examples of alkyl groups with 1 to 10 carbon atoms represented by R7 and R8 in the above general formulas (a2-1) to (a2-3) include: methylene, diallyl, trimethylene, methyl-substituted diallyl, tetramethylene (tetramethylene may have a branched structure), etc. Examples of alkylaryl groups represented by R7 and R8 in the above general formulas (a2-1) to (a2-3) include cases where the alkyl part is the aforementioned alkyl group and the aryl part is the aforementioned aryl group. In the above general formulas (a2-1) to (a2-3), R7 and R8 are preferably alkyl groups having 1 to 10 carbon atoms, and more preferably any structure selected from the group consisting of diallyl (-(CH2)2-), methyl-substituted diallyl (-CH2CHMe-), trimethylene (-(CH2)3-), and tetramethylene (-(CH2)4-). The above structures are preferred from the viewpoint of improving affinity with the diol monomer (a1) and promoting uniform polymerization.

[0046] Preferably, in the above general formulas (a2-1) to (a2-3), R1 to R4 are all methyl, R5 and R6 are all trimethylene and R7 and R8 are all ethyl, which are polyorganosiloxanes.

[0047] 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, the divalent groups represented by the following general formulas (iii) to (vii). [Chemistry 13]

[0048] In the above general formulas (a2-0) and (a2-1) to (a2-3), 'a' represents the chain length of the polyorganosiloxane, and is an integer representing 2 to 500, preferably 2 to 300, more preferably 10 to 100, further preferably 15 to 70, and further preferably 20 to 65. If 'a' is within the above range, the polycarbonate-polyorganosiloxane copolymer has a higher total light transmittance and becomes a highly transparent copolymer, which is therefore preferred. The above structure is preferred from the viewpoint of improving the affinity with the glycol monomer (a1) and uniformly carrying out polymerization. In the above general formulas (a2-1) to (a2-3), 'b' and 'b1' independently represent 0 to 200, preferably 2 to 100, more preferably 5 to 50, and further preferably 8 to 25. If the values ​​are within the above range, the raw materials can be easily obtained, which is preferable. If b and b1 are 100 or less, the decrease in workability caused by the increase in viscosity or melting point of the polyorganosiloxane can be suppressed, which is even better. If b and b1 are 50 or less, the content of polyorganosiloxane blocks in the resin can be maintained at an amount that can maintain the property improvement effect, which is even better. In the above general formulas (a2-1) to (a2-3), z and z1 independently represent 0 or 1, preferably 0.

[0049] The polycarbonate-polyorganosiloxane copolymer of the present invention comprises: a polyorganosiloxane block (A-1), which comprises repeating units represented by the following general formula (1); and a polycarbonate block (A-2), which comprises repeating units represented by the following general formula (2). [Chemical 14] [Where R1 and R2, R10, a and y are as described above]

[0050] In the polycarbonate-polyorganosiloxane copolymer of the present invention, the polyorganosiloxane block (A-1) containing the structural unit represented by general formula (1) preferably has the structure of general formula (1A). In this case, the silicon-side bond of the structure represented by general formula (1A) is bonded to the oxygen bond of the polyorganosiloxane block represented by (1) above. [Chemical 15]

[0051] In the above general formula (1A), R1 to R4, R6 and a are as described above. R40' represents a divalent aliphatic hydrocarbon group with 2 to 380 carbon atoms, a divalent alicyclic hydrocarbon group with 3 to 380 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 380 carbon atoms, which may be substituted by substituents. The above-mentioned divalent aliphatic hydrocarbon group, the above-mentioned divalent alicyclic hydrocarbon group or the above-mentioned divalent aromatic hydrocarbon group may contain at least one heteroatom selected from oxygen atom, nitrogen atom and sulfur atom, and at least one halogen atom selected from fluorine atom, chlorine atom, bromine atom and iodine atom. R40" represents a divalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group with 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms, which may be substituted by substituents. e and u represent 0 or 1.

[0052] As R40', it is preferable to include a repeating chain structure comprising at least two hydrocarbon groups selected from divalent aliphatic hydrocarbon groups of 1 to 20 carbon atoms, divalent alicyclic hydrocarbon groups of 3 to 20 carbon atoms, or divalent aromatic hydrocarbon groups of 6 to 20 carbon atoms, and at least one heteroatom selected from the group consisting of oxygen, nitrogen, and sulfur atoms. Examples of the repeating chain structure include polyether, polyacetal, polylactone, polyacrylate, polyester, polycarbonate, polyketone, polysulfide, polyurethane, polyamide, or polyimide. Preferably, it is selected from at least one of the groups consisting of polyether, polyacrylate, and polycarbonate, with polyether being the most preferred. As the polyether, polyalkylene ether is preferred, and more preferably polyethylene glycol, polypropylene glycol, polytrimethylene glycol, or polytetramethylene glycol.

[0053] The polycarbonate-polyorganosiloxane copolymer of the present invention preferably has the structure represented by the following general formula (3). In this case, the silicon-side bond of the structure represented by general formula (3) is bonded to the oxygen bond of the polyorganosiloxane block represented by (1) above. [Chemical 16] [In the formula, R3 and R4 may be the same or different, and independently represent hydrogen atom, halogen atom, alkyl with 1 to 10 carbons, alkoxy with 1 to 10 carbons, aryl with 6 to 12 carbons or alkylaryl with 1 to 10 carbons in the alkyl part; R6 represents aryl with 6 to 20 carbons, alkyl with 1 to 10 carbons or alkylaryl with 1 to 10 carbons in the alkyl part, and may include -O-, -COO-, -CO-, -S-, -NH-, -NR111 - As a functional group; R8 can be the same or different, and can independently represent an aryl group with 6 to 20 carbon atoms, an alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, or an alkylaryl group with 1 to 10 carbon atoms in the alkyl group, and can include -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R111 represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms; z represents 0 or 1; b represents an integer from 0 to 200]

[0054] More specifically, the polyorganosiloxane block (A-1) containing the repeating unit represented by the above general formula (1) is preferably a structure containing the structure represented by the following general formula (I). [Chemical 17] [In the formula, R1 to R4 may be the same or different, and independently represent hydrogen atom, halogen atom, alkyl with 1 to 10 carbons, alkoxy with 1 to 10 carbons, aryl with 6 to 12 carbons or alkylaryl with 1 to 10 carbons in the alkyl part; R5 and R6 may be the same or different, and independently represent aryl with 6 to 20 carbons, alkyl with 1 to 10 carbons or alkylaryl with 1 to 10 carbons in the alkyl part, and may contain -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R7 and R8 may be the same or different, and independently represent an aryl group with 6 to 20 carbon atoms, an alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, or an alkylaryl group with 1 to 10 carbon atoms in the alkyl group, and may include -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R111 represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms; z and z1 independently represent 0 or 1; a represents an integer from 2 to 500, and b and b1 independently represent an integer from 0 to 200.

[0055] More specifically, the polyorganosiloxane block (A-1) containing the repeating unit represented by the above general formula (1) is preferably a unit having the units represented by the following general formulas (II) to (I-III). [Chem. 18] In the formula, R1 to R4 may be the same or different, and independently represent hydrogen atoms, halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, aryl groups with 6 to 12 carbon atoms, or alkylaryl groups with 1 to 10 carbon atoms in the alkyl group; R5 and R6 may be the same or different, and independently represent aryl groups with 6 to 20 carbon atoms, alkyl groups with 1 to 10 carbon atoms, or alkylaryl groups with 1 to 10 carbon atoms in the alkyl group, and may include -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R7 and R8 may be the same or different, and independently represent aryl groups with 6 to 20 carbon atoms, alkyl groups with 1 to 10 carbon atoms, alkylaryl groups with 1 to 10 carbon atoms, and alkylaryl groups with 1 to 10 carbon atoms. The polyorganosiloxane is a branched alkyl group having 3 to 10 carbon atoms, or an alkylaryl group having 1 to 10 carbon atoms in the alkyl group, and may contain -O-, -COO-, -CO-, -S-, -NH-, or -NR111- as functional groups; R111 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; z and z1 independently represent 0 or 1 respectively; 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; a represents an integer from 1 to 500, representing the average chain length of the polyorganosiloxane; a-1 represents the number of repetitions of the polyorganosiloxane unit, which is an integer greater than 2; b and b1 independently represent integers from 2 to 200 respectively.

[0056] Preferred examples of R1 to R4, R5 and R6, R7 and R8, z, z1, β, a, b and b1 in formulas (1), (1A), (3), (I), or (II) to (I-III) are as described above. The preferred combinations of these examples are also preferred in polycarbonate-polyorganosiloxane copolymers. More preferably, R1 and R2 in general formula (1), or R1 to R4 in general formulas (1) and (3) all represent methyl polycarbonate-polyorganosiloxane copolymers. More preferably, R6 in general formula (3) is trimethylene (-(CH2)3-) and / or R8 in general formula (3) is a polycarbonate-polyorganosiloxane copolymer selected from any one of the following structures: dimethylene (-(CH2)2-), methyl-substituted dimethylene (-CH2CHMe-), trimethylene (-(CH2)3-), and tetramethylene (-(CH2)4-).

[0057] The average chain length 'a' of the polyorganosiloxane block (A-2) in the above-mentioned polycarbonate-polyorganosiloxane copolymer represents an integer ranging from 2 to 500, preferably from 3 to 300, more preferably from 10 to 100, further preferably from 15 to 70, and further preferably from 20 to 65. If 'a' is within the above range, the polycarbonate-polyorganosiloxane copolymer has a higher total light transmittance and becomes a highly transparent copolymer, which is therefore preferred. This average chain length can be calculated by nuclear magnetic resonance (NMR) measurement.

[0058] The content of the polyorganosiloxane block represented by formula (1) in the above-mentioned polycarbonate-polyorganosiloxane copolymer is preferably 0.1 to 60% by mass, more preferably 0.5 to 50% by mass, further preferably 1 to 30% by mass, and even more preferably 3 to 20% by mass. If the content of the polyorganosiloxane block in the above-mentioned polycarbonate-polyorganosiloxane copolymer is within the above range, better impact resistance and transparency can be obtained.

[0059] The polycarbonate block (A-2) comprising the repeating unit represented by the above general formula (2) has the above-described structure derived from the diol monomer (a1). Specifically, it is preferable to have at least one of the repeating units selected from the group consisting of repeating units represented by the following general formulas (a1) to (a-xiii). In terms of transparency and synthetic advantages, it is more preferable to have at least one of the group consisting of repeating units selected from the following general formulas (a1) to (a2), and in terms of higher transparency, it is preferable to have one or more of the group consisting of repeating units selected from the group consisting of repeating units represented by formulas (a1), (a2), and (a2). [Chemical 19][Chemical 20][Chemical 21]

[0060] The polycarbonate block (A-2) represented by general formula (2) is preferably a structural unit comprising an aromatic bisphenol or an aliphatic diol, wherein the aromatic bisphenol is selected from 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-methylcyclohexane, 1,1-bis( The group consisting of 4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 1,1-bis(4-hydroxyphenyl)cyclododecene, wherein the aliphatic diols are selected from the group consisting of isosorbitol, cyclohexane-1,4-diethanol, tricyclodecane-diethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol and 1,4-butanediol.

[0061] Wherein, the polycarbonate block (A-2) containing the repeating unit represented by general formula (2) is preferably one or more of the repeating units selected from the group consisting of repeating units represented by the following general formulas (ai) to (av). [Chemical 22]

[0062] The number of units y, representing the polycarbonate block (A-2) shown in general formula (2), is preferably 20 to 200, and more preferably 40 to 100. Setting y to 20 or more suppresses the increase of low molecular weight components in the resin, which is preferable. Setting y to 40 or more improves the toughness of the resin, which is preferable. Setting y to 200 or less allows for adequate fluidity during molding, which is preferable. If y is 100 or less, the reaction mixture during manufacturing has adequate fluidity, improving productivity, which is preferable.

[0063] The polycarbonate-organosiloxane copolymer of the present invention is characterized by high transparency. Specifically, in one embodiment, the total light transmittance of the polycarbonate-organosiloxane copolymer of the present invention when made into a 1 mm sheet can be 60% or more. The total light transmittance is a value measured according to ISO 13468-1:1996. When the content of the polyorganosiloxane block represented by formula (1) in the polycarbonate-organosiloxane copolymer is less than 5% by mass and the average chain length a of the polyorganosiloxane block (A-2) in the polycarbonate-organosiloxane copolymer is less than 70, the above-mentioned total light transmittance is more preferably 70% or more, more preferably 85% or more, and more preferably 90% or more. When the content of the polyorganosiloxane block represented by formula (1) in the polycarbonate-polyorganosiloxane copolymer is 5% by mass or more, the total light transmittance is preferably 25% or more. In one embodiment, the haze value of a 1 mm plate obtained by molding the polycarbonate-polyorganosiloxane copolymer of the present invention, measured according to ISO 14782:1999, is 40 or less. This is because, as described above, the polycarbonate-polyorganosiloxane copolymer of the present invention has high transparency due to its specific structure. The haze value is more preferably 30 or less, more preferably 15 or less, more preferably 5 or less, and particularly preferably 2 or less.

[0064] The viscosity-average molecular weight of the polycarbonate-polyorganosiloxane copolymer of the present invention is preferably 5,000 or more and 50,000 or less, more preferably 12,000 or more, even more preferably 14,000 or more, particularly preferably 16,000 or more, even more preferably 30,000 or less, even more preferably 23,000 or less, and particularly preferably 21,000 or less. The viscosity-average molecular weight (Mv) is the value calculated by measuring the limiting viscosity [η] of a dichloromethane solution (concentration: g / L) at 20°C according to the following Schnell formula: [η] = 1.23 × 10⁻⁵ Mv 0.83

[0065] The polycarbonate-polyorganosiloxane copolymer of the present invention can be manufactured by polymerizing the raw material monomers using melt polymerization (transesterification). In the case of manufacturing using interfacial polymerization, for example, the method described in Japanese Patent Application Publication No. 2014-80462 can be referred to. The polycarbonate-polyorganosiloxane copolymer can be manufactured by reacting the diol monomer (a1), the polyorganosiloxane (a2), and the carbonate compound, which are raw material monomers, under an alkaline catalyst in the presence of a preferred end-capping agent.

[0066] (Dice carbonate) The acetic acid carbonate is selected from at least one compound selected from diaryl carbonate, dialkyl carbonate, and alkylaryl carbonate. The diaryl carbonate is a compound represented by the following general formula (11) or a compound represented by the following general formula (12). [Chemical 23] [In formula (11), Ar1 and Ar2 represent aryl groups, which may be the same or different from each other; in formula (12), Ar3 and Ar4 represent aryl groups, which may be the same or different from each other, and D1 represents a residue obtained by removing two hydroxyl groups from the above-mentioned aromatic dihydroxyl compound or aliphatic dihydroxyl compound]

[0067] The dialkyl carbonate compound is a compound represented by the following general formula (13) or a compound represented by the following general formula (14). [Chemical 24] [In formula (13), R21 and R22 represent alkyl groups having 1 to 20 carbon atoms or cycloalkyl groups having 4 to 20 carbon atoms, respectively, and may be the same or different from each other; in formula (14), R23 and R24 represent alkyl groups having 1 to 20 carbon atoms or cycloalkyl groups having 4 to 20 carbon atoms, respectively, and may be the same or different from each other; D2 represents a residue obtained by removing two hydroxyl groups from the above-mentioned aromatic dihydroxy compound or aliphatic dihydroxy compound]

[0068] The alkyl aryl carbonate compound is a compound represented by the following general formula (15) or a compound represented by the following general formula (16). [Chemical 25] [In formula (15), Ar5 represents an aryl group, R25 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms; in formula (16), Ar6 represents an aryl group, R26 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, and D1 represents a residue obtained by removing two hydroxyl groups from the above-mentioned aromatic dihydroxy compound or aliphatic dihydroxy compound]

[0069] Examples of diaryl carbonate compounds include: diphenyl carbonate, dimethyl carbonate, bis(chlorophenyl) carbonate, bis(m-tolyl) carbonate, dinaphthalene carbonate, bis(diphenyl) carbonate, bisphenol A diphenyl carbonate, etc. Examples of dialkyl carbonate compounds include: diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A dimethyl carbonate, etc. Examples of alkylaryl carbonate compounds include: methylphenyl carbonate, ethylphenyl carbonate, butylphenyl carbonate, cyclohexylphenyl carbonate, bisphenol A methylphenyl carbonate, etc. When manufacturing the polycarbonate-polyorganosiloxane copolymer of the present invention, one or more of the above compounds may be appropriately selected as the dicarbonate, wherein diphenyl carbonate is preferred.

[0070] (End-capping agent) When manufacturing the polycarbonate-polyorganosiloxane copolymer of the present invention, an end-capping agent may be used as needed. As the end-capping agent, any known end-capping agent used in the manufacture of polycarbonate resin may be used. Specific compounds include: phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-isopropylphenylphenol, p-nonylphenol, and p-tert-pentylphenol. These monohydric phenols may be used individually or in combination of two or more.

[0071] (Branching Agent) A branching agent may also be used when manufacturing the polycarbonate-polyorganosiloxane copolymer of the present invention. Examples of branching agents include: phloroglucinol; trimellitic acid; 1,1,1-tris(4-hydroxyphenyl)ethane; 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(4"-hydroxyphenyl)ethyl]benzene; α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene; indigobis(o-cresol), etc.

[0072] Specifically, the polycarbonate-polyorganosiloxane copolymer of the present invention can be manufactured by melt polymerization, for example, according to the following steps. A transesterification reaction is carried out on the diol monomer (a1), the polyorganosiloxane (a2), and the carbonate compound. The carbonate compound is preferably 0.9 to 1.2 moles, more preferably 0.98 to 1.02 moles, relative to the diol monomer. During the transesterification reaction, if the amount of the end-capping agent is in the range of 0.05 to 10 moles relative to the diol monomer (a1) and the polyorganosiloxane (a2), the hydroxyl ends of the obtained polycarbonate-polyorganosiloxane copolymer are capped, thus obtaining a polycarbonate resin with sufficiently excellent heat resistance and water resistance, which is preferable. The end-capping agent can be added entirely to the reaction system beforehand, or a portion can be added to the reaction system beforehand, with the remainder added as the reaction proceeds. Preferably, the antioxidant is added to the reactor along with the glycol monomer (a1), the polyorganosiloxane (a2), and the carbonate compound, and the transesterification reaction is carried out in the presence of the antioxidant.

[0073] There are no particular limitations on the reaction temperature during transesterification. It can generally be selected within the range of 100–330°C, preferably within the range of 180–300°C, and even more preferably within the range of 200–240°C. A particularly preferred method is to gradually increase the temperature to 180–300°C as the reaction proceeds. If the transesterification temperature is above 100°C, the reaction rate increases. On the other hand, if the temperature is below 330°C, no side reactions will occur, and the resulting polycarbonate-polyorganosiloxane copolymer is less prone to problems such as coloring.

[0074] The reaction pressure is set according to the vapor pressure of the monomer used or the reaction temperature. There are no particular limitations as long as the setting allows the reaction to proceed efficiently. Generally, in most cases, the pressure is set to atmospheric pressure (normal pressure) of 1 to 50 atm (760 to 38,000 torr) or under pressure in the early stage of the reaction, and under reduced pressure in the later stage of the reaction, preferably 1.33 to 1.33 × 10⁴ Pa (0.01 to 100 torr) at the end. Regarding the reaction time, it is sufficient to carry out the reaction until the target molecular weight is achieved, which is usually about 0.2 to 10 hours.

[0075] The above-mentioned transesterification reaction is usually carried out in the absence of an inert solvent. However, it may be carried out in the presence of an inert solvent in an amount of 1 to 150 parts by mass relative to 100 parts by mass of the obtained polycarbonate resin, as needed. Examples of inert solvents include: aromatic compounds such as diphenyl ether, halophenyl ether, benzophenone, polyphenylene ether, dichlorobenzene, and methylnaphthalene; and cycloalkanes such as tricyclic [5.2.1.02,6]decane, cyclooctane, and cyclodecane. It may also be carried out in an inert gas atmosphere, and examples of inert gases include: gases such as argon, carbon dioxide, nitrous oxide, and nitrogen; chlorofluorocarbons; alkanes such as ethane or propane; and various inert gases such as ethylene or propylene.

[0076] In melt polymerization, an alkaline catalyst can be used as the catalyst. Examples of alkaline catalysts include at least one selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, aryl-containing quaternary phosphonium salts, and other organic catalysts and metal compounds. These compounds can be used alone or in combination. Preferably, the following can be used as alkaline catalysts: organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals or alkaline earth metals; quaternary ammonium hydroxide; aryl-containing quaternary phosphonium salts, etc. Alkaline catalysts can be used alone or in combination of two or more.

[0077] Examples of alkali metal compounds include: sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt of bisphenol A, dipotassium salt, dicesium salt, dilithium salt, sodium salt of phenol, potassium salt, cesium salt, lithium salt, etc. Examples of alkaline earth metal compounds include: magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, barium diacetate, etc.

[0078] Examples of nitrogen-containing compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, and other quaternary ammonium hydroxides containing alkyl or aryl groups. Examples also include tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. Furthermore, examples include bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0079] Examples of metallic compounds include: zinc-aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, etc.

[0080] Specific examples of aryl-containing quaternary phosphonium salts include: tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra(chlorophenyl)phosphonium hydroxide, tetra(biphenyl)phosphonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, etc., tetra(aryl or alkyl)phosphonium hydroxides, tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, benzyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium phenolate, tetra(p-tert-butylphenyl)phosphonium diphenylphosphate, triphenylbutylphosphonium phenolate, triphenylbutylphosphonium tetraphenylborate, etc. The aryl-containing quaternary phosphonium salt is preferably combined with a nitrogen-containing organic basic compound, such as a combination of tetramethylammonium hydroxide and tetraphenylphosphonium tetraphenylborate.

[0081] The amount of alkaline catalyst used can be selected from the range of 1×10-9 to 1×10-2 mol relative to 1 mol of diol monomer, preferably 1×10-8 to 1×10-2 mol, and more preferably 1×10-7 to 1×10-3 mol.

[0082] A catalyst deactivator may also be added in the later stage of the reaction. Known catalyst deactivators are used effectively, preferably ammonium salts or phosphonium salts of sulfonic acids. More preferably, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium dodecylbenzenesulfonate, or salts of p-toluenesulfonic acid such as tetrabutylammonium p-toluenesulfonate.

[0083] As sulfonic acid esters, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate are also preferred. Among these, tetrabutylphosphonium dodecylbenzenesulfonate or butyl p-toluenesulfonate are the most preferred.

[0084] Regarding the amount of catalyst deactivator used, when using at least one polymerization catalyst selected from alkali metal compounds and alkaline earth metal compounds, it can be used at a ratio of preferably 0.5 to 50 mol per mol of the catalyst, more preferably 0.5 to 10 mol, and even more preferably 0.8 to 5 mol. It is preferable to add the catalyst deactivator and then mix in the antioxidant after the polymerization reaction is completed.

[0085] The reaction in melt polymerization can be carried out using either continuous or batch methods. The reaction apparatus used for melt polymerization can be either a longitudinally mounted reaction apparatus equipped with anchor-type stirring blades, Mack mixing stirring blades, or spiral ribbon stirring blades, or a transversely mounted reaction apparatus equipped with paddle blades, grid blades, or mirror blades. Furthermore, it can also be an extruder equipped with a screw. In the case of continuous polymerization, the above-mentioned reaction apparatus can be used in appropriate combinations.

[0086] When manufacturing the polycarbonate-polyorganosiloxane copolymer of the present invention, as described above, it is necessary to include a glycol monomer (a1), a polyorganosiloxane (a2), a carbonate compound, and the mixture obtained by contacting the glycol monomer (a1), the polyorganosiloxane (a2), the carbonate compound, and an alkaline catalyst at 100 to 250°C for 0.5 to 5 hours has a haze value of 30 or less as measured according to ISO 14782:1999 under conditions of 23°C and an optical path length of 10 mm.

[0087] The refractive index of the polycarbonate-polyorganosiloxane copolymer of the present invention is not particularly limited. For example, for light with a wavelength of 589.3 nm, it is preferably 1.430 or more and 1.590 or less, more preferably 1.450 or more and 1.570 or less, and even more preferably 1.470 or more and 1.550 or less. The difference (nF - nC) between the refractive index (nF) of the polycarbonate resin for light with a wavelength of 486.1 nm and the refractive index (nC) for light with a wavelength of 656.3 nm is preferably 0.015 or less, more preferably 0.013 or less, and even more preferably 0.011 or less.

[0088] <Polycarbonate Resin Composition> The polycarbonate resin composition of the present invention comprises the above-mentioned polycarbonate-organosiloxane copolymer (polycarbonate-organosiloxane copolymer (A)). In the polycarbonate resin composition of the present invention, known additives may be used within a range that does not impair the properties of the above-mentioned polycarbonate-organosiloxane copolymer (A).

[0089] (Additives) Known additives may be incorporated into the polycarbonate resin composition of the present invention, depending on the application or as needed. Examples of additives include: various fillers, antioxidants, heat stabilizers, plasticizers, light stabilizers, polymeric metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, mold release agents, etc. Antioxidants can inhibit resin decomposition during the manufacture or molding of the thermoplastic resin composition.

[0090] [Filler] Examples of fillers that can be incorporated into the polycarbonate resin composition of the present invention include: inorganic fillers, such as spherical fillers, plate-shaped fillers, and fibrous fillers. Examples of spherical fillers include: calcium carbonate, kaolin (aluminum silicate), silica, iron oxide, hollow white sand spheres, sericite, diatomaceous earth, calcium sulfite, calcined alumina, calcium silicate, crystalline zeolite, and amorphous zeolite. Examples of plate-shaped fillers include: talc, mica, and wollastonite. Examples of fibrous fillers include: glass fiber, carbon fiber, needle-like materials such as wollastonite, basic magnesium sulfate, potassium titanate fiber, and fibrous materials such as fibrous calcium carbonate. Glass fiber or carbon fiber are preferred among the above-mentioned inorganic fillers.

[0091] As the glass fiber, any type of glass fiber made from alkali glass, low-alkali glass, or alkali-free glass is preferably used. The form of these glass fibers is not particularly limited; for example, roving, ground fiber, or plied fiber can be used. Examples of commercially available glass fibers include CSH-3PA (manufactured by Nitto Boshoku Co., Ltd.), T511 (manufactured by Nippon Electric Glass Co., Ltd.), and MA409C (manufactured by Asahi Fiber Glass Co., Ltd.). From the viewpoint of reinforcing the resin composition, the polycarbonate-based resin composition of the present invention preferably contains glass filler.

[0092] The refractive index of the glass filler is not particularly limited, but for example, the refractive index at a wavelength of 589.3 nm is preferably 1.485 to 1.520. When the refractive index of the glass filler is within this range, the transparency of the molded article obtained using the polycarbonate-based resin composition of the present invention can be improved. Furthermore, from the viewpoint of improving the transparency of the molded article containing the polycarbonate-based resin composition, the refractive index of the glass filler at a wavelength of 589.3 nm is preferably 1.490 or higher, more preferably 1.500 or higher, more preferably 1.515 or lower, and more preferably 1.514 or lower.

[0093] [Composition Ratio] The polycarbonate resin composition of the present invention may contain, more preferably, 1 to 150 parts by weight, more preferably 11 to 100 parts by weight, further preferably 15 to 60 parts by weight, and further preferably 15 to 40 parts by weight of inorganic filler relative to 100 parts by weight of polycarbonate-polyorganosiloxane copolymer (A). By setting it within the above range, it is possible to obtain various mechanical property effects produced by inorganic filler, such as increased strength and elastic modulus, without compromising the characteristics of polycarbonate-polyorganosiloxane copolymer (A).

[0094] The method for manufacturing the polycarbonate-based resin composition of the present invention is not particularly limited as long as it includes the step of mixing polycarbonate-polyorganosiloxane copolymer and any additive. For example, it can be manufactured by using a mixer or the like to mix the polycarbonate-polyorganosiloxane copolymer and any additive, and then performing melt mixing. Melt mixing can be performed using commonly used methods, such as belt mixers, Henschel mixers, Bamboo mixers, drum mixers, single-screw extruders, twin-screw extruders, biaxial kneaders, multi-screw extruders, etc. The heating temperature during melt mixing is usually appropriately selected within the range of 150°C to 300°C, preferably around 220°C to 300°C.

[0095] [Molded Articles] The molded articles of the present invention comprise the polycarbonate-based resin composition of the present invention. These molded articles can be manufactured using injection molding, injection compression molding, extrusion molding, blow molding, pressure molding, vacuum forming, and foam molding, etc., as raw materials, from a melt-blended polycarbonate-based resin composition or granules obtained by melt-blending. Preferably, the molded articles are manufactured using injection molding or injection compression molding, particularly using the obtained granules.

[0096] The thickness of the molded article can be set arbitrarily according to the application. Especially when the transparency of the molded article is required, it is preferably 0.2 to 4.0 mm, more preferably 0.3 to 3.0 mm, and even more preferably 0.3 to 2.0 mm. If the thickness of the molded article is 0.2 mm or more, good mechanical strength can be obtained without warping. Furthermore, if the thickness of the molded article is 4.0 mm or less, high transparency can be obtained.

[0097] Depending on the requirements, a hard coating film, an anti-fog film, an antistatic film, or an anti-reflective film can be formed on the molded article, or a composite film of two or more types can be made. Among these, a hard coating film is particularly preferred in terms of good weather resistance and the ability to prevent wear and tear on the surface of the molded article over time. There are no particular limitations on the material of the hard coating film, and known materials such as acrylic hard coating agents, silicone hard coating agents, and inorganic hard coating agents can be used.

[0098] When a molded article contains glass filler, at least a portion of the glass filler is present on the outermost surface of the molded article. This increases the surface roughness of the molded article and the diffuse reflection on its surface, sometimes resulting in decreased transparency. Therefore, methods to reduce the surface roughness of the molded article include: forming a layer (surface layer) with a higher resin content on the outermost surface of the molded article to reduce its surface roughness. As a method for forming this surface layer, in injection molding, by setting the mold temperature higher than normal, the resin in contact with the mold flows more easily, thereby reducing the surface roughness of the outermost surface of the molded article. Furthermore, in compression molding, by setting the molding pressure higher than normal, the surface roughness of the outermost surface of the molded article can be reduced. By using these methods to reduce the surface roughness of the molded article, diffuse reflection on the surface of the molded article decreases, haze decreases, and the transparency of the molded article is improved.

[0099] When the content of the polyorganosiloxane block represented by formula (1) in the polycarbonate-polyorganosiloxane copolymer is less than 5% by mass and the average chain length a of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer is less than 70, the total transmittance of visible light obtained in this manner is preferably 60% or more when molded into a flat plate. The total transmittance is more preferably 70% or more, more preferably 80% or more, more preferably 85% or more, and more preferably 90% or more. When the content of the polyorganosiloxane block represented by formula (1) in the polycarbonate-polyorganosiloxane copolymer is 5% by mass or more, the total transmittance of visible light is preferably 25% or more. When the content of the polyorganosiloxane block represented by formula (1) in the polycarbonate-polyorganosiloxane copolymer is less than 5% by mass and the average chain length a of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer is less than 70, the haze when formed into a flat plate is preferably 40 or less, more preferably 30 or less, further preferably 15 or less, further preferably 5 or less, and especially preferably 2 or less. Molded articles possessing the above optical properties have excellent transparency and can therefore be used in applications requiring high transparency. Furthermore, the total transmittance of visible light can be measured according to ISO 13468-1:1996, and the haze can be measured according to ISO 14782:1999.

[0100] Molded articles of the polycarbonate resin comprising the present invention are preferably used in components requiring transparency and rigidity, and consequently, damage resistance and weather resistance, such as: 1) automotive parts such as sunroofs, rain windows, rear windows, and side windows; 2) architectural parts such as architectural glass, soundproof walls, garages, solariums, and grilles; 3) windows for railway vehicles and ships; 4) various parts for televisions, cassette recorders, camcorders, video recorders, audio-visual players, DVD (Digital Versatile Disc) players, telephones, monitors, computers, cash registers, photocopiers, printers, fax machines, etc., as well as various parts for outer panels and shells, and other electrical equipment parts; 5) mobile phones, PDAs (Personal Digital Audio Devices). Parts for precision machinery such as housings and covers for personal digital assistants, cameras, slide projectors, clocks, calculators, measuring instruments, and display machines; 6) agricultural parts for plastic greenhouses and other similar structures; 7) furniture parts such as lighting covers or baffles and interior decorative fixtures. [Example]

[0101] Hereinafter, the present invention will be described in further detail by way of embodiments, but the present invention is not limited to these embodiments.

[0102] The characteristic values ​​in each example are obtained according to the following principles.

[0103] <Quantitative Method for the Content of Polydimethylsiloxane> Example) Quantitative Method for the Content of Polydimethylsiloxane in the Polycarbonate-Polyorganosiloxane Copolymer Obtained in Example 3 NMR Apparatus: ECA-500 manufactured by JEOL RESONANCE (Co., Ltd.) Probe: TH5 and 5ϕ NMR Sample Tube Corresponding Observation Range: -5 to 15 ppm Observation Center: 5 ppm Pulse Repetition Time: 9 seconds Pulse Width: 45° Total Number of Pulses: 256 NMR Sample Tube: 5ϕ Sample Volume: 30 to 40 mg Solvent: Deuterium chloroform; Measurement temperature: Room temperature; A: Integral value of the position between the phenyl groups observed near δ 7.3–7.5; B: Integral value of the methyl group of the dimethylsiloxane group observed near δ -0.02–0.3; C: Integral value of the methine group of the ISB (isosorbitol) group observed near δ 4.8–5.3; D: Integral value of the methylene group of the PEG group observed near δ 3.3–3.8; E: Integral values ​​of the methine and methylene groups of the CHDM group observed near δ 0.8–2.0; F: Integral value of the methylene group of the terminal dimethylsiloxane group observed near δ 0.4–0.6; a = A / 2; b = B / 6; c = C / 3; d = D / 4; e = (E – F) / 10; T = a + b + c + d + ef = a / T × 100; g = b / T × 100; h = c / T × 100 i=d / T×100 j=e / T×100 TW=f×93+g×74.1+h×172+i×44+j×170 PDMS(wt%)=g×74.1 / TW×100

[0104] <Viscosity-average molecular weight of polycarbonate-polyorganosiloxane copolymer> The viscosity of a dichloromethane solution (concentration: g / L) at 20°C was measured using an Ubbelohde viscometer to determine the limiting viscosity [η]. The viscosity-average molecular weight (Mv) was then calculated using the following formula (Schnell's formula): [η] = 1.23 × 10⁻⁵ Mv 0.83

[0105] [Evaluation Test] <Total Light Transmittance of Resin Molded Articles: Tt (%), Haze Value> Using an injection molding machine (manufactured by NIGATA MACHINE TECHNO, Inc., "MD50XB", screw diameter 30 mm), under conditions of a cylinder temperature of 240°C and a mold temperature of 80°C, the evaluation particles obtained in each example and comparative example were made into a three-section plate for transparency evaluation (90 mm × 50 mm, 45 mm × 50 mm for the 3 mm thick section, 22.5 mm × 50 mm for the 2 mm thick section, and 22.5 mm × 50 mm for the 1 mm thick section). The total light transmittance was measured for the 1 mm thick section of the above three-section plate according to ISO 13468-1:1996. The haze value was measured for the 1 mm thick section of the sample according to ISO 14782:1999. Both values ​​were measured using an NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd. A lower haze value indicates higher sample transparency. Haze = Td / Tt × 100 (where Td: diffuse transmittance; Tt: total light transmittance)

[0106] <Total Light Transmittance (%) and Haze Value of Raw Material Mixture> The total light transmittance and haze value of the raw material mixture were determined using the following measuring apparatus, glass tank, and measuring method. Measuring Apparatus: NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd. Glass Tank: Optical path length: 10 mm Dimensions: External dimensions 14 mm (depth) × 40 mm (width) × 55 mm (height) Glass thickness on each side: 2 mm Before measuring the haze of the raw material mixture, the glass tank was filled with pure water for zero-point calibration. Specifically, the measured value with pure water filling the tank was calibrated to a state where the total light transmittance was 100% and the haze value was 0.00. Then, the pure water was removed from the glass tank, and the liquid mixture obtained by the following method was filled into it for measurement. The haze value at 23°C was determined according to ISO 14782:1999. Haze = Td / Tt × 100 (where Td: diffuse transmittance; Tt: total light transmittance)

[0107] Manufacturing Example 1: PDMS-1 was manufactured under a nitrogen atmosphere. In 100 g of a polyorganosiloxane with an average chain length of 24 (represented by the following formula), [Chemical 26] polyethylene glycol with an average oxyethyl chain length of 15 (represented by the following formula) was added in an amount equal to 2 moles (82.3 g) relative to the polyorganosiloxane. [Chemical 27] 455 g of isopropanol (2.5 parts relative to the total mass of the polyorganosiloxane and polyethylene glycol) was added, and the mixture was stirred thoroughly while maintaining the temperature at 80°C. Then, a toluene solution of a platinum vinylsiloxane complex was added at a mass ratio of 5 ppm (represented by the mass of platinum atoms) relative to the silicate, and the mixture was stirred for 10 hours. Isopropanol and the platinum catalyst were removed from the obtained mixture, thereby obtaining polyether-modified polyorganosiloxane PDMS-1.

[0108] Manufacturing Example 2: PDMS-2 is manufactured using α,ω-dihydroorganopolysiloxane with an average silica chain length of 61. Otherwise, it is manufactured in the same manner as in Manufacturing Example 1.

[0109] Manufacturing Example 3: PDMS-3 was manufactured using α,ω-dihydroorganopolysiloxane with an average silica chain length of 88, otherwise in the same manner as Manufacturing Example 1.

[0110] Manufacturing Example 4: The average oxygen-stretched ethyl chain length of the polyethylene glycol used was set to 12. Otherwise, it was manufactured in the same manner as in Manufacturing Example 1.

[0111] Manufacturing Example 5: PDMS-5 was manufactured under a nitrogen atmosphere by adding 2-allylphenol in a polyorganosiloxane with an average siloxane chain length of 39 (represented by the following formula) at a rate of 2 moles relative to the polyorganosiloxane. [Chemical 28] The mixture was stirred thoroughly while maintaining the temperature at 100°C. Subsequently, a toluene solution of a platinum vinylsiloxane complex was added at a mass ratio of 5 ppm (per mole) of platinum atoms relative to the siloxane, and the mixture was stirred for 10 hours. Isopropanol and the platinum catalyst were removed from the obtained mixture to obtain allylphenol-modified polyorganosiloxane PDMS-5.

[0112] Manufacturing Example 6: PDMS-6 was manufactured in the same manner as Manufacturing Example 5, except that eugenol was used instead of 2-allylphenol.

[0113] Manufacturing Example 7: PDMS-7 is manufactured in the same manner as Manufacturing Example 1, except that ethylene glycol monoallyl ether (CH2=CHCH2-O-CH2CH2-OH) is used instead of polyethylene glycol.

[0114] Manufacturing Example 8: The average chain length of the polyorganosiloxane used was set to 45, the average oxyethyl chain length of the polyethylene glycol used was set to 8, the solvent was set to toluene, and the reaction temperature was set to 110°C. Otherwise, it was manufactured in the same manner as in Manufacturing Example 1.

[0115] Manufacturing Example 9: The average oxygen-stretched ethyl chain length of the polyethylene glycol used was set to 38, the solvent was set to toluene, and the reaction temperature was set to 110°C. Otherwise, it was manufactured in the same manner as in Manufacturing Example 8.

[0116] Manufacturing Example 10: The average chain length of the polyorganosiloxane used was set to 5, the solvent was set to toluene, and the reaction temperature was set to 110°C. Otherwise, it was manufactured in the same manner as in Manufacturing Example 1.

[0117] Manufacturing Example 11: PDMS-11 was manufactured by adding 350 mL of dichloromethane to a flask under a nitrogen atmosphere, along with 21.5 g of 2,6-di-tert-butylpyridine and 21 g of trifluoromethanesulfonic anhydride. The mixture was cooled to below 15°C. 4.3 g of allyl alcohol was added dropwise to form a reaction initiator. After stirring for approximately 15 minutes, 1 L of dehydrated tetrahydrofuran was added, and the mixture was stirred at 20–23°C for 5 minutes. Then, 30 mL of deionized water was added to stop the reaction. Extraction was performed using heptane, followed by washing with 10% hydrochloric acid. After separating the liquid bath, the mixture was washed twice more with deionized water. The solvent was then removed by distillation under reduced pressure to obtain 120 g of mono-terminated allyl-modified polytetramethylene glycol (chain length of the tetramethylene glycol portion = 20), as shown in the following formula. [Chemical 29] The monoterminated allyl modified polytetramethylene glycol obtained in the above reaction was used instead of polyethylene glycol. The solvent was changed to a 1:1 (mass ratio) mixture of toluene and isopropanol. The amount of solvent used was set to three times the total volume of the polyorganosiloxane and the monoterminated allyl modified polytetramethylene glycol. The reaction temperature was controlled between 80 and 90°C. Otherwise, the manufacturing was carried out in the same manner as in Manufacturing Example 8.

[0118] Manufacturing Example 12: Manufacturing of PDMS-12 Polydimethylsiloxane (average chain number of SiMe2O units: 40) with two terminal -C3H6OC2H4OH groups and trimethylene carbonate in a nitrogen atmosphere were added to a flask. Dehydrated dichloromethane was added at a concentration of 10 wt%. 1,8-diazabicycloundecene in a 3-equivalent amount to the terminal OH groups of the polydimethylsiloxane was added as a catalyst to the obtained transparent reaction solution. The reaction was maintained at room temperature for 48 hours. Subsequently, benzoic acid was added to stop the reaction. The reaction mixture after the reaction was stopped was then precipitated in a mixed solvent containing methanol, 2-propanol and hexane (volume ratio of 10:1:10). The precipitate was then vacuum dried to obtain PDMS-12 (chain number of polytrimethylene carbonate at each end: 18).

[0119] Manufacturing Example 13: Manufacturing of PDMS-13 Under a nitrogen atmosphere, 450 mL of dichloromethane was added to a flask, followed by 45.0 g of 3-iodo-1-propanol. The mixture was cooled in an ice bath. 40.1 g of tributyldimethylchlorosilane was added, and the mixture was stirred at room temperature for 20 hours. The resulting mixture was quenched using a 5% sodium bicarbonate aqueous solution, and the product was extracted using ethyl acetate / deionized water. The obtained product was generated using a silicone column to obtain a TBS protectant of 3-iodo-1-propanol (yield 67.7 g). Under a nitrogen atmosphere, 2.9 g of the above-mentioned TBS protectant of 3-iodo-1-propanol and 270 mL of tetrahydrofuran were mixed in a flask and cooled to below -65°C. 12.5 mL of 1.6 mol / L tributyllithium (pentane solution) was added dropwise, and the mixture was stirred for 15 minutes while maintaining this state. 2.5 mL of stilbene was added dropwise, and the mixture was stirred for 30 minutes while maintaining this state. Then, 55 mL of 0.52 mol / L lithium chloride THF solution was added, and the mixture was stirred for 10 minutes. Next, 10.1 mL of methyl methacrylate was added, and the mixture was stirred for 10 minutes. Then, 3.36 mL of allyl bromide was added to quench the reaction, and the mixture was then mixed at room temperature for 12 hours. The resulting reaction mixture was concentrated under reduced pressure and then reprecipitated in a THF / heptane system. The mixture was then purified by passing it onto a silicone column and removing the solvent to obtain a TBS protecting agent of mono-terminated allyl-modified PMMA. This product was dissolved in THF, and deprotection was performed using a 2 mol / L hydrochloric acid aqueous solution. The resulting reaction mixture was then added to heptane to separate the target compound (the deprotected compound). The deprotected form was applied to a silicone column for purification and solvent removal, thereby obtaining a single-terminal allyl-modified PMMA (PMMA chain number = 20) represented by the following formula. [Chemical 30] The above-described single-terminal allyl-modified PMMA was used instead of polyethylene glycol, and the manufacturing process was otherwise carried out in the same manner as in Manufacturing Example 8.

[0120] Manufacturing Example 14: PDMS-14 was manufactured using polypropylene glycol with an average oxypropyl chain length of 15, as expressed by the following formula, instead of polyethylene glycol. Otherwise, it was manufactured in the same manner as in Manufacturing Example 1. [Chemical 31]

[0121] The PDMS-1 to PDMS-14 obtained in Manufacturing Examples 1 to 14 are shown in Table 1.

[0122] [Table 1] Table 1 Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 7 Manufacturing Example 8 Manufacturing Example 9 Manufacturing Example 10 Manufacturing Example 11 Manufacturing Example 12 Manufacturing Example 13 Manufacturing Example 14

[0123] [Others] BisP-A: Bisphenol A [Manufactured by Idemitsu Kosan Co., Ltd.] 1,4-CHDM: 1,4-Cyclohexanediethanol [Manufactured by Tokyo Chemical Industry Co., Ltd.] TCDDM: Tricyclodecanediethanol [Manufactured by OXEA GmbH] 1,3-PG: 1,3-Propanediol [Manufactured by Tokyo Chemical Industry Co., Ltd.] PEG400: Polyethylene Glycol 400 [Average molecular weight 380-420 g / mol, manufactured by Tokyo Chemical Industry Co., Ltd.] DPC: Diphenyl Carbonate [Manufactured by Mitsui Fine Chemicals Co., Ltd.] 0.01 N Sodium Hydroxide Aqueous Solution [Manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.]

[0124] Example 1 <Evaluation of the transparency of the raw material mixture after heat treatment> BisP-A (2,489.9 g) and DPC (2,500 g) (mol ratio of each raw material: BisP-A / DPC = 100 / 107), and 28.2 g of polyether-modified polyorganosiloxane PDMS-1 were added to a 10 L stainless steel reactor equipped with a double helical blade as a stirring device. After the raw material monomers were completely melted at 150°C, stirring was started at 70 rpm, and the inside of the reactor was purged with nitrogen. Then, 1.64 mL of 0.01 N sodium hydroxide as a catalyst (1.5 × 10⁻⁶ times the mol number of all diol monomers) was added, and the nitrogen pressure was maintained at 101 kPa, the same as atmospheric pressure, to raise the temperature of the mixture to 200°C and maintain this temperature for 60 minutes. Then, the contents were extracted from the valve at the bottom of the reactor to obtain a liquid and transparent raw material mixture. The liquid raw material mixture after heat treatment has a total light transmittance of 98.4% and a haze value of 0.5, showing high transparency.

[0125] <Preparation of Polycarbonate-Polyorganosiloxane (PC-POS) Copolymer> The polycarbonate-polyorganosiloxane copolymer was prepared according to the following raw materials and conditions. The raw materials used were the same as those used in the transparency evaluation described above, and the polymerization conditions were as follows. BisP-A (2,489.9 g) and DPC (2,500 g) as diol monomers (mol ratio of each raw material: BisP-A / DPC = 100 / 107), and 28.2 g of polyether-modified polyorganosiloxane PDMS-1 were added to a 10 L stainless steel reactor equipped with a stirring device, a collector for collecting distilled phenols, and a vacuum device. The monomers were completely melted at 150°C, and the inside of the reactor was purged with nitrogen. Polymerization was initiated by adding 1.64 mL of 0.01 N sodium hydroxide as a catalyst (equivalent to 1.5 × 10⁻⁶ moles of all glycol monomers). After approximately 60 minutes, the reactor temperature was raised to 180°C and the pressure reduced to 200 mmHg (26.6 kPa), maintaining these conditions until 0.2 L of phenol was distilled off. Subsequently, after approximately 60 minutes, the reactor temperature was raised to 200°C and the pressure reduced to 10 mmHg (1.3 kPa), maintaining these conditions until 1.0 L of phenol was distilled off. Then, after approximately 120 minutes, the reactor temperature was raised to 240°C, maintaining these conditions until 1.5 L of phenol was distilled off. Next, after approximately 120 minutes, the reactor temperature was adjusted to 280°C, and the pressure reduced to below 1 mmHg (0.1 kPa), allowing more than 2 L of phenol to distill off. The reaction continued until the desired stirring torque was reached. Subsequently, nitrogen pressure was applied, and 0.037 g of butyl p-toluenesulfonate (10 times the amount of NaOH in moles) was added as a deactivating agent. Irganox 1010 and Irgafos 168 were added separately at a concentration of 1,500 ppm in the obtained polymer, and the mixture was thoroughly stirred. The resin filament was then extracted from the bottom of the reactor under nitrogen pressure and cut using a granulator to obtain highly transparent granular polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0126] Example 2 Using BisP-A (1293.3 g), 1,4-CHDM (817.0 g), and DPC (2,500 g) as diol monomers (mol ratio of each raw material: BisP-A / 1,4-CHDM / DPC = 50 / 50 / 103), and 24.4 g of polyether-modified polyorganosiloxane PDMS-1, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 1. The heat-treated liquid raw material mixture exhibited high transparency, with a total light transmittance of 98.5% and a haze value of 0.5. Using BisP-A (1293.3 g), 1,4-CHDM (817.0 g), and DPC (2,500 g) as diol monomers (mol ratio of each raw material: BisP-A / 1,4-CHDM / DPC = 50 / 50 / 103), and 24.4 g of polyether-modified polyorganosiloxane PDMS-1, polymerization was carried out under the same conditions as in Example 1 to obtain a highly transparent particulate polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0127] Example 3 <Evaluation of Transparency of Raw Material Mixture After Heat Treatment> Isosorbide (ISB) (1193.8 g), 1,4-CHDM (504.9 g), DPC (2,500 g) (mol ratio of each raw material: ISB / 1,4-CHDM / DPC = 70:30:100), and 20.2 g of polyether-modified polyorganosiloxane PDMS-1 were used. The raw materials were heat-treated in the same manner as in Example 1. The liquid raw material mixture after heat treatment exhibited high transparency, with a total light transmittance of 99.5% and a haze value of 0.4.

[0128] <Preparation of PC-POS copolymer> ISB (1193.8 g), 1,4-CHDM (504.9 g), DPC (2,500 g) (mol ratio of each raw material: ISB / 1,4-CHDM / DPC=70:30:100), and 20.2 g of polyether modified polyorganosiloxane PDMS-1 as diol monomers were added to a 10 L stainless steel reactor equipped with a stirring device, a collector for collecting distilled phenols, and a depressurization device. The raw material monomers were completely melted at 100°C, and the inside of the reactor was purged with nitrogen. Polymerization was initiated by adding 1.64 mL of 0.01 N sodium hydroxide as a catalyst (equivalent to 1.5 × 10⁻⁶ moles of all diol monomers). After approximately 50–100 minutes, the reactor temperature was raised to 180°C and the pressure reduced to 200 mmHg (26.6 kPa), maintaining these conditions until 0.2 L of phenol was distilled off. Subsequently, after approximately 150 minutes, the reactor temperature was raised to 200°C and the pressure reduced to 10 mmHg (1.3 kPa), maintaining these conditions until 1.8 L of phenol was distilled off. Then, after approximately 60 minutes, the reactor temperature was adjusted to 220°C and the pressure reduced to below 1 mmHg (0.1 kPa), allowing more than 2 L of phenol to distill off. The reaction continued until the desired stirring torque was reached. Subsequently, nitrogen pressure was applied, and 0.037 g of butyl p-toluenesulfonate (10 times the amount of NaOH in moles) was added as a deactivating agent. Irganox 1010 and Irgafos 168 were added separately at a concentration of 1,500 ppm in the obtained polymer, and the mixture was thoroughly stirred. The resin filament was then extracted from the bottom of the reactor under nitrogen pressure and cut using a granulator to obtain highly transparent granular polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0129] Example 4: 20.2 g of PDMS-2 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture exhibited high transparency, with a total light transmittance of 98.4% and a haze value of 0.8. 20.2 g of PDMS-2 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 3, thereby obtaining a highly transparent particulate polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0130] Example 5: 20.2 g of PDMS-3 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture exhibited high transparency, with a total light transmittance of 98.1% and a haze value of 1.3. 20.2 g of PDMS-3 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 3, thereby obtaining a highly transparent particulate polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0131] Example 6 20.2 g of PDMS-4 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture exhibited high transparency, with a total light transmittance of 97.9% and a haze value of 0.7. 20.2 g of PDMS-4 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 3, thereby obtaining a highly transparent particulate polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0132] Example 7: 105.4 g of PDMS-1 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture exhibited high transparency, with a total light transmittance of 97.5% and a haze value of 0.9. 105.4 g of PDMS-1 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 3, thereby obtaining a highly transparent particulate polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0133] Example 8: 222.5 g of PDMS-1 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture exhibited high transparency, with a total light transmittance of 97.1% and a haze value of 1.1. 222.5 g of PDMS-1 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 3, thereby obtaining a highly transparent particulate polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0134] Example 9: Using ISB (1193.8 g), TCDDM (687.2 g), DPC (2,500 g) as diol monomers (mol ratio of each raw material: ISB / TCDDM / DPC = 70:30:100), and 22.1 g of polyether-modified polyorganosiloxane PDMS-1, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture exhibited high transparency, with a total light transmittance of 98.5% and a haze value of 0.4. Using ISB (1193.8 g), TCDDM (687.2 g), DPC (2,500 g) as diol monomers (mol ratio of ISB / TCDDM / DPC = 70:30:100), and 22.1 g of polyether-modified polyorganosiloxane PDMS-1, polymerization was carried out under the same conditions as in Example 3 to obtain a highly transparent particulate polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0135] Example 10: ISB (1193.8 g), 1,4-CHDM (420.7 g), 1,3-PG (44.4 g), DPC (2,500 g) as diol monomers (mol ratio of each raw material: ISB / 1,4-CHDM / 1,3-PG / DPC = 70:25:5:100), and 19.8 g of polyether-modified polyorganosiloxane PDMS-1 were used. The transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture exhibited high transparency, with a total light transmittance of 98.3% and a haze value of 0.4. Using ISB (1193.8 g), 1,4-CHDM (420.7 g), 1,3-PG (44.4 g), DPC (2,500 g) as diol monomers (mol ratio of raw materials: ISB / 1,4-CHDM / 1,3-PG / DPC = 70:25:5:100), and 19.8 g of polyether-modified polyorganosiloxane PDMS-1, polymerization was carried out under the same conditions as in Example 3 to obtain a highly transparent particulate polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0136] Example 11 used ISB (1193.8 g), 1,4-CHDM (504.9 g), PEG400 (93.4 g), DPC (2,500 g) as diol monomers [mol ratio of each raw material: ISB / 1,4-CHDM / PEG400 / DPC = 70:28:2:100 (the mol number of PEG400 is obtained by dividing the mass used by the average molecular weight of 400)], and 21.3 g of polyether-modified polyorganosiloxane PDMS-1. The transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture exhibited high transparency, with a total light transmittance of 98.3% and a haze value of 0.4. Using ISB (1193.8 g), 1,4-CHDM (504.9 g), PEG400 (93.4 g), DPC (2,500 g) as diol monomers [mol ratio of raw materials: ISB / 1,4-CHDM / PEG400 / DPC = 70:28:2:100 (the mol number of PEG400 is obtained by dividing the mass used by the average molecular weight of 400)], and 21.3 g of polyether-modified polyorganosiloxane PDMS-1, polymerization was carried out under the same conditions as in Example 3 to obtain a highly transparent granular polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0137] Example 12 <Evaluation of Transparency of Raw Material Mixture After Heat Treatment> Using 179.7 g of PDMS-8 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment exhibited high transparency, with a total light transmittance of 90.8% and a haze value of 2.5. <Preparation of PC-POS Copolymer> Using 179.7 g of PDMS-8 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a particulate polycarbonate-polyorganosiloxane copolymer with high transparency. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20100, a polydimethylsiloxane content of 5.00% by mass, a total light transmittance of 33.7%, a haze value of 97.0, and a Charpy impact strength (notched) of 81.0 kJ / m2.

[0138] Example 13 <Evaluation of Transparency of Raw Material Mixture After Heat Treatment> Using 312.8 g of PDMS-8 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment exhibited high transparency, with a total light transmittance of 89.1% and a haze value of 2.6. <Preparation of PC-POS Copolymer> Using 312.8 g of PDMS-8 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a particulate polycarbonate-polyorganosiloxane copolymer with high transparency. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20100, a polydimethylsiloxane content of 8.30% by mass, a total light transmittance of 28.3%, a haze value of 98.1, and a Charpy impact strength (notched) of 85.0 kJ / m2.

[0139] Example 14 <Evaluation of Transparency of Raw Material Mixture After Heat Treatment> Using 179.7 g of PDMS-9 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 90.1% and a haze value of 2.0. <Preparation of PC-POS Copolymer> Using 179.7 g of PDMS-9 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a particulate polycarbonate-polyorganosiloxane copolymer with high transparency. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20,000, a polydimethylsiloxane content of 3.10% by mass, a total light transmittance of 62.0%, a haze value of 89.4, and a Charpy impact strength (notched) of 75.0 kJ / m2.

[0140] Example 15 <Evaluation of Transparency of Raw Material Mixture After Heat Treatment> Using 179.7 g of PDMS-10 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment exhibited high transparency, with a total light transmittance of 91.0% and a haze value of 1.3. <Preparation of PC-POS Copolymer> Using 179.7 g of PDMS-10 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a particulate polycarbonate-polyorganosiloxane copolymer with high transparency. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20150, a polydimethylsiloxane content of 0.90% by mass, a total light transmittance of 86.1%, a haze value of 6.8, and a Charpy impact strength (notched) of 76.0 kJ / m2.

[0141] Example 16 <Evaluation of Transparency of Raw Material Mixture After Heat Treatment> Using 28.2 g of PDMS-11 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment exhibited high transparency, with a total light transmittance of 89.9% and a haze value of 7.3. <Preparation of PC-POS Copolymer> Using 28.2 g of PDMS-11 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a particulate polycarbonate-polyorganosiloxane copolymer with high transparency. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20200, a polydimethylsiloxane content of 0.53% by mass, a total light transmittance of 65.1%, and a haze value of 83.5.

[0142] Example 17 <Evaluation of Transparency of Raw Material Mixture After Heat Treatment> Using 57.1 g of PDMS-11 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment exhibited high transparency, with a total light transmittance of 78.6% and a haze value of 12.0. <Preparation of PC-POS Copolymer> Using 57.1 g of PDMS-11 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a particulate polycarbonate-polyorganosiloxane copolymer with high transparency. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20,100, a polydimethylsiloxane content of 1.10% by mass, a total light transmittance of 48.1%, and a haze value of 87.5.

[0143] Example 18 <Evaluation of Transparency of Raw Material Mixture After Heat Treatment> Using 28.2 g of PDMS-12 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 97.9% and a haze value of 0.9. <Preparation of PC-POS Copolymer> Using 28.2 g of PDMS-12 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a particulate polycarbonate-polyorganosiloxane copolymer with high transparency. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 19900, a polydimethylsiloxane content of 0.45% by mass, a total light transmittance of 81.0%, and a haze value of 11.3.

[0144] Example 19 <Evaluation of Transparency of Raw Material Mixture After Heat Treatment> Using 179.7 g of PDMS-12 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment exhibited high transparency, with a total light transmittance of 91.3% and a haze value of 2.1. <Preparation of PC-POS Copolymer> Using 179.7 g of PDMS-12 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a particulate polycarbonate-polyorganosiloxane copolymer with high transparency. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20,100, a polydimethylsiloxane content of 2.70% by mass, a total light transmittance of 61.0%, and a haze value of 82.1.

[0145] Example 20 <Evaluation of Transparency of Raw Material Mixture After Heat Treatment> Using 28.2 g of PDMS-13 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment exhibited high transparency, with a total light transmittance of 91.5% and a haze value of 8.5. <Preparation of PC-POS Copolymer> Using 28.2 g of PDMS-13 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a particulate polycarbonate-polyorganosiloxane copolymer with high transparency. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20050, a polydimethylsiloxane content of 0.42% by mass, a total light transmittance of 63.5%, and a haze value of 81.2.

[0146] Example 21 <Evaluation of Transparency of Raw Material Mixture After Heat Treatment> Using 20.2 g of PDMS-14 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 98.1% and a haze value of 1.0. <Preparation of PC-POS Copolymer> Using 20.2 g of PDMS-14 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 2 to obtain a particulate polycarbonate-polyorganosiloxane copolymer with high transparency. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 15,000, a polydimethylsiloxane content of 0.68% by mass, a total light transmittance of 69.7%, and a haze value of 84.0.

[0147] Comparative Example 1: 28.2 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 1. The heat-treated liquid raw material mixture became cloudy, with a total light transmittance of 77.6% and a haze value of 95.4. 28.2 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 1, thereby obtaining a particulate polycarbonate-polyorganosiloxane copolymer that exhibited strong cloudiness. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0148] Comparative Example 2: 24.4 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 2. The heat-treated liquid raw material mixture became cloudy, with a total light transmittance of 78.5% and a haze value of 93.2. 24.4 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 2, thereby obtaining a particulate polycarbonate-polyorganosiloxane copolymer that exhibited strong cloudiness. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0149] Comparative Example 3: 20.2 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture became cloudy, with a total light transmittance of 79.1% and a haze value of 92.1. 20.2 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 3, thereby obtaining a particulate polycarbonate-polyorganosiloxane copolymer that exhibited strong cloudiness. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0150] Comparative Example 4: 105.4 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture became cloudy, with a total light transmittance of 63.2% and a haze value of 95.5. 105.4 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 3, thereby obtaining a particulate polycarbonate-polyorganosiloxane copolymer that exhibited strong cloudiness. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0151] Comparative Example 5: 20.2 g of PDMS-6 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture became cloudy, with a total light transmittance of 79.5% and a haze value of 93.1. 20.2 g of PDMS-6 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 3, thereby obtaining a particulate polycarbonate-polyorganosiloxane copolymer that exhibited strong cloudiness. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0152] Comparative Example 6: 20.2 g of PDMS-7 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 3. The heat-treated liquid raw material mixture became cloudy, with a total light transmittance of 81.1% and a haze value of 88.9. 20.2 g of PDMS-7 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 3, thereby obtaining a particulate polycarbonate-polyorganosiloxane copolymer that exhibited strong cloudiness. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0153] Comparative Example 7: 22.1 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 9. The heat-treated liquid raw material mixture became cloudy, with a total light transmittance of 80.1% and a haze value of 90.1. 22.1 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 9, thereby obtaining a particulate polycarbonate-polyorganosiloxane copolymer that exhibited strong cloudiness. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0154] Comparative Example 8: 19.8 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 10. The heat-treated liquid raw material mixture became cloudy, with a total light transmittance of 78.5% and a haze value of 89.9. 19.8 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 10, thereby obtaining a particulate polycarbonate-polyorganosiloxane copolymer that exhibited strong cloudiness. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0155] Comparative Example 9: 21.3 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 11. The heat-treated liquid raw material mixture became cloudy, with a total light transmittance of 79.9% and a haze value of 88.5. 21.3 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 11, thereby obtaining a particulate polycarbonate-polyorganosiloxane copolymer that exhibited strong cloudiness. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0156] Comparative Example 10: 179.7 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 1. The heat-treated liquid raw material mixture became cloudy, with a total light transmittance of 65.1% and a haze value of 97.5. 179.7 g of PDMS-5 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 1, thereby obtaining a particulate polycarbonate-polyorganosiloxane copolymer that exhibited strong cloudiness. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20,000, a polydimethylsiloxane content of 5.30% by mass, a total light transmittance of 19.3%, a haze value of 99.6, and a Charpy impact strength (notched) of 61.0 kJ / m².

[0157] Comparative Example 11: 179.7 g of PDMS-7 was used as the polyorganosiloxane. Otherwise, the transparency of the heat-treated raw material mixture was evaluated in the same manner as in Example 1. The heat-treated liquid raw material mixture became cloudy, with a total light transmittance of 66.5% and a haze value of 96.2. 179.7 g of PDMS-7 was used as the polyorganosiloxane. Otherwise, polymerization was carried out under the same conditions as in Example 1, thereby obtaining a particulate polycarbonate-polyorganosiloxane copolymer that exhibited strong cloudiness. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20100, a polydimethylsiloxane content of 5.50% by mass, a total light transmittance of 17.5%, a haze value of 99.5, and a Charpy impact strength (notched) of 61.0 kJ / m².

[0158] [Table 2] Table 2 unit Example 1 2 3 4 5 6 7 8 9 10 11 Add conditions Diol monomer (A) BisP-A Mole ratio 100 50 ISB 70 70 70 70 70 70 70 70 70 1,4-CHDM 50 30 30 30 30 30 30 25 28 TCDDM 30 1,3-PG 5 PEG400 2 Dicarbonate DPC 107 103 100 100 100 100 100 100 100 100 100 Polyorganosiloxane (B) PDMS-1 wt% * 1 1 1 5 10 1 1 1 PDMS-2 1 PDMS-3 1 PDMS-4 1 PDMS-5 PDMS-6 PDMS-7 Evaluation results Raw material mixture after heat treatment Total light transmittance % 98.4 98.5 99.5 98.4 98.1 97.9 97.5 97.1 98.5 98.3 98.3 Haze value - 0.5 0.5 0.4 0.8 1.3 0.7 0.9 1.1 0.4 0.4 0.4 PC-POS copolymer Formula (1) Polyorganosiloxane wt% 0.62 0.63 0.62 0.73 0.82 0.67 3.3 6.3 0.61 0.62 0.62 Viscosity average molecular weight Mv 15,500 15,100 14,900 15,100 15,100 14,500 15,400 15,300 15,100 14,800 14,900 Total light transmittance (1 mmt) % 82.0 84.0 91.1 86.5 80.1 90.2 90.5 88.9 90.8 91.2 90.9 Haze value - 5.5 4.1 0.7 3.1 5.8 1.3 1.9 3.6 0.7 0.9 0.9 Charpy impact strength (with notch) kJ / m 2 20.3 22.4 9.8 10.8 12.1 8.7 12.5 14.5 8.9 10.5 10.8 *The wt% of polyorganosiloxane (B) indicates the amount of added polyorganosiloxane (B) included in the mass (theoretical value) of the obtained PC-POS copolymer. This value is calculated using the following formula. The theoretical value of PC-POS copolymer mass = mass of all glycol monomers + mass of diester + mass of polyorganosiloxane (B) - mass of phenol produced (2 moles of phenol compared to diester)

[0159] [Table 3] Table 3 unit Comparative example 1 2 3 4 5 6 7 8 9 Add conditions Diol monomer (A) BisP-A Mo Er ratio 100 50 ISB 70 70 70 70 70 70 70 1,4-CHDM 50 30 30 30 30 25 28 TCDDM 30 1,3-PG 5 PEG400 2 Dicarbonate DPC 107 103 100 100 100 100 100 100 100 Polyorganosiloxane (B) PDMS-1 wt% * PDMS-2 PDMS-3 PDMS-4 PDMS-5 1 1 1 5 1 1 1 PDMS-6 1 PDMS-7 1 Evaluation results Raw material mixture after heat treatment Total light transmittance % 77.6 78.5 79.1 63.2 79.5 81.1 80.1 78.5 79.9 Haze value - 95.4 93.2 92.1 95.5 93.1 88.9 90.1 89.9 88.5 PC-POS copolymer Formula (1) Polyorganosiloxane wt% 0.87 0.87 0.88 4.01 0.87 0.89 0.86 0.87 0.88 Viscosity average molecular weight Mv 15,000 15,100 15,300 15,100 15,300 14,900 14,900 15,100 15,000 Total light transmittance (1 mmt) % 49.6 51.1 52.7 41.0 51.2 50.1 51.6 49.9 53.1 Haze value - 99.6 99.3 99.6 99.8 98.2 98.5 99.2 98.2 97.5 Charpy impact strength (with notch) kJ / m 2 15.4 14.2 6.1 6.8 6.2 6.0 6.3 6.3 6.4 *The wt% of polyorganosiloxane (B) indicates the amount of added polyorganosiloxane (B) included in the mass (theoretical value) of the obtained PC-POS copolymer. This value is calculated using the following formula. The theoretical value of PC-POS copolymer mass = mass of all glycol monomers + mass of diester + mass of polyorganosiloxane (B) - mass of phenol produced (2 moles of phenol compared to diester)

Claims

1. A polycarbonate-polyorganosiloxane copolymer, manufactured using a diol monomer (a1) and a polyorganosiloxane (a2) satisfying the following conditions, and comprising: a polyorganosiloxane block (A-1) having a structure represented by the following general formula (1A); and a polycarbonate block (A-2) containing only repeating units represented by the following general formula (2); The mixture obtained by contacting the diol monomer (a1), the polyorganosiloxane (a2), the diester, and the alkaline catalyst in the same proportions as in the manufacture of the above-mentioned polycarbonate-polyorganosiloxane copolymer at 100–250°C for 0.5–5 hours has a haze value of 30 or less as measured according to ISO 14782:1999 at 23°C and an optical path length of 10 mm. [In the formula, R1 to R4 may be the same or different, and independently represent hydrogen atoms, halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, aryl groups with 6 to 12 carbon atoms, or alkylaryl groups with 1 to 10 carbon atoms in the alkyl group; R6 represents aryl groups with 6 to 20 carbon atoms, alkyl groups with 1 to 10 carbon atoms, or alkylaryl groups with 1 to 10 carbon atoms in the alkyl group, and may include -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R111 represents alkyl groups with 1 to 10 carbon atoms or aryl groups with 6 to 10 carbon atoms; a represents an integer from 2 to 70; R10 represents a divalent aliphatic hydrocarbon group with 2 to 40 carbon atoms, and may include branched or cyclic structures, and may be substituted by substituents; the above-mentioned divalent aliphatic hydrocarbon group may include oxygen atoms as heteroatoms.] R40' is a repeating chain structure, which is formed by linking at least two hydrocarbon groups containing at least one hydrocarbon group selected from divalent aliphatic hydrocarbon group of carbon 1 to 20, divalent alicyclic hydrocarbon group of carbon 3 to 20, or divalent aromatic hydrocarbon group of carbon 6 to 20, and at least one heteroatom selected from the group consisting of oxygen atom, nitrogen atom and sulfur atom; R40" represents divalent aliphatic hydrocarbon group of carbon 1 to 20, divalent alicyclic hydrocarbon group of carbon 3 to 20, or divalent aromatic hydrocarbon group of carbon 6 to 20, which can be substituted by substituents; e and u represent 0 or 1; y represents an integer from 10 to 500).

2. The polycarbonate-polyorganosiloxane copolymer of claim 1, wherein the diol monomer (a1) is an aliphatic dihydroxy compound represented by the following general formula (112): [wherein, R100 represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, and may contain a branched structure or a cyclic structure; R100 may contain an oxygen atom as a heteroatom].

3. The polycarbonate-polyorganosiloxane copolymer of claim 1 or 2, wherein the diol monomer (a1) is selected from isosorbide, cyclohexane-1,4-diethanol, tricyclodecane-diethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol and 1,4-butanediol, which are aliphatic diols.

4. The polycarbonate-polyorganosiloxane copolymer of claim 1 or 2, wherein the polycarbonate block (A-2) has one or more of the repeating units selected from the group represented by the following general formulas (ai) to (a-iv):

5. The polycarbonate-polyorganosiloxane copolymer of claim 1 or 2, wherein the aforementioned polyorganosiloxane block (A-1) comprises at least one of the group consisting of structural units selected from those represented by the following general formulas (1-1) to (1-3): [wherein, R1 to R4 and a are as described above; R5 and R6 may be the same or different, and independently represent aryl groups having 6 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or alkylaryl groups having 1 to 10 carbon atoms in the alkyl group, and may include -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R7 and R8 may be the same or different, and independently represent aryl groups having 6 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms, alkyl groups having 3 to 10 carbon atoms, or alkylaryl groups having 1 to 10 carbon atoms in the alkyl group, and may include -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R7 and R8 may be the same or different, and independently represent aryl groups having 6 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or alkylaryl groups having 3 to 10 carbon atoms.] 0 is a branched alkyl group or an alkyl aryl group with 1 to 10 carbon atoms in the alkyl group, and may contain -O-, -COO-, -CO-, -S-, -NH-, -NR111- as functional groups; R111 represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms; z and z1 each independently represent 1; b and b1 each independently represent an integer from 2 to 100; 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.

6. The polycarbonate-polyorganosiloxane copolymer of claim 1 or 2, wherein R1 to R4 in the above general formula (1A) all represent methyl.

7. The polycarbonate-polyorganosiloxane copolymer of claim 1 or 2, wherein in the above general formula (1A), R6 is trimethylene (-(CH2)3-).

8. The polycarbonate-polyorganosiloxane copolymer of claim 5, wherein in the above general formulas (1-1) to (1-3), R8 is selected from any one of the structures in the group consisting of diallyl (-(CH2)2-), methyl-substituted diallyl (-CH2CHMe-), trimethylene (-(CH2)3-), and tetramethylene (-(CH2)4-).

9. The polycarbonate-polyorganosiloxane copolymer of claim 1 or 2 has a viscosity average molecular weight (Mv) of 5,000 to 50,000.

10. The polycarbonate-polyorganosiloxane copolymer of claim 1 or 2, wherein the haze value of the 1 mm thick plate obtained by molding the above polycarbonate-polyorganosiloxane copolymer is 40 or less as measured according to ISO 14782:1999.

11. The polycarbonate-polyorganosiloxane copolymer of claim 1 or 2 is obtained by melt polymerization.

12. The polycarbonate-polyorganosiloxane copolymer of claim 1 or 2, wherein the carbonate diester is selected from at least one compound selected from diaryl carbonate compounds, dialkyl carbonate compounds, and alkylaryl carbonate compounds.

13. The polycarbonate-polyorganosiloxane copolymer of claim 1 or 2, wherein the alkaline catalyst is selected from at least one of the group consisting of alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, aryl-containing quaternary phosphonium salts and metal compounds.

14. A polycarbonate-based resin composition comprising a polycarbonate-polyorganosiloxane copolymer as claimed in any one of claims 1 to 13.

15. The polycarbonate-based resin composition of claim 14, further comprising an inorganic filler.

16. The polycarbonate-based resin composition of claim 15, wherein, relative to 100 parts by weight of the above-mentioned polycarbonate-polyorganosiloxane copolymer, it comprises 1 to 150 parts by weight of the above-mentioned inorganic filler.

17. The polycarbonate-based resin composition of claim 15 or 16, wherein the inorganic filler is glass fiber or carbon fiber.

18. A molded article comprising a polycarbonate-based resin composition as claimed in any one of claims 14 to 17.