POLYCARBONATE RESIN COMPOSITION AND FORM ITEMS THEREOF

Abstract

The present invention relates to a polycarbonate-based resin composition comprising: an aromatic polycarbonate-based resin (A-1) comprising a structural unit represented by the following formula (II); and an aromatic polycarbonate-based resin (A-2) comprising a repeating unit represented by the following formula (I), wherein the proportion of the structural unit represented by formula (II) to the total amount of the structural unit represented by formula (II) and a repeating unit represented by formula (III) is 50% by mass or more, and a molded article therefrom.

Description

Technical field

[0001] The present invention relates to a polycarbonate-based resin composition and a molded article formed therefrom. background

[0002] For example, a polycarbonate-based resin is characterized by excellent impact resistance, transparency, heat resistance, and self-extinguishing properties, and is therefore frequently used as a multi-purpose plastic in various sectors, such as electrical and electronic equipment and the automotive industry. However, polycarbonate-based resins have low surface hardness and are therefore insufficient in terms of scratch resistance in some cases.

[0003] In PTL 1, a polycarbonate copolymer with improved scratch resistance is disclosed, comprising: a unit derived from a hydroxy-terminated monocyclic, polycyclic or condensed cyclic compound with a (meth)acrylate group; and a carbonate unit.

[0004] PTL 2 discloses a fire-resistant polycarbonate resin that is branched or cross-linked, and an intermediate thereof. Citation list for patent literature PTL 1: KR 2016-0141268 A PTL 2: JP H02-219818 A Summary of the invention Technical

[0005] A process involving the coating of the top layer of a structural body formed from a polycarbonate-based resin is known to improve its surface hardness. However, this process requires a coating step, which complicates the manufacturing process and increases the environmental impact.

[0006] Furthermore, the invention described in PTL 1 is insufficient with regard to surface hardness. PTL 2 does not describe a method for improving surface hardness.

[0007] As described above, further investigations were needed to achieve an improvement in scratch resistance using only the polycarbonate-based resin.

[0008] An objective of the present invention is to provide a polycarbonate-based resin composition and a molded article, each exhibiting improved scratch resistance. Solution to the problem

[0009] The inventors of the present invention have found that the above-mentioned problems are solved by a polycarbonate-based resin composition comprising an aromatic polycarbonate-based resin comprising a specific structural unit.

[0010] That is to say, the present invention comprises the following points 1 to 13. 1. Polycarbonate-based resin composition, comprising: an aromatic polycarbonate-based resin (A-1) containing a structural unit represented by the following formula (II); and an aromatic polycarbonate-based resin (A-2) containing a repeating unit represented by the following formula (I), wherein the ratio of the structural unit represented by formula (II) to the total quantity of the structural unit represented by formula (II) and the repeating unit represented by formula (III) is 50 mass % or more: where in formula (II) R 11 and R 12Each independently represents a halogen atom or a group selected from the group consisting of: an alkyl group with 1 to 18 carbon atoms; an alkoxy group with 1 to 18 carbon atoms; a cycloalkyl group with 3 to 20 carbon atoms; a cycloalkoxy group with 3 to 20 carbon atoms; an alkenyl group with 2 to 10 carbon atoms; an aryl group with 6 to 14 carbon atoms; an aryloxy group with 6 to 14 carbon atoms; an aralkyl group with 7 to 20 carbon atoms; an aralkyloxy group with 7 to 20 carbon atoms; a nitro group; an aldehyde group; a cyano group; and a carboxyl group. R 13a hydrogen atom or a group selected from the group consisting of an alkyl group with 1 to 5 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, a cycloalkoxy group with 3 to 20 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, and an aryl group with 6 to 14 carbon atoms, R 14 a group selected from the group consisting of: a saturated or unsaturated cyclic hydrocarbon group with 3 to 20 carbon atoms; a substituted or unsubstituted alkyl group; and a 3- to 20-membered saturated or unsaturated heterocyclic group, “c” and “d” each independently represent an integer from 0 to 4 and “m” represents an integer from 0 to 20; where in formula (I) R 1 and R 2Each independently represents a halogen atom or a group selected from the group consisting of: an alkyl group with 1 to 18 carbon atoms; an alkoxy group with 1 to 18 carbon atoms; a cycloalkyl group with 3 to 20 carbon atoms; a cycloalkoxy group with 3 to 20 carbon atoms; an alkenyl group with 2 to 10 carbon atoms; an aryl group with 6 to 14 carbon atoms; an aryloxy group with 6 to 14 carbon atoms; an aralkyl group with 7 to 20 carbon atoms; an aralkyloxy group with 7 to 20 carbon atoms; a nitro group; an aldehyde group; a cyano group; and a carboxyl group. X represents a single bond, an alkylene group with 1 to 8 carbon atoms, an alkylidene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 15 carbon atoms, a cycloalkylidene group with 5 to 15 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, -S-, -SO-, -SO2-, -O- or -CO-, and “a” and “b” each independently represent an integer from 0 to 4; where in formula (III) R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms or an aryl group with 6 to 12 carbon atoms.

[0011] 2. Polycarbonate-based resin composition according to point 1, wherein R 14represents an alkyl group with 1 to 18 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group with 3 to 12 carbon atoms, or a 3- to 12-membered saturated or unsaturated heterocyclic group.

[0012] 3. Polycarbonate-based resin composition according to point 2, wherein R 14 represents a methyl group, a cyclopentyl group, or a cyclohexyl group.

[0013] 4. Polycarbonate-based resin composition according to one of points 1 to 3, where “m” represents an integer from 0 to 4.

[0014] 5. Polycarbonate-based resin composition according to any one of points 1 to 4, wherein the aromatic polycarbonate-based resin (A-2) further comprises a polyorganosiloxane block containing the repeating unit represented by formula (III).

[0015] 6. Polycarbonate-based resin composition according to point 5, wherein the repeating unit represented by formula (III) is included as a structural unit represented by one of the following general formulas (III-I) to (III-III):

[0016] where in formulas (III-I) to (III-III) R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or an aryl group with 6 to 12 carbon atoms, and several R 3 to R 6 may be identical or different from each other, Y-R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R 9 -O- or -R 7 OR 10 -O- represents, and several Y-groups can be the same or different from each other, where R 7a single bond, a linear, branched or cyclic alkylene group, -R 71 R 72 -, represents a substituted or unsubstituted arylene group or a diarylene group, R 71 a linear, branched or cyclic alkylene group, R 72 a substituted or unsubstituted arylene group, R 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, R 9 represents a diarylene group, R 10 a linear, branched or cyclic alkylene group or a diarylene group, β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide, 'n' represents an integer of 31 or greater and less than 91, and 'p' represents an integer of 1 or greater and n-2 or less.

[0017] 7. Polycarbonate-based resin composition according to any one of points 1 to 6, wherein the proportion of the repeating unit represented by formula (III) in the total content of the repeating unit represented by formula (I), the repeating unit represented by formula (II) and the repeating unit represented by formula (III) is 0.1 wt% to 3.2 wt%.

[0018] 8. Polycarbonate-based resin composition according to any one of points 1 to 7, wherein the aromatic polycarbonate-based resin (A-1) further comprises the repeating unit represented by formula (I).

[0019] 9. Polycarbonate-based resin composition according to any one of points 1 to 8, wherein the proportion of the structural unit represented by formula (II) in the total content of the repeating unit represented by formula (I), the repeating unit represented by formula (II) and the repeating unit represented by formula (III) is 1.0 wt% to 25 wt%.

[0020] 10. Polycarbonate-based resin composition according to any one of points 1 to 9, wherein the aromatic polycarbonate-based resin (A-1) has a viscosity-averaged molecular weight (Mv) of 10,000 to 100,000.

[0021] 11. Polycarbonate-based resin composition according to any one of items 1 to 10, wherein the aromatic polycarbonate-based resin (A-2) has a viscosity-averaged molecular weight (Mv) of 15,000 to 25,000.

[0022] 12. Polycarbonate-based resin composition according to any one of items 1 to 11, wherein a molded article made from the polycarbonate-based resin composition has a scratch resistance of HB or greater, tested according to JIS K5600-5-4.

[0023] 13. Molded articles made from the polycarbonate-based resin composition according to one of points 1 to 12. Advantageous effects of the invention

[0024] The present invention can provide the polycarbonate-based resin composition and the molded article therefrom, each exhibiting improved scratch resistance. Description of the embodiments

[0025] In the following, a polycarbonate-based resin composition and a molded article made therefrom are described in detail. In this description, any specification considered preferred may be adopted arbitrarily, and it may be said that a combination of preferred descriptions is more preferred. The term "XX to YY" used here means "XX or more and YY or less". 1. Polycarbonate-based resin composition

[0026] The polycarbonate-based resin composition of the present invention comprises: an aromatic polycarbonate-based resin (A-1) containing a structural unit represented by formula (II) described below; and an aromatic polycarbonate-based resin (A-2) containing a repeating unit represented by formula (I) described below. Furthermore, the proportion of the structural unit represented by formula (II) to the total amount of the structural unit represented by formula (II) and the repeating unit represented by formula (III) described below is 50% by mass or more. The repeating unit represented by formula (III) may be included in either of the aromatic polycarbonate resins (A-1) and (A-2), or it may not be included therein.

[0027] In the polycarbonate-based resin composition of the present invention, the proportion of the structural unit represented by formula (II) to the total amount of the structural unit represented by formula (II) and the repeating unit represented by formula (III) is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and is preferably 100% by mass or less, more preferably 100% by mass, in order to improve the scratch resistance of the resin composition.If the polycarbonate-based resin composition contains the repeating unit represented by formula (III), the proportion of the structural unit represented by formula (II) to the total amount of the structural unit represented by formula (II) and the repeating unit represented by formula (III) is 50 to 100 wt%, preferably 60 to 100 wt%, more preferably 70 to 100 wt%, and more preferably 80 to 100 wt%.

[0028] The term ‘total quantity of the structural unit represented by formula (II) and the repeating unit represented by formula (III)’ refers to the percentage of the mass of the structural unit represented by formula (II) to the total mass of the structural unit represented by formula (II) and the repeating unit represented by formula (III), as required. [Aromatic polycarbonate-based resin (A-1)]

[0029] The aromatic polycarbonate-based resin (A-1) comprises the structural unit represented by the following formula (II). where in formula (II) R 11 and R 12 Each independently represents a halogen atom or a group selected from the group consisting of: an alkyl group with 1 to 18 carbon atoms; an alkoxy group with 1 to 18 carbon atoms; a cycloalkyl group with 3 to 20 carbon atoms; a cycloalkoxy group with 3 to 20 carbon atoms; an alkenyl group with 2 to 10 carbon atoms; an aryl group with 6 to 14 carbon atoms; an aryloxy group with 6 to 14 carbon atoms; an aralkyl(arylalkylene) group with 7 to 20 carbon atoms; an aralkyloxy group with 7 to 20 carbon atoms; a nitro group; an aldehyde group; a cyano group; and a carboxyl group. R 13represents a hydrogen atom or a group selected from the group consisting of: an alkyl group with 1 to 5 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, a cycloalkoxy group with 3 to 20 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, and an aryl group with 6 to 14 carbon atoms. R 14 represents a saturated or unsaturated cyclic hydrocarbon group with 3 to 20 carbon atoms, a substituted or unsubstituted alkyl group, or a 3- to 20-membered saturated or unsaturated heterocyclic group, “c” and “d” each independently represent an integer from 0 to 4 and "m" represents an integer from 0 to 20.

[0030] Examples of the halogen atom, the R 11 and R 12In formula (II), each atom comprises a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, which are represented independently of each other.

[0031] Examples of the alkyl group with 1 to 18 carbon atoms, which R 11 and R 12 Each of these groups, which can be represented independently, include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups (the term "various" means that a linear group and all types of branched groups are included, and the same applies to what follows), various pentyl groups, and various hexyl groups.

[0032] Examples of the alkoxy group with 1 to 18 carbon atoms, which R 11 and R 12 Each of which can be represented independently of the others, includes alkoxy groups whose alkyl group residues are the alkyl groups mentioned above.

[0033] Examples of the cycloalkyl group with 3 to 20 carbon atoms, which R 11and R 12 Each, which can be represented independently of each other, comprises a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.

[0034] Examples of the cycloalkoxy group with 3 to 20 carbon atoms, which R 11 and R 12 Each of which can be represented independently of the others, comprises cycloalkoxy groups whose cycloalkyl group residues are the cycloalkyl groups mentioned above.

[0035] Examples of the alkenyl group with 2 to 10 carbon atoms, which R 11 and R 12 Each representing an independent group comprises an ethenyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group.

[0036] Examples of the aryl group with 6 to 14 carbon atoms, which R 11 and R 12Each, representing an independent entity, comprises a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.

[0037] Examples of the aryloxy group with 6 to 14 carbon atoms, which R 11 and R 12 Each of which can be represented independently of the others, comprises aryloxy groups whose aryl group residues are the aryl groups mentioned above.

[0038] Examples of the aralkyl group with 7 to 20 carbon atoms, which R 11 and R 12 Each, representing the two independently, comprises a phenylmethyl group and a phenylethyl group.

[0039] Examples of the aralkyloxy group with 7 to 20 carbon atoms, which R 11 and R 12 Each of which can be represented independently of the others, comprises aralkyloxy groups whose aralkyl group residues are the aralkyl groups mentioned above.

[0040] Examples of the alkyl group with 1 to 5 carbon atoms, represented by R13 as represented in formula (II), comprise a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups and various pentyl groups.

[0041] Examples of those caused by R (13) The depicted cycloalkyl groups with 3 to 20 carbon atoms comprise a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.

[0042] Examples of those caused by R (13) The depicted cycloalkoxy groups with 3 to 20 carbon atoms include cycloalkoxy groups whose cycloalkyl group residues are the cycloalkyl groups mentioned above.

[0043] Examples of those caused by R (13) Alkenyl group with 2 to 10 carbon atoms, represented by R 13 , comprise an ethenyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group.

[0044] Examples of those caused by R 13 The depicted aryl group with 6 to 14 carbon atoms comprises a phenyl group, a naphthyl group, a biphenyl group and an anthryl group.

[0045] The saturated or unsaturated cyclic hydrocarbon group represented by R 14The compound represented in formula (II) has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. Specific examples include: cycloalkyl groups serving as saturated alicyclic groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, and a norbonyl group; cycloalkenyl groups serving as unsaturated alicyclic groups, such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group; and aryl groups, such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.

[0046] Examples of those caused by R 14The substituted or unsubstituted alkyl groups shown include: unsubstituted alkyl groups with 1 to 18 carbon atoms each, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups and various hexyl groups; and substituted alkyl groups, such as a benzyl group.

[0047] The number of atoms required to form the ring defined by R 14 The number of atoms in the depicted heterocyclic group is 3 to 20, and the ring preferably has 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms. The heterocyclic group is a cyclic group containing at least one heteroatom, for example one, two, or three heteroatoms, as ring-forming atoms. Specific examples of the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a boron atom.

[0048] Examples of the heterocyclic group include a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, an indolinyl group, a quinolinyl group, an acridinyl group, a pyrrolidinyl group, a dioxanyl group, a piperidinyl group, an oxiranyl group (epoxy group), an oxetanyl group, a morpholidinyl group, a piperazinyl group, a carbazolyl group, a furanyl group, a thiophenyl group, an oxazolyl group, an oxadiazolyl group, a benzoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a triazolyl group, an imidazolyl group, a benzimidazolyl group, and a furanyl group.

[0049] R 14preferably represents an alkyl group with 1 to 18 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group with 3 to 12 carbon atoms or a 3- to 12-membered saturated or unsaturated heterocyclic group, more preferably an alkyl group with 1 to 3 carbon atoms or a cycloalkyl group with 3 to 8 carbon atoms, and even more preferably a methyl group, a cyclopentyl group or a cyclohexyl group.

[0050] “c” and “d” each independently represent an integer from 0 to 4, preferably an integer from 0 to 2, more preferably 0 or 1.

[0051] “m” represents an integer from 0 to 20, preferably an integer from 0 to 10, more preferably an integer from 0 to 4, further more preferably 0, 1, 2, 3 or 4, and even more preferably 2.

[0052] In a preferred aspect of formula (II) R represents 14From the perspective of improving the scratch resistance of the resin composition, represents a methyl group, a cyclopentyl group, or a cyclohexyl group, and 'm' preferably represents 0 to 2, more preferably 2. Furthermore, 'c' and 'd' each preferably represent 0, and R (13) preferably represents an alkyl group with 1 to 3 carbon atoms, more preferably a methyl group.

[0053] In the aromatic polycarbonate-based resin (A-1), the structural units represented by formula (II) can be used alone or in combination with each other.

[0054] The aromatic polycarbonate-based resin (A-1) may contain an additional repeating unit besides the structural unit represented by formula (II). An example of such a repeating unit is the repeating unit represented by formula (I) in the following aromatic polycarbonate-based resin (A-2).

[0055] If the above-mentioned aromatic polycarbonate-based resin (A-1) contains the repeating unit represented by formula (I), then the aromatic polycarbonate-based resin is an aromatic polycarbonate-based copolymer containing the repeating unit represented by formula (I) and the structural unit represented by formula (II).

[0056] If the aromatic polycarbonate-based resin (A-1) contains the repeating unit represented by formula (I), the repeating unit represented by formula (I) in the aromatic polycarbonate-based resin (A-1) and the repeating unit represented by formula (I) in the aromatic polycarbonate-based resin (A-2) may be identical or different, but are identical with respect to high compatibility between the aromatic polycarbonate-based resin (A-1) and the aromatic polycarbonate-based resin (A-2).

[0057] The aromatic polycarbonate-based resin (A-1) may contain a structural unit that differs from the repeating unit represented by formula (I) and the structural unit represented by formula (II). Examples of such units are a terminal structure derived from an end stop, to be described later, and a silicon-containing structural unit. An example of the silicon-containing structural unit is the repeating unit represented by formula (III), to be described later.

[0058] The content of the structural unit represented by formula (II) in the aromatic polycarbonate-based resin (A-1) is preferably 4 to 35 wt%, more preferably 6 to 30 wt%, more preferably 8 to 27 wt% and more preferably 10 to 25 wt%.

[0059] In the aromatic polycarbonate-based resin (A-1), the term “content of the structural unit represented by formula (II)” refers to the percentage of the mass of the structural unit represented by formula (II) in relation to the total mass of the structural unit represented by formula (II) and the repeating unit represented by formula (I), and, where applicable, the repeating unit represented by formula (III). The same applies to the “content of the repeating unit represented by formula (I)”.

[0060] The content of the structural unit represented by formula (II) in the aromatic polycarbonate-based resin (A-1) is calculated by nuclear magnetic resonance (NMR) measurement. In particular, a 1H-NMR measurement was performed and the content was calculated from the integrated values ​​of a peak derived from the structural unit represented by formula (II), a peak derived from the structural unit represented by formula (II), a peak derived from the repeating unit represented by formula (I), and a peak derived from the repeating unit represented by formula (III).

[0061] The viscosity-averaged molecular weight (Mv) of the aromatic polycarbonate-based resin (A-1) is preferably between 10,000 and 100,000, more preferably 10,000 to 80,000, further more preferably 15,000 to 30,000 and even more preferably 17,000 to 25,000 with regard to its mechanical properties and formability.

[0062] In the present invention, the viscosity-averaged molecular weight (Mv) is calculated from the following quick equation after determining the intrinsic viscosity [η] by measuring the viscosity of a methylene chloride solution (concentration: g / L) at 20 °C with an Ubbelohde viscometer. [η]=1.23×10−5Mv0.83 <Verfahren zur Herstellung eines aromatischen Polycarbonat-basierten Harzes (A-1)> (Compound based on divalent phenol)

[0063] The aromatic polycarbonate-based resin (A-1) mentioned above can be suitably prepared using a divalent phenol-based compound represented by the following formula (ii). The structural unit of the aromatic polycarbonate-based resin mentioned above, represented by formula (II), is derived from the divalent phenol-based compound represented by formula (ii).

[0064] Accordingly, the present invention also provides the use of the compound represented by the following formula (ii) based on divalent phenol for the production of an aromatic polycarbonate-based resin:

[0065] where in formula (ii) R 11 , R 12 , R 13 , R 14 , “c”, “d” and “m” are defined as above and preferred examples are also the same as described above.

[0066] Preferred specific examples of the compound represented by formula (ii) based on divalent phenol include cyclohexyl diphenolate, represented by the following formula (ii-1), cyclopentyl diphenolate, represented by the following formula (ii-2), cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate, represented by the following formula (ii-3), methyl diphenolate, represented by the following formula (ii-4), and methyl 2,2-bis(4-hydroxy-3-methylphenyl)propanoate, represented by the following formula (ii-5).

[0067] The compound represented by formula (ii) based on divalent phenol can be prepared, for example, by reacting a carboxylic acid compound (ax), represented by the following formula (ii-x), and an alcohol compound (ay), represented by the following formula (ii-y), if necessary in the presence of an acid catalyst:

[0068] where in formula (ii-x) R11 , R 12 , R 13 , “c”, “d” and “m” are defined as above and preferred examples are also the same as described above;

[0069] where in formula (ii-y) R 14 as defined above, and preferred examples also correspond to those described above. (Method for the production of an aromatic polycarbonate-based resin (A-1))

[0070] The aromatic polycarbonate resin (A-1) mentioned above can be prepared by a known process for the preparation of a polycarbonate resin using the divalent phenol-based compound represented by formula (ii). Examples of the process for the preparation of a polycarbonate resin include: (i) an interfacial polymerization process (phosgene process) in which the compound based on divalent phenol and phosgene is reacted together in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, and subsequently a polymerization catalyst, such as a tertiary amine or a quaternary ammonium salt, is added to polymerize the resulting product; (ii) a melt polymerization process (ester exchange process) in which the compound based on divalent phenol and a carboxylic acid diester are subjected to an ester exchange reaction in the molten state, without the use of a solvent, by adding a basic catalyst; and (iii) a pyridine process in which the compound based on divalent phenol is dissolved in pyridine or a mixed solution of pyridine and an inert solvent and phosgene is introduced into the solution to produce the resin directly.

[0071] In the above-mentioned reaction, a molecular weight modifier (end stopper), a branching agent or similar is used as needed.

[0072] Among these, the following manufacturing process is preferred: a process for producing an aromatic polycarbonate-based resin comprising a step in which the divalent phenol-based compound and a polycarbonate oligomer are subjected to interfacial polycondensation in the presence of a water-insoluble organic solvent and an aqueous solution of an alkali compound, wherein the divalent phenol-based compound comprises the divalent phenol-based compound of formula (ii).

[0073] Specifically, in the case of the interfacial polymerization process, the aforementioned aromatic polycarbonate-based resin can be prepared by: dissolving a previously prepared polycarbonate oligomer, described later, in a water-insoluble organic solvent (e.g., methylene chloride); adding a solution of a compound based on divalent phenol in an aqueous solution of an alkaline compound (e.g., aqueous sodium hydroxide) to the solution; and subjecting the mixture to an interfacial polycondensation reaction using a tertiary amine (e.g., triethylamine) or a quaternary ammonium salt (e.g., trimethylbenzylammonium chloride) as a polymerization catalyst, if necessary in the presence of an end-stopper (a monovalent phenol, such as p-tert-butylphenol).Furthermore, in the case of the above-mentioned interfacial polymerization process, the above-mentioned aromatic polycarbonate-based resin can be produced by copolymerization of a divalent phenol with phosgene, a carbonic acid ester or a chloroformate.

[0074] The polycarbonate oligomer can be prepared by a reaction between a divalent phenol-based compound and a carbonate precursor, such as phosgene or triphosgene, in an organic solvent such as methylene chloride, chlorobenzene, or chloroform. If the polycarbonate oligomer is prepared using an ester exchange process, it can be generated by a reaction between the divalent phenol-based compound and a carbonate precursor, such as diphenyl carbonate.

[0075] The divalent phenol preferably further comprises a compound based on divalent phenol, represented by formula (i), from which the repeating unit represented by formula (I) is derived. The compound based on divalent phenol represented by formula (i) is described in detail in the following process for the preparation of the aromatic polycarbonate resin (A-2).

[0076] In a preferred manufacturing process, only the compound represented by formula (i) based on divalent phenol can be used to prepare the aforementioned polycarbonate oligomer. In this case, in the interfacial polycondensation reaction step, the compound represented by formula (ii) and the compound represented by formula (i) based on divalent phenol are used in combination, or only the compound represented by formula (ii) based on divalent phenol is used.

[0077] If the aromatic polycarbonate-based resin (A-1) contains the repeating unit represented by formula (III), the aromatic polycarbonate-based resin (A-1) can be prepared by the same process as the process described in the following process for the preparation of the aromatic polycarbonate-based resin (A-2), and the compounds represented by the general formulas (iii-i) to (iii-iii) described in the process for the preparation of the aromatic polycarbonate-based resin (A-2) can each be used in the same way as the polyorganosiloxane serving as raw material.

[0078] An endstop (molecular weight modifier) ​​can be used to adjust the molecular weight of the resulting aromatic polycarbonate-based resin. Examples of endstops include monovalent phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol, and p-tert-amylphenol. These monovalent phenols can be used alone or in combination. [Aromatic polycarbonate-based resin (A-2)]

[0079] The aromatic polycarbonate-based resin (A-2) comprises the repeating unit represented by the following formula (I). The aromatic polycarbonate-based resin (A-2) does not contain a structural unit represented by formula (II). where in formula (I) R 1 and R 2Each independently represents a halogen atom or a group selected from the group consisting of: an alkyl group with 1 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, a cycloalkoxy group with 3 to 20 carbon atoms, an alkenyl group with 2 to 10 carbon atoms; an aryl group with 6 to 14 carbon atoms; an aryloxy group with 6 to 14 carbon atoms; an aralkyl group with 7 to 20 carbon atoms; an aralkyloxy group with 7 to 20 carbon atoms; a nitro group; an aldehyde group; a cyano group; and a carboxyl group. X represents a single bond, an alkylene group with 1 to 8 carbon atoms, an alkylidene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 15 carbon atoms, a cycloalkylidene group with 5 to 15 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, -S-, -SO-, -SO2-, -O- or -CO-, and “a” and “b” each independently represent an integer from 0 to 4.

[0080] Examples of the halogen atom, the R 1 and R 2 In formula (I) each represent independently, they comprise a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0081] Examples of the alkyl group that R 1 and R 2 Each of which can be represented independently of the others, includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups and various hexyl groups.

[0082] Examples of the alkoxy group, which R 1 and R 2 Each of which can be represented independently of the others, includes alkoxy groups whose alkyl group residues are the alkyl groups mentioned above.

[0083] Examples of the cycloalkyl group that R 1 and R 2 Each, which can be represented independently of each other, comprises a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.

[0084] Examples of the cycloalkyl group that R 1 and R 2 Each of which can be represented independently of the others, comprises cycloalkoxy groups whose cycloalkyl group residues are the cycloalkyl groups mentioned above.

[0085] Examples of the alkenyl group that R 1 and R 2 Each representing an independent group comprises an ethenyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group.

[0086] Examples of the aryl group that R 1 and R 2 Each, representing an independent entity, comprises a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.

[0087] Examples of the aryloxy group that R 1 and R 2 Each of which can be represented independently of the others, comprises aryloxy groups whose aryl group residues are the aryl groups mentioned above.

[0088] Examples of the aralkyl group that R 1 and R 2 Each, representing the two independently, comprises a phenylmethyl group and a phenylethyl group.

[0089] Examples of the aralkyloxy group, which R 1 and R 2 Each of which can be represented independently of the others, comprises aralkyloxy groups whose aralkyl group residues are the aralkyl groups mentioned above.

[0090] The alkylene group represented by X has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. Specific examples include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group.

[0091] Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group.

[0092] The cycloalkylene group represented by X has 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms. Specific examples include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group.

[0093] Examples of the arylene group represented by X include a phenylene group, a naphthylene group, a biphenylene group, and a tetraphenylene group.

[0094] The cycloalkylidene group represented by X has 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms. Specific examples include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a 2-adamantylidene group.

[0095] The aralkyl group represented by X has 7 to 20 carbon atoms, and examples of its aryl residue include aryl groups with 6 to 14 ring-forming carbon atoms each, such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.

[0096] A case in which X represents an isopropylidene group, a cyclohexylidene group, or a 3,5,5-trimethylcyclohexylidene group is preferred among those described above, as it can improve the scratch resistance of a molded article made from the polycarbonate-based resin composition.

[0097] “a” and “b” each independently represent an integer from 0 to 4, preferably from 0 to 2, more preferably 0 or 1.

[0098] Among these, a suitable case is one in which “a” and “b” each represent 0 and X represents a single bond or an alkylene group with 1 to 8 carbon atoms, or a case in which “a” and “b” each represent 0 and X represents an alkylidene group, in particular an isopropylidene group.

[0099] Furthermore, a case in which “a” and “b” each represent 1 and X represents a single bond or an alkylene group with 1 to 8 carbon atoms, or a case in which “a” and “b” each represent 1 and X represents an alkylidene group, in particular an isopropylidene group, is preferred, as the scratch resistance of the molded part can be improved with the polycarbonate-based resin composition.

[0100] Specific examples of the repetition unit represented by formula (I) include repetition units represented by the following general formulas (Ii) to (I-iv).

[0101] In the aromatic polycarbonate-based resin (A-2), the repeating units represented by formula (I) can be used individually or in combination with one another. In particular, the following aspects are given, for example: an aspect in which the resin is formed only from the repeating unit represented by general formula (Ii); and an aspect in which the resin is formed from a combination of the repeating unit represented by general formula (Ii) and one or more species selected from the group consisting of the repeating units represented by general formulas (I-ii) to (I-iv). Such an aromatic polycarbonate-based resin (A-2) can be readily prepared by an interfacial polymerization process in which a polycarbonate oligomer, to be described later, is pre-prepared.

[0102] The aromatic polycarbonate-based resin (A-2) preferably contains, in addition to the repeating unit represented by formula (I), a polyorganosiloxane block structure with a repeating unit. An example of such a repeating unit is the repeating unit represented by the following formula (III):

[0103] where in formula (III) R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms or an aryl group with 6 to 12 carbon atoms.

[0104] Examples of the halogen atom, the R 3 and R 4 In formula (III) each independent of the others, they comprise a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0105] Examples of the alkyl group with 1 to 6 carbon atoms, which R 3 and R 4Each of which can be represented independently of the others, includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups and various hexyl groups.

[0106] Examples of the alkoxy group with 1 to 6 carbon atoms, which R 3 and R 4 Each of which can be represented independently of the others, includes alkoxy groups whose alkyl group residues are the alkyl groups mentioned above.

[0107] Examples of the aryl group with 6 to 12 carbon atoms, which R 3 and R 4 Each, representing a group independently of the other, comprises a phenyl group and a naphthyl group.

[0108] R 3 and R 4each preferably represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms or an aryl group with 6 to 12 carbon atoms, and each more preferably represents a methyl group.

[0109] If the aromatic polycarbonate-based resin (A-2) contains the polyorganosiloxane block comprising the repeating unit represented by formula (III), the average number of repeats of the polyorganosiloxane block in the aromatic polycarbonate-based resin (A-2) is preferably 20 to 100, more preferably 25 to 95, more preferably 28 to 90, and still more preferably 30 to 90. If the average number of repeats is within the above-mentioned ranges, the impact strength of a polycarbonate-polyorganosiloxane copolymer can be improved.

[0110] The term "average number of polyorganosiloxane block repetitions" refers to the average number of -SiR 3 R 4 -groups per polyorganosiloxane block present between the two nearest polycarbonate bonds in the main chain of the aromatic polycarbonate-based resin (A-2). Furthermore, the average number of repeats of the repeating unit represented by formula (III) in the polyorganosiloxane block is the average number of repeats n-1 of the polyorganosiloxane block.

[0111] The average number of repetitions “n” of the repeating unit represented by formula (III) in the aromatic polycarbonate-based resin (A-2) is calculated by nuclear magnetic resonance (NMR) measurement.

[0112] The repeating unit represented by formula (III) in the aromatic polycarbonate-based resin (A-2) is preferably incorporated into the aromatic polycarbonate-based resin (A-2) as a structural unit represented by one of the following formulas (III-I) to (III-III), wherein in formulas (III-I) to (III-III) R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or an aryl group with 6 to 12 carbon atoms, and several R 3 to R 6 may be identical or different from each other, Y-R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R 9 -O- or -R 7 OR 10 -O- represents, where several Y-groups can be the same or different from each other, R 7a single bond, a linear, branched or cyclic alkylene group, -R 71 R 72 -, represents a substituted or unsubstituted arylene group or a diarylene group, R 71 represents a linear, branched, or cyclic alkylene group, R 72 represents a substituted or unsubstituted arylene group, R 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, R 9 represents a diarylene group, R 10 a linear, branched or cyclic alkylene group or a diarylene group, β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide, 'n' represents an integer of 31 or greater and less than 91, and 'p' represents an integer of 1 or greater and n-2 or less.

[0113] Examples of the halogen atom, the R 3 to R 6 Each, representing one another independently, comprises a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0114] Examples of the alkyl group with 1 to 6 carbon atoms, which R 3 to R 6 Each of which can be represented independently of the others, includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups and various hexyl groups.

[0115] Examples of the alkoxy group with 1 to 6 carbon atoms, which R 3 to R 6 Each of which can be represented independently of the others, includes alkoxy groups whose alkyl group residues are the alkyl groups mentioned above.

[0116] Examples of the aryl group with 6 to 12 carbon atoms, which R 3 to R 6 Each, representing a group independently of the other, comprises a phenyl group and a naphthyl group.

[0117] R 3 to R 6 each preferably represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms or an aryl group with 6 to 12 carbon atoms.

[0118] R 3 to R 6 In formula (III-I), formula (III-II) and / or formula (III-III), each preferably represents a methyl group.

[0119] In -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -R 7 COO-R 9 -O- or -R 7 OR 10 -O-, represented by Y, is R 7 bonded to a Si atom. In -COO-, represented by Y, a C atom is bonded to the Si atom.

[0120] The linear or branched alkylene group, represented by R 7 in -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -R 7 COO-R9 -O- or -R 7 OR 10 -O-, represented by Y, is, for example, an alkylene group with 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. The cyclic alkylene group, represented by R 7 , is, for example, a cycloalkylene group with 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms.

[0121] -R 71 R 72 -, represented by R 7 , can have a substituent, such as an alkoxy group or an alkyl group, attached to the R 72 exhibit the depicted arylene group, and a specific structure thereof may, for example, be a structure represented by the following formula (1) or (2). If R7 -R 71 R 72 -represents the one represented by R 71The alkylene group shown is bonded to a Si atom, where in formulas (1) and (2) “v” represents a positive integer and is typically an integer from 1 to 6.

[0122] The one through each of R 7 , R 9 and R 10 The diarylene group shown is a group obtained by joining two arylene groups, directly or via a divalent organic group, and is in particular a group with a structure defined by -Ar 1 -W-Ar 2 - is represented. Herein are Ar(1 ) and Ar(2 ) Each represents an arylene group, and W stands for a single bond or a divalent organic group. Examples of divalent organic groups represented by W include an isopropylidene group, a methylene group, a dimethylene group, and a trimethylene group.

[0123] Examples of the results achieved by each of R 7 , Ar 1 and Ar 2The depicted arylene groups comprise arylene groups with 6 to 14 ring-forming carbon atoms each, such as a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. These arylene groups may each have an optional substituent, such as an alkoxy group or an alkyl group.

[0124] The by R 8 The alkyl group represented is a linear or branched alkyl group with 1 to 8, preferably 1 to 5, carbon atoms. The group represented by R 8 The alkenyl group represented, for example, is a linear or branched alkenyl group with 2 to 8, preferably 2 to 5, carbon atoms. The one represented by R 8 The aryl group represented is, for example, a phenyl group or a naphthyl group. The one represented by R 8 The depicted aralkyl group is, for example, a phenylmethyl group or a phenylethyl group.

[0125] The by R 10The linear, branched, or cyclic alkylene group shown is the same as that of R. 7 .

[0126] Y preferentially sets -R 7 O- represents, where R 7 -R 71 R' 2 - represents. R 7 more preferably represents a phenol-based compound residue, which in particular has an alkyl group, and more preferably an organic residue derived from allylphenol or an organic residue derived from eugenol.

[0127] With respect to “p” in formula (III-II), p = np-2 is preferably satisfied.

[0128] β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide, and examples include divalent groups represented by the following formulas (3) to (7).

[0129] A block unit represented by the following formula (III-I) is, for example, a block unit represented by any of the following formulas (III-I-1) to (III-I-11): where in formulas (III-I-1) to (III-I-11) R 3 to R 6 , “n” and R 8 the same as described above, and preferred examples are also the same as described above, and “q” and “r” each independently represent a positive integer and typically each represent an integer from 1 to 6.

[0130] Of these, the block unit represented by formula (III-I-1) is preferred from the point of view of the ease with which a polyorganosiloxane can be polymerized. Furthermore, the block unit represented by formula (III-I-2) or the block unit represented by formula (III-I-3) is preferred from the point of view of easy availability.

[0131] Furthermore, another preferred aspect of the polyorganosiloxane block is, for example, a block unit represented by the following formula (III-IV): where in formula (III-IV) R 3 and R 4 have the same meanings as described above and s×t is equivalent to the above-mentioned “n”.

[0132] If the aromatic polycarbonate-based resin (A-2) contains the repeating unit represented by formula (III), the content of the repeating unit represented by formula (III) in the aromatic polycarbonate-based resin (A-2) is preferably 0.5 to 8 wt%, more preferably 2 to 7.5 wt%, more preferably 4 to 7 wt% and most preferably 5 to 7 wt%.

[0133] In the aromatic polycarbonate-based resin (A-2), the term “content of the repeating unit represented by formula (I)” refers to the percentage of the mass of the repeating unit represented by formula (I) to the total mass of the repeating unit represented by formula (I) and, if necessary, the repeating unit represented by formula (III). The same applies to the “content of the repeating unit represented by formula (III)”.

[0134] The content of the repeating unit represented by formula (I) in the aromatic polycarbonate-based resin (A-2) is calculated by nuclear magnetic resonance (NMR) measurement. In particular, 1an H-NMR measurement was performed and the content was calculated from the integrated values ​​of a peak derived from the repeating unit represented by formula (I) and a peak derived from the repeating unit represented by formula (III).

[0135] The aromatic polycarbonate-based resin (A-2) may contain a structural unit that differs from the repeating unit represented by formula (I) and the repeating unit represented by formula (III). Such a unit is, for example, a terminal structure derived from an end stop to be described later.

[0136] The viscosity-averaged molecular weight (Mv) of the aromatic polycarbonate-based resin (A-2) is preferably 15,000 to 25,000, more preferably 16,000 to 24,000, further more preferably 16,500 to 23,000 and particularly preferably 17,000 to 22,000 with regard to its mechanical properties and formability.

[0137] The viscosity-averaged molecular weight (Mv) of the aromatic polycarbonate-based resin (A-2) can be measured using the same method as that of the aromatic polycarbonate-based resin (A-1). <Verfahren zur Herstellung von aromatischem Polycarbonat-basiertem Harz (A-2)>

[0138] The aromatic polycarbonate-based resin (A-2) can be produced by a known manufacturing process, such as the interfacial polymerization process (phosgene process) described above, the pyridine process, or the ester exchange process. In particular, when using the interfacial polymerization process, the step of separating an organic phase containing the aromatic polycarbonate resin (A-2) from an aqueous phase containing an unreacted product, catalyst residue, and the like becomes simpler. Therefore, the separation of the organic phase containing the aromatic polycarbonate resin (A-2) from the aqueous phase in each washing step, for example, based on alkaline washes, acid washes, or pure water washes, is simplified. Accordingly, the aromatic polycarbonate resin (A-2) is obtained efficiently.

[0139] Specifically, the polycarbonate-based resin can be prepared by: dissolving a previously prepared polycarbonate oligomer using a compound based on a divalent phenol, represented by the following formula (i), and a polyorganosiloxane as required in a water-insoluble organic solvent (e.g., methylene chloride); adding a solution of a compound based on a divalent phenol (e.g., bisphenol A) in an aqueous solution of an alkaline compound (e.g., aqueous sodium hydroxide) to the solution; and subjecting the mixture to an interfacial polycondensation reaction using a tertiary amine (e.g., triethylamine) or a quaternary ammonium salt (e.g., trimethylbenzylammonium chloride) as a polymerization catalyst in the presence of an end-stopper (a monovalent phenol, such as p-tert-butylphenol), where in formula (i) R 1 , R 2, X, “a” and “b” are defined as above and preferred examples are also the same as described above.

[0140] Examples of the divalent phenol-based compound represented by formula (i) include: bis(hydroxyphenyl)alkane-based compounds such as 2,2-bis(4-hydroxyphenyl)propane [bisphenol A (BPA)], bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxydiphenyl; bis(4-hydroxyphenyl)cycloalkanes; bis(4-hydroxyphenyl)oxide; bis(4-hydroxyphenyl)sulfide; bis(4-hydroxyphenyl)sulfone; bis(4-hydroxyphenyl)sulfoxide; and bis(4-hydroxyphenyl)ketone. These divalent phenol-based compounds can be used alone or as a mixture thereof.

[0141] Among these, divalent phenols based on bis(hydroxyphenyl)alkanes are preferred, with bisphenol A being more strongly preferred.

[0142] If the aromatic polycarbonate-based resin (A-2) contains the repeating unit represented by formula (III), a process described in JP 2014-80462 A, for example, can be used as a method for producing the aromatic polycarbonate-based resin (A-2).

[0143] The polyorganosiloxane used as a raw material can be one represented by the following general formulas (iii-i), (iii-ii) and / or (iii-iii): where R 3 to R 6 , Y, β, “n” and “p” as described above.

[0144] Specific examples of R 3 to R 6 , Y, β, “n” and “p” as well as preferred examples thereof are also as described above.

[0145] Z represents a hydrogen atom or a halogen atom, and multiple Zs can be identical or different from each other.

[0146] Examples of the polyorganosiloxane represented by the general formula (iii-i) include compounds represented by the following general formulas (iii-i-1) to (iii-i-11): where in the general formulas (iii-i-1) to (iii-i-11) R 3 to R 6 , n and R 8 the same as described above, and preferred examples are also the same as described above, and “q” and “r” each independently represent a positive integer and typically each represent an integer from 1 to 6.

[0147] Among these, a phenol-modified polyorganosiloxane represented by the general formula (iii-i-1) is preferred from the point of view of the ease with which the polyorganosiloxane polymerizes. Furthermore, an α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, which is a type of compound of the general formula (iii-i-2), or an α,ω-bis[3-(4-hydroxy-3-methoxyphenyl)propyl]polydimethylsiloxane, which is a type of compound of the general formula (iii-i-3), is preferred from the point of view of ease of availability.

[0148] In addition to the above, a compound represented by the following general formula (iii-iv) may be included as a polyorganosiloxane starting material:

[0149] where R 3 , R 4 , “s” and “t” have the same meanings as above. [Polycarbonate-based resin composition]

[0150] The polycarbonate-based resin composition of the present invention comprises the above-mentioned aromatic polycarbonate resin (A-1) and the aromatic polycarbonate resin (A-2) as well as, if required, any other component.

[0151] Examples of the other components can be additives such as a hydrolysis resistance agent, an antioxidant, a UV absorber, a flame retardant, a flame retardant aid, a reinforcing material, a filler, an elastomer to improve impact resistance, a pigment, and a dye.

[0152] The polycarbonate-based resin composition may contain an antioxidant, for example, to prevent its oxidative decomposition during melting and thus prevent discoloration or the like due to oxidative decomposition.

[0153] The antioxidant content is preferably 0.001 to 0.5 parts by mass, more preferably 0.01 to 0.3 parts by mass, and even more preferably 0.02 to 0.2 parts by mass, based on 100 parts by mass of the polycarbonate-based resin composition. If the antioxidant content is within the aforementioned ranges, sufficient antioxidant effect is achieved, and mold contamination during molding can be suppressed.

[0154] A method for producing the polycarbonate-based resin composition of the present invention is not particularly limited, provided that the method includes a step of mixing the aforementioned aromatic polycarbonate resin (A-1) and the aromatic polycarbonate resin (A-2), as well as any other optional components. The polycarbonate-based resin composition can, for example, be produced by mixing the aforementioned aromatic polycarbonate resin (A-1) and the aromatic polycarbonate resin (A-2), as well as any other optional component, with a mixer or the like, and then melting and kneading the mixture.Melting and kneading can be carried out by a typically used method, for example, by using a belt mixer, a Henschel mixer, a Banbury mixer, a drum mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, or a multi-screw extruder. The heating temperature at the time of melting and kneading is suitably selected from the range of, for example, 150 °C to 300 °C, preferably from about 220 °C to about 300 °C.

[0155] In the polycarbonate-based resin composition, the mass ratio ((A-1):(A-2)) between the aromatic polycarbonate resin (A-1) and the aromatic polycarbonate resin (A-2) is preferably 45:55 to 95:5, more preferably 50:50 to 90:10, even more preferably 55:45 to 85:15 and yet more preferably 60:40 to 80:20.

[0156] With regard to improving the scratch resistance of the resin composition, the content of the structural unit represented by formula (II) in the total content of the units represented by formulas (I) to (III) in the polycarbonate-based resin composition is preferably 1.0 to 25 wt%, more preferably 3.0 to 23 wt%, further more preferably 5.0 to 21 wt%, and still more preferably 6.0 to 20 wt%.

[0157] The polycarbonate-based resin composition preferably contains the repeating unit represented by formula (III) to improve scratch resistance. The content of the repeating unit represented by formula (III) in the total content of the repeating units represented by formulas (I) to (III) in the polycarbonate-based resin composition is preferably 0.1 to 3.2 wt%, more preferably 0.5 to 3.0 wt%, even more preferably 0.8 to 3.0 wt%, and yet more preferably 1.0 to 2.5 wt%.

[0158] In the polycarbonate-based resin composition, the term "content of the structural unit represented by formula (II)" refers to the percentage of the mass of the structural unit represented by formula (II) in relation to the total mass of the structural unit represented by formula (II) and the repeating unit represented by formula (I) and, where applicable, the repeating unit represented by formula (III). The same applies to the "content of the repeating unit represented by formula (III)."

[0159] The polycarbonate-based resin composition of the present invention can improve the scratch resistance of a molded article made therefrom.

[0160] Scratch resistance can be assessed using the pencil scratch test. The pencil scratch test of the molded article made from the above-mentioned polycarbonate-based resin composition, assessed according to JIS K5600-5-4:1999, is preferably HB or higher.

[0161] The polycarbonate-based resin composition of the present invention can be used appropriately in a scratch-resistant application, since a molded article produced therefrom can exhibit improved, excellent scratch resistance.

[0162] The scratch-resistant application is, for example, a structural body whose outer surface is formed from the aforementioned polycarbonate-based resin composition, and more specific examples include a plastic window, a touch panel, an internal feeder, an external feeder, an internal or external part of a vehicle, a housing, an electrical appliance, a building material, and automated office equipment. The polycarbonate-based resin composition of the present invention can be suitably used to manufacture the aforementioned articles. 2. Molded articles

[0163] The molded article according to the invention comprises the polycarbonate-based resin composition mentioned above. The molded article can be produced using a melt-formed product of the polycarbonate-based resin composition or a pellet obtained therefrom by melting and kneading as raw material by an injection molding process, an injection compression molding process, an extrusion molding process, a blow molding process, a compression molding process, a vacuum forming process, an expansion molding process, or the like. In particular, the molded article is preferably produced by an injection molding process or an injection compression molding process using a pellet obtained by melting and kneading.

[0164] The thickness of the molded part can be arbitrarily determined depending on the application. Particularly when transparency of the molded part is required, the thickness is preferably 0.2 mm to 4.0 mm, more preferably 0.3 mm to 3.0 mm, and even more preferably 0.3 mm to 2.0 mm. If the thickness of the molded part is 0.2 mm or more, no deformation occurs, and thus satisfactory mechanical strength is achieved. Furthermore, high transparency is achieved if the thickness of the molded part is 4.0 mm or less.

[0165] The molded article formed from the polycarbonate-based resin composition of the present invention can be used, for example, as a plastic window, touch panel, internal conduit, external conduit, internal or external part of a vehicle, as a housing, part of an electrical appliance, building material or part of an office appliance. Examples

[0166] Examples of the present invention are described below. The present invention is by no means limited to these examples. The measurements and evaluations in the respective examples were carried out using the following methods. 1. Measurement of the viscosity-averaged molecular weight (Mv)

[0167] The viscosity-averaged molecular weight (Mv) was calculated using the following equation (Schnell equation) after the intrinsic viscosity [η] had been determined by measuring the viscosity of a methylene chloride solution (concentration: g / L) at 20 °C using an Ubbelohde viscometer. [η]=1.23×10−5Mv0.83

[0168] 2. Conditions for 1 H-NMR measurement Nuclear magnetic resonance (NMR) scanner: “ECA-500” manufactured by JEOL RESONANCE Co.,Ltd. Probe: 50TH5AT / FG2 Messkern: 1 H Observation range: from -5 ppm to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° NMR sample tubes: 5 mmϕ Sample quantity: from 30 mg to 40 mg Solvent: Deuterochloroform Amount of solvent: 0,4 ml Measurement temperature: 25 °C Number of scans: 256 Chemical shift correction: The peak of a methyl group originating from Bisphenol A in a sample is set to a reference value of 1.68 ppm.

[0169] 3. Determination of the composition ratio of a polycarbonate-based resin composition

[0170] The 1H-NMR measurement of a polycarbonate-based resin composition was performed under the same measurement conditions as described above, and the structure of the polycarbonate-based resin composition was assigned. Synthesis Example 1 (Synthesis of cyclohexyl diphenolate)

[0171] 620 mL of cyclohexanol, 111 g (388 mmol) of diphenolic acid, and 5.69 g (58.0 mmol) of sulfuric acid were placed in a 1-liter flask to prepare a reaction liquid, and a magnetic stir bar, a thermometer, and a reflux condenser were installed. The temperature of the reaction liquid was raised to 80 °C using an oil bath, and the liquid was stirred with a magnetic stirrer for 19 hours. The disappearance of the diphenolic acid was confirmed by thin-layer chromatography (TLC), and the temperature of the reaction liquid was then brought back to room temperature. 600 mL of toluene were added to the reaction liquid, and the mixture was washed twice with 800 mL of baking soda (saturated aqueous sodium bicarbonate solution) and once with 800 mL of brine (saturated salt solution).The organic phase was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 316 g of a light brown liquid as the crude product. The resulting crude product was purified using a silica gel column (neutral silica gel: 1.05 kg, solvent: heptane / ethyl acetate = 4:1) to obtain 263 g of a pale yellow liquid. The resulting pale yellow liquid was subjected to eight azeotropy cycles with a mixed solvent of acetonitrile and water in a 2:1 ratio (300 g). The precipitated solid was recovered by reduced-pressure filtration and suspended and washed twice in 500 mL of hexane. The resulting solid was dried under reduced pressure at 40 °C for 12 hours to obtain 113 g of a white cyclohexyl diphenolate solid. Synthesis Example 2 (Synthesis of Cyclopentyldiphenolate)

[0172] 694 mL of cyclopentanol, 124 g (434 mmol) of diphenolic acid, and 6.37 g (65.0 mmol) of sulfuric acid were placed in a 1-liter flask to obtain a reaction liquid, and a magnetic stir bar, a thermometer, and a reflux cooling tube were installed. The temperature of the reaction liquid was raised to 80 °C using an oil bath, and the liquid was stirred with a magnetic stirrer for 19 hours. The disappearance of the diphenolic acid was confirmed by thin-layer chromatography (TLC), and the temperature of the reaction liquid was then brought back to room temperature. 600 mL of toluene were added to the reaction liquid, and the mixture was washed twice with 600 mL of bacsoda (saturated aqueous solution of sodium bicarbonate) and once with 600 mL of brine (saturated salt solution).The organic phase was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 172 g of a light brown liquid as the crude product. The resulting crude product was dissolved in a mixture (350 g) of hexane and ethyl acetate in a 9:1 ratio, and the solution was allowed to stand overnight at room temperature. The precipitated solid was recovered by reduced-pressure filtration and dried for 12 hours at 40 °C under reduced pressure to obtain a white solid (55.3 g) of cyclopentyldiphenolate. The filtrate was allowed to stand overnight at 4 °C, and the precipitated solid was recovered by reduced-pressure filtration. The recovered solid was dried for 12 hours at 40 °C under reduced pressure to obtain a white solid (38.5 g) of cyclopentyldiphenolate.The filtrate was concentrated under reduced pressure, and the resulting liquid was dissolved in chloroform (100 g). Toluene (180 g) was added to the solution, and the mixture was allowed to stand overnight at 4 °C. The precipitated solid was recovered by filtration under reduced pressure and suspended and washed twice in hexane. The washed solid was dried for 12 hours at 50 °C under reduced pressure to yield a white solid (14.4 g) of cyclopentyldiphenolate. A total of 108.2 g of cyclopentyldiphenolate was obtained. Synthesis Example 3 (Synthesis of cyclohexyl-2,2-bis(4-hydroxyphenyl)propanoate)

[0173] Phenol (131 g, 1.39 mol), pyruvic acid (60.3 g, 0.68 mol), and ion-exchanged water (45.6 g) were placed in a 1-liter four-necked flask, and a magnetic stir bar and thermometer were installed. The flask was cooled with ice, and 95% sulfuric acid (112 g, 1.14 mol) was added dropwise over 50 minutes. The temperature of the reaction liquid was then raised to room temperature, and the liquid was stirred for 14 hours. Diethyl ether (11) was added to the reaction liquid, and the mixture was washed once with ion-exchanged water (11). The organic layer was extracted twice with 0.1 M aqueous sodium hydroxide solution (11). The pH of the extract was adjusted to 2 with 1 M hydrochloric acid, and the extract was extracted twice with diethyl ether (11). The extract was dried over sodium sulfate and then dried under reduced pressure to obtain a light brown solid (139 g).The light brown solid (130 g), cyclohexanol (2.011 mol), and 95% sulfuric acid (27.7 g, 0.28 mol) were placed in a 5-liter four-necked flask, and a stirring plate, a thermometer, and a reflux condenser were installed. The temperature of the reaction liquid was then raised to 100 °C and stirred for 15 days. The reaction liquid was diluted twice with diethyl ether and washed twice with baking soda solution, once with water, and once with brine. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to obtain a crude product (815 g). The crude product was purified three times using a silica gel column (neutral silica gel: 5.0 kg, solvent: chloroform / ethyl acetate = 1 / 0→0 / 1).The purified product was then dissolved in a 1:1 solution of chloroform and ethyl acetate and the solution was subjected to recrystallization to obtain a white solid (52.9 g) of cyclohexyl-2,2-bis(4-hydroxyphenyl)propanoate. Synthesis Example 4 (Synthesis of Diphenolate Methyl Ester)

[0174] 500 mL of methanol, 50 g (175 mmol) of diphenolic acid, and 2.5 mL of sulfuric acid were placed in a 1-liter flask, and a magnetic stir bar, a thermometer, and a reflux condenser were inserted. The temperature of the reaction liquid was raised to 70 °C using an oil bath, and the liquid was stirred with a magnetic stirrer for 5 hours. The temperature of the reaction liquid was then brought back to room temperature, and the liquid was concentrated under reduced pressure. Ethyl acetate was added to the reaction liquid, and the mixture was washed three times with 100 mL of baking soda solution and twice with 100 mL of water. The solution was concentrated under reduced pressure to obtain 55.3 g of a colorless solid as the crude product. The resulting crude product and 100 mL of toluene were placed in a 200 mL flask, and a magnetic stir bar, a thermometer, and a reflux condenser were inserted.The temperature of the reaction liquid was raised using the oil bath until the toluene refluxed, followed by complete dissolution of the crude product in toluene. The solution was then allowed to cool to room temperature, and the precipitated solid was recovered by filtration under reduced pressure. The recovered solid was dissolved again in 100 ml of toluene, and the process was repeated. This yielded 32.7 g of a white solid of methyl diphenolate. Synthesis Example 5 (Synthesis of Methyl 2,2-bis(4-hydroxy-3-methylphenyl)propanoate)

[0175] Methyl 2,2-bis(4-hydroxy-3-methylphenyl)propanoate was prepared in the same way as in Synthesis Example 3, except that phenol was replaced by o-cresol. Synthesis Example 6 (Synthesis of Polycarbonate Oligomer 1)

[0176] Sodium dithionite (Na₂S₂O₄) was added to a 5.6 wt% aqueous sodium hydroxide solution, resulting in a bisphenol A (BPA) concentration of 2,000 ppm. BPA was dissolved in this solution, bringing the BPA concentration to 13.5 wt%. Thus, a solution of BPA in aqueous sodium hydroxide was prepared.

[0177] A solution of BPA in aqueous sodium hydroxide solution, methylene chloride, and phosgene was continuously passed through a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m at flow rates of 40 l / h, 13 l / h, and 4.5 kg / h, respectively. The tubular reactor had a jacket, and the temperature of the reaction liquid was maintained at 40 °C or lower by passing cooling water through the jacket. An aqueous phase was separated and removed by continuously withdrawing the reaction liquid from the tubular reactor and allowing it to stand. Subsequently, a methylene chloride phase was collected.

[0178] The resulting solution of the polycarbonate oligomer in methylene chloride had a concentration of 301 g / l and a chloroformate group concentration of 1.03 mol / l. Synthesis Example 7 (Synthesis of Polycarbonate Oligomer 2)

[0179] Sodium dithionite was added to 5.6% by mass of aqueous sodium hydroxide solution, resulting in a concentration of bisphenol A (BPA) of 2,000 ppm. BPA was dissolved in this solution, bringing the BPA concentration to 13.5% by mass. Thus, a solution of BPA in aqueous sodium hydroxide solution was prepared.

[0180] A solution of BPA in aqueous sodium hydroxide solution, methylene chloride, and phosgene was continuously passed through a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m at flow rates of 40 L / h, 15 L / h, and 4.0 kg / h, respectively. The tubular reactor had a jacket, and the temperature of the reaction liquid was maintained at 40 °C or lower by passing cooling water through the jacket. The reaction liquid exiting the tubular reactor was continuously fed into a baffled reactor vessel with a capacity of 40 L. Solutions of BPA in aqueous sodium hydroxide solution, 25 wt% aqueous sodium hydroxide solution, water, and a 1 wt% aqueous triethylamine solution were added to the reactor at flow rates of 2.8 L / h, 0.07 L / h, 17 L / h, and 0.64 L / h, respectively, to carry out a reaction.An aqueous phase was separated and removed by continuously withdrawing the reaction liquid that overflowed the reactor vessel and allowing the liquid to settle. Subsequently, a methylene chloride phase was collected.

[0181] The polycarbonate oligomer obtained in this way had a concentration of 341 g / l and a chloroformate group concentration of 0.71 mol / l. <Herstellungsbeispiel 1: Herstellung eines aromatischen Polycarbonat-basierten Harzes (A-1-1)>

[0182] 255 milliliters of the solution of polycarbonate oligomer 1, prepared in Synthesis Example 6, 495 ml of methylene chloride, 21.2 g of cyclohexyl diphenolate, prepared in Synthesis Example 1 described above, and 178 µl of triethylamine (TEA) were placed in a 1-liter baffled flask. With stirring, aqueous sodium hydroxide solution (obtained by dissolving 3.3 g of sodium hydroxide in 38.1 ml of pure water) was added to the flask, and the mixture was subjected to a reaction for 20 minutes to obtain a polymerization fluid.

[0183] A solution of p-tert-butylphenol (PTBP) in methylene chloride (obtained by dissolving 1.84 g of PTBP in 13 ml of methylene chloride) and a solution of BPA in aqueous sodium hydroxide solution (obtained by dissolving 17.9 g of BPA in an aqueous solution obtained by dissolving 9.9 g of sodium hydroxide and 36 mg of sodium dithionite in 145 ml of pure water) were added to the polymerization liquid, and the mixture was subjected to a polymerization reaction for 40 minutes.

[0184] To dilute the reaction liquid, 100 milliliters of methylene chloride were added, and the mixture was stirred for 10 minutes. The mixture was then separated into an organic phase containing an aromatic polycarbonate-based resin (A-1-1) and an aqueous phase containing excess amounts of BPA and sodium hydroxide, and the organic phase was isolated. The resulting solution of the aromatic polycarbonate resin (A-1-1) in methylene chloride was washed successively with 0.03 mol / l aqueous sodium hydroxide solution and 0.2 mol / l hydrochloric acid, each at 15 vol% based on the solution. The washed product was then repeatedly washed with pure water until the electrical conductivity of its aqueous phase after washing was 5 µS / cm or less. The washed organic phase was converted into flakes by evaporation of the solvent using an evaporator.The aromatic polycarbonate-based resin (A-1-1) was obtained as a white product. The aromatic polycarbonate-based resin (A-1-1) had a content of the structural unit represented by formula (II) of 21.3 wt% and a viscosity-averaged molecular weight (Mv) of 22,100. <Herstellungsbeispiel 2: Herstellung eines aromatischen Polycarbonatharzes (A-1-2)>

[0185] 279 ml of the solution of polycarbonate oligomer 1 prepared in Synthesis Example 6, 541 ml of methylene chloride, 10.5 g of the cyclohexyl diphenolate prepared in Synthesis Example 1 described above, and 195 µl of triethylamine (TEA) were placed in a 1-liter baffle-equipped flask. With stirring, aqueous sodium hydroxide solution (obtained by dissolving 3.6 g of sodium hydroxide in 41.6 ml of pure water) was added to the flask, and the mixture was subjected to a reaction for 20 minutes to obtain a polymerization fluid.

[0186] A solution of p-tert-butylphenol (PTBP) in methylene chloride (obtained by dissolving 1.94 g of PTBP in 13 ml of methylene chloride) and a solution of BPA in aqueous sodium hydroxide solution (obtained by dissolving 21.7 g of BPA in an aqueous solution obtained by dissolving 10.9 g of sodium hydroxide and 43 mg of sodium dithionite in 159 ml of pure water) were added to the polymerization liquid, and the mixture was subjected to a polymerization reaction for 40 minutes.

[0187] To dilute the reaction liquid, 30 milliliters of methylene chloride were added, and the mixture was stirred for 10 minutes. The mixture was then separated into an organic phase containing an aromatic polycarbonate-based resin (A-1-2) and an aqueous phase containing excess amounts of BPA and sodium hydroxide, and the organic phase was isolated. The resulting solution of the aromatic polycarbonate resin (A-1-2) in methylene chloride was washed successively with 0.03 mol / l aqueous sodium hydroxide solution and 0.2 mol / l hydrochloric acid, each at 15 vol% based on the solution. The washed product was then repeatedly washed with pure water until the electrical conductivity in the aqueous phase after washing was 5 µS / cm or less. The washed organic phase was converted into flakes by evaporation of the solvent using an evaporator.The aromatic polycarbonate-based resin (A-1-2) was obtained as a white product. The aromatic polycarbonate-based resin (A-1-2) had a content of the structural unit represented by formula (II) of 10.6 wt% and a viscosity-averaged molecular weight (Mv) of 21,600. <Herstellungsbeispiel 3: Herstellung eines aromatischen Polycarbonatharzes (A-1-3)>

[0188] 58 mL of the solution of polycarbonate oligomer 1 prepared in Synthesis Example 6, 19 mL of methylene chloride, 4.15 g of cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate prepared in Synthesis Example 3 described above, and 41 µL of triethylamine (TEA) were placed in a 300 mL baffled flask. With stirring, aqueous sodium hydroxide solution (obtained by dissolving 0.9 g of sodium hydroxide in 9.8 mL of pure water) was added to the flask, and the mixture was subjected to reaction for 20 minutes to obtain a polymerization fluid.

[0189] A solution of p-tert-butylphenol (PTBP) in methylene chloride (obtained by dissolving 0.34 g PTBP in 2.4 ml methylene chloride) and a solution of BPA in aqueous sodium hydroxide solution (obtained by dissolving 4.5 g BPA in an aqueous solution obtained by dissolving 2.2 g sodium hydroxide and 9 mg sodium dithionite in 32 ml pure water) were added to the polymerization liquid, and the mixture was subjected to a polymerization reaction for 40 minutes.

[0190] To dilute the reaction liquid, 105 ml of methylene chloride was added, and the mixture was stirred for 10 minutes. The mixture was then separated into an organic phase containing an aromatic polycarbonate-based resin (A-1-3) and an aqueous phase containing excess amounts of BPA and sodium hydroxide, and the organic phase was isolated. The resulting solution of the aromatic polycarbonate resin (A-1-3) in methylene chloride was washed successively with 0.03 mol / l aqueous sodium hydroxide solution and 0.2 mol / l hydrochloric acid, each at 15 vol% based on the solution. The washed product was then repeatedly washed with pure water until the electrical conductivity in the aqueous phase after washing was 5 µS / cm or less. The washed organic phase was converted into flakes by evaporation of the solvent using an evaporator.The aromatic polycarbonate-based resin (A-1-3) was obtained as a white product. The aromatic polycarbonate-based resin (A-1-3) had a content of the structural unit represented by formula (II) of 23.0 wt% and a viscosity-averaged molecular weight (Mv) of 22,300. <Herstellungsbeispiel 4: Herstellung eines aromatischen Polycarbonatharzes (A-1-4)>

[0191] 283 ml of the solution of polycarbonate oligomer 1 prepared in Synthesis Example 6, 94 ml of methylene chloride, 19.8 g of cyclopentyldiphenolate prepared in Synthesis Example 2 described above, and 198 µl of triethylamine (TEA) were placed in a 1-liter baffle-equipped flask. With stirring, aqueous sodium hydroxide solution (obtained by dissolving 3.7 g of sodium hydroxide in 42.2 ml of pure water) was added to the flask, and the mixture was subjected to a reaction for 20 minutes to obtain a polymerization fluid.

[0192] A solution of p-tert-butylphenol (PTBP) in methylene chloride (obtained by dissolving 1.56 g of PTBP in 11 ml of methylene chloride) and a solution of BPA in aqueous sodium hydroxide solution (obtained by dissolving 20.9 g of BPA in an aqueous solution obtained by dissolving 11 g of sodium hydroxide and 42 mg of sodium dithionite in 161 ml of pure water) were added to the polymerization liquid, and the mixture was subjected to a polymerization reaction for 40 minutes.

[0193] To dilute the reaction liquid, 450 milliliters of methylene chloride were added, and the mixture was stirred for 10 minutes. The mixture was then separated into an organic phase containing an aromatic polycarbonate-based resin (A-1-4) and an aqueous phase containing excess amounts of BPA and sodium hydroxide, and the organic phase was isolated. The resulting solution of the aromatic polycarbonate resin (A-1-4) in methylene chloride was washed successively with 0.03 mol / l aqueous sodium hydroxide solution and 0.2 mol / l hydrochloric acid, each at 15 vol% based on the solution. The washed product was then repeatedly washed with pure water until the electrical conductivity in the aqueous phase after washing was 5 µS / cm or less. The washed organic phase was converted into flakes by evaporation of the solvent using an evaporator.The aromatic polycarbonate-based resin (A-1-4) was obtained as a white product. The aromatic polycarbonate-based resin (A-1-4) had a content of the structural unit represented by formula (II) of 22.1 wt% and a viscosity-averaged molecular weight (Mv) of 25,400. < Production example 5: Production of an aromatic polycarbonate-based resin (A-1-5)>

[0194] 58 mL of the solution of polycarbonate oligomer 1 prepared in Synthesis Example 6, 19 mL of methylene chloride, 4.1 g of methyl 2,2-bis(4-hydroxy-3-methylphenyl)propanoate prepared in Synthesis Example 5 described above, and 41 µL of triethylamine (TEA) were placed in a 300 mL baffled flask. With stirring, aqueous sodium hydroxide solution (obtained by dissolving 0.8 g of sodium hydroxide in 8.7 mL of pure water) was added to the flask, and the mixture was subjected to a reaction for 20 minutes to obtain a polymerization fluid.

[0195] A solution of p-tert-butylphenol (PTBP) in methylene chloride (obtained by dissolving 0.34 g PTBP in 2.4 ml methylene chloride) and a solution of BPA in aqueous sodium hydroxide solution (obtained by dissolving 4.3 g BPA in an aqueous solution obtained by dissolving 2.3 g sodium hydroxide and 9 mg sodium dithionite in 33 ml pure water) were added to the polymerization liquid, and the mixture was subjected to a polymerization reaction for 40 minutes.

[0196] To dilute the reaction liquid, 100 milliliters of methylene chloride were added, and the mixture was stirred for 10 minutes. The mixture was then separated into an organic phase containing an aromatic polycarbonate-based resin (A-1-5) and an aqueous phase containing excess amounts of BPA and sodium hydroxide, and the organic phase was isolated. The resulting solution of the aromatic polycarbonate resin (A-1-5) in methylene chloride was washed successively with 0.03 mol / l aqueous sodium hydroxide solution and 0.2 mol / l hydrochloric acid, each at 15 vol% based on the solution. The washed product was then repeatedly washed with pure water until the electrical conductivity in the aqueous phase after washing was 5 µS / cm or less. The washed organic phase was converted into flakes by evaporation of the solvent using an evaporator.The aromatic polycarbonate-based resin (A-1-5) was obtained as a white product. The aromatic polycarbonate-based resin (A-1-5) had a content of the structural unit represented by formula (II) of 21.9 wt% and a viscosity-averaged molecular weight (Mv) of 22,200. <Herstellungsbeispiel 6: Herstellung eines aromatischen Polycarbonatharzes (A-1-6)>

[0197] 50 mL of the solution of polycarbonate oligomer 1, prepared in Synthesis Example 6, 70 mL of methylene chloride, 0.28 g of p-tert-butylphenol (PTBP), 3.4 g of methyl diphenolate, prepared in Synthesis Example 4 described above, and 35 µL of triethylamine (TEA) were placed in a 300 mL baffled flask. With stirring, aqueous sodium hydroxide solution (obtained by dissolving 0.6 g of sodium hydroxide in 7.5 mL of pure water) was added to the flask, and the mixture was subjected to reaction for 20 minutes to obtain a polymerization fluid.

[0198] A solution of BPA in aqueous sodium hydroxide solution (obtained by dissolving 3.7 g of BPA in an aqueous solution obtained by dissolving 1.6 g of sodium hydroxide and 7 mg of sodium dithionite in 24 ml of pure water) was added to the polymerization liquid, and the mixture was subjected to a polymerization reaction for 40 minutes.

[0199] To dilute the reaction liquid, 50 milliliters of methylene chloride were added, and the mixture was stirred for 10 minutes. The mixture was then separated into an organic phase containing an aromatic polycarbonate-based resin (A-1-6) and an aqueous phase containing excess amounts of BPA and sodium hydroxide, and the organic phase was isolated. The resulting solution of the aromatic polycarbonate resin (A-1-6) in methylene chloride was washed successively with 0.03 mol / l aqueous sodium hydroxide solution and 0.2 mol / l hydrochloric acid, each at 15 vol% based on the solution. The washed product was then repeatedly washed with pure water until the electrical conductivity in the aqueous phase after washing was 5 µS / cm or less. The washed organic phase was converted into flakes by evaporation of the solvent using an evaporator.The aromatic polycarbonate-based resin (A-1-6) was obtained as a white product. The aromatic polycarbonate-based resin (A-1-6) had a content of the structural unit represented by formula (II) of 18.6 wt% and a viscosity-averaged molecular weight (Mv) of 10,100. <Herstellungsbeispiel 7: Herstellung eines aromatischen Polycarbonatharzes (A-2-1)>

[0200] 15 liters of the solution of polycarbonate oligomer 2 prepared in Synthesis Example 7, 8.6 liters of methylene chloride (a solution obtained by dissolving 400 g of a terminal o-allylphenol-modified polydimethylsiloxane with an average chain length “n” of 37 in 2 liters of methylene chloride), and 11.2 ml of TEA were placed in a 50-liter reactor vessel equipped with a baffle, paddle stirrer, and cooling jacket. Aqueous sodium hydroxide solution (obtained by dissolving 170 g of sodium hydroxide in 2 liters of pure water) was added to the reactor while stirring, and a reaction between the polycarbonate oligomer and the terminal o-allylphenol-modified polydimethylsiloxane was carried out for 20 minutes.

[0201] A solution of PTBP in methylene chloride (obtained by dissolving 112.5 g of PTBP in 0.5 l of methylene chloride) and a solution of BPA in aqueous sodium hydroxide solution (obtained by dissolving 826 g of BPA in an aqueous solution obtained by dissolving 562 g of sodium hydroxide and 1.7 g of sodium dithionite in 8.2 l of pure water) were added to the polymerization liquid, and the mixture was subjected to a polymerization reaction for 40 minutes.

[0202] To dilute the reaction liquid, 8 liters of methylene chloride were added, and the mixture was stirred for 20 minutes. The mixture was then separated into an organic phase containing an aromatic polycarbonate-based resin (A-2-1) and an aqueous phase containing excess amounts of BPA and sodium hydroxide, and the organic phase was isolated.

[0203] The resulting solution of aromatic polycarbonate resin (A-2-1) in methylene chloride was washed successively with 0.03 mol / l aqueous sodium hydroxide solution and 0.2 mol / l hydrochloric acid, each in amounts of 15 vol% based on the solution. The washed product was then repeatedly washed with pure water until the electrical conductivity in the aqueous phase after washing was 5 µS / cm or less.

[0204] The solution of the aromatic polycarbonate-based resin (A-2-1) obtained by washing in methylene chloride was concentrated and pulverized, and the resulting flakes were dried under reduced pressure at 120 °C to produce the aromatic polycarbonate-based resin (A-2-1). The aromatic polycarbonate-based resin (A-2-1) had a content of the repeating unit represented by formula (I) of 94.0 wt%, a content of the repeating unit represented by formula (III) of 6.0 wt%, an average number of repeats of the repeating unit represented by formula (III) of 38, and a viscosity-averaged molecular weight (Mv) of 21,300. < Production example 8: Production of an aromatic polycarbonate-based resin (A-2-2)>

[0205] 15 liters of the solution of polycarbonate oligomer 2 prepared in Synthesis Example 7, 10.1 liters of methylene chloride, 407 g of a terminal o-allylphenol-modified polydimethylsiloxane with an average chain length “n” of 88, and 8.4 ml of TEA were placed in a 50-liter vessel reactor equipped with a baffle, paddle stirrer, and cooling jacket. 1065 grams of aqueous sodium hydroxide solution, obtained by dissolving 85 g of sodium hydroxide in 980 ml of pure water, were added to the reactor while stirring, and a reaction between the polycarbonate oligomer and the terminal o-allylphenol-modified polydimethylsiloxane was carried out for 20 minutes.

[0206] A solution of PTBP in methylene chloride (obtained by dissolving 147 g of PTBP in 1.0 l of methylene chloride) and a solution of BPA in aqueous sodium hydroxide solution (obtained by dissolving 1.093 g of BPA in an aqueous solution obtained by dissolving 618 g of sodium hydroxide and 2.1 g of sodium dithionite in 9.0 l of pure water) were added to the polymerization liquid, and the mixture was subjected to a polymerization reaction for 40 minutes.

[0207] Thirteen liters of methylene chloride were added to dilute the reaction liquid, and the mixture was stirred for 20 minutes. The mixture was then separated into an organic phase containing an aromatic polycarbonate-based resin (A-2-2) and an aqueous phase containing excess amounts of BPA and sodium hydroxide, and the organic phase was isolated.

[0208] The resulting solution of the aromatic polycarbonate-based resin (A-2-2) in methylene chloride was washed successively with 0.03 mol / l aqueous sodium hydroxide solution and 0.2 mol / l hydrochloric acid, each in amounts of 15 vol% based on the solution. The washed product was then repeatedly washed with pure water until the electrical conductivity of the aqueous phase after washing was 5 µS / cm or less.

[0209] The solution of the aromatic polycarbonate-based resin (A-2-2) obtained by washing in methylene chloride was concentrated and pulverized, and the resulting flakes were dried under reduced pressure at 120 °C to produce the aromatic polycarbonate-based resin (A-2-2). The aromatic polycarbonate-based resin (A-2-2) had a content of the repeating unit represented by formula (I) of 94.0 wt%, a content of the repeating unit represented by formula (III) of 6.0 wt%, an average number of repeats of the repeating unit represented by formula (III) of 88, and a viscosity-averaged molecular weight (Mv) of 17,700. Examples 1 to 9 and comparative examples 1 to 5

[0210] The aromatic polycarbonate-based resins (A-1-1) to (A-1-6) and (A-2-1) and (A-2-2) obtained in Production Examples 1 to 8, and TARFLON FN2200 (viscosity-averaged molecular weight (Mv): 21,700) from Idemitsu Kosan Co., Ltd., were mixed in the ratios given in Table 1 and then dissolved in methylene chloride. The resulting methylene chloride solutions were concentrated and pulverized, and the resulting flakes were dried at reduced pressure at 120 °C to provide test samples of the polycarbonate-based resin compositions 1 to 9 and 11 to 15.

[0211] The test samples were each used to determine the content of the repeating units represented by formulas (I) to (III), the content of the structural unit represented by formula (II) in relation to the total amount of the structural unit represented by formula (II) and the repeating unit represented by formula (III), and the average number of repeating units of the repeating unit represented by formula (III) in the polycarbonate-based resin composition. The results are shown in Table 1. (Assessment of scratch resistance (pencil method))

[0212] The pellets of the polycarbonate-based resin compositions 1 to 9 and 11 to 15 to be evaluated were each subjected to injection molding using an injection molding machine (“Mini Jet Pro” from Thermo Fisher Scientific, Inc.) under conditions of a cylinder temperature of 290 °C and a mold temperature of 110 °C to produce a disc-shaped molded body (with a diameter of 30 mm and a thickness of 1.5 mm).

[0213] Based on JIS K 5600-5-4:1999, a line was drawn with a pencil at a 45° angle and a force of 750 g. The presence or absence of a scratch on the surface was visually inspected, and the scratch resistance (pencil method) was assessed. A pencil hardness determined by the scratch resistance (pencil method) is a pencil hardness at one of the following 14 levels: 6B to B, HB, F, and H to 6H.

[0214] The results are shown in Table 1. [Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Resin composition based on polycarbonate 1 2 3 4 5 Composition ratio* 1 Aromatic polycarbonate-based resin (A-1) A-1-1 80 60 60 60 - A-1-2 - - - - 80 A-1-3 - - - - - A-1-4 - - - - - A-1-5 - - - - - A-1-6 - - - - - Aromatic polycarbonate-based resin (A-2) A-2-1 20 40 - - 20 A-2-2 - - 40 - - FN2200 - - - 40 - Salary Unit of repetition, represented by formula (I) (mass%)* 2 81,2 84,5 84,3 87,0 90,2 Structural unit, represented by formula (II) (mass%)* 2 17,6 13,1 13,3 13,0 8,6 Unit of repetition, represented by formula (III) (mass%)* 2 1,2 2,3 2,4 0,0 1,2 Structural unit, represented by formula (II) (mass%)* 3 93,5 84,9 84,4 100,0 87,5 Average number of repetitions of the repetition unit represented by formula (III) 34 36 82 - 40 Evaluation result Scratch resistance - HB HB HB F HB Table 1 (continued) Example 6 Example 7 Example 8 Example 9 Resin composition based on polycarbonate 6 7 8 9 Composition ratio* 1 Aromatic polycarbonate-based resin (A-1) A-1-1 - - - - A-1-2 - - - - A-1-3 80 - - - A-1-4 - 80 - - A-1-5 - - 80 - A-1-6 - - - 80 Aromatic polycarbonate-based resin (A-2) A-2-1 20 20 20 20 A-2-2 - - - - FN2200 - - - - Salary Unit of repetition, represented by formula (I) (mass%)* 2 79,4 80,5 80,7 84,3 Structural unit, represented by formula (II) (mass%)* 2 18,2 17,1 16,7 14,4 Unit of repetition, represented by formula (III) (mass%)* 2 1,2 1,2 1,3 1,3 Structural unit, represented by formula (II) (mass%)* 3 93,8 93,4 92,7 91,7 Average number of repetitions of the repetition unit represented by formula (III) 36 40 38 40 Evaluation result Scratch resistance - HB HB HB HB Table 1 (continued) Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Polycarbonate-based resin composition 11 12 13 14 15 Composition ratio* 1 Aromatic polycarbonate-based resin (A-1) A-1-1 - - - - 20 A-1-2 - - - - - A-1-3 - - - - - A-1-4 - - - - - A-1-5 - - - - - A-1-6 - - - - - Aromatic polycarbonate-based resin (A-2) A-2-1 100 - - 40 80 A-2-2 - - 100 - - FN2200 - 100 - 60 - Salary Unit of repetition, represented by formula (I) (Mass %* 2 94,0 100 94,0 97,6 90,5 Structural unit, represented by formula (II) (mass %* 2 0 0 0 0 4,6 Unit of repetition, represented by formula (III) (mass %* 2 6,0 0 6,0 2,4 4,9 Structural unit, represented by formula (II) (mass %* 3 0 0 0 0 48,4 Average number of repetitions of the repetition unit represented by formula (III) 38 - 88 40 39 Evaluation result Scratch resistance - B B B B B *1: The ratio refers to mass parts per 100 mass parts of the total quantity of the polycarbonate-based resin compositions (A-1) and (A-2). *2: The content refers to the content (mass %) of each unit in the total quantity of units represented by formulas (I) to (III) in the polycarbonate-based resin composition. *3: The content refers to the content (mass %) of the structural unit represented by formula (II) in the total amount of the structural unit represented by formula (II) and the repeating unit represented by formula (III) in the polycarbonate-based resin composition.

[0215] As shown in Table 1, the scratch resistance of the polycarbonate-based resin compositions 1 to 9 of the present invention was improved in each case.

[0216] In contrast, the polycarbonate-based resin compositions 11 to 14, which did not contain aromatic polycarbonate-based resin (A-1) containing the structural unit represented by formula (II), and the polycarbonate-based resin composition 15, which contained the structural unit represented by formula (II) but did not contain it sufficiently in relation to the total amount of the structural unit represented by formula (II) and the repeating unit represented by formula (III), each exhibited poor scratch resistance. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] KR 2016-0141268 A

[0004] JP H02-219818 A

[0004] JP 2014-80462 A

[0142] Cited non-patent literature

[0000] JIS K 5600-5-4:1999

[0213]

Claims

[1] Polycarbonate-based resin composition comprising: an aromatic polycarbonate-based resin (A-1) comprising a structural unit represented by the following formula (II), and an aromatic polycarbonate-based resin (A-2) comprising a repeating unit represented by the following formula (I), wherein the proportion of the structural unit represented by formula (II) to the total amount of the structural unit represented by formula (II) and a repeating unit represented by formula (III) is 50% by mass or more: where in formula (II) R 11 and R 12Each independently represents a halogen atom or a group selected from the group consisting of: an alkyl group with 1 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, a cycloalkoxy group with 3 to 20 carbon atoms, an alkenyl group with 2 to 10 carbon atoms; an aryl group with 6 to 14 carbon atoms; an aryloxy group with 6 to 14 carbon atoms; an aralkyl group with 7 to 20 carbon atoms; an aralkyloxy group with 7 to 20 carbon atoms; a nitro group; an aldehyde group; a cyano group; and a carboxyl group. R 13a hydrogen atom or a group selected from the group consisting of: an alkyl group with 1 to 5 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, a cycloalkoxy group with 3 to 20 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, and an aryl group with 6 to 14 carbon atoms, R 14 a group selected from the group consisting of: a saturated or unsaturated cyclic hydrocarbon group with 3 to 20 carbon atoms; a substituted or unsubstituted alkyl group; and a 3- to 20-membered saturated or unsaturated heterocyclic group, “c” and “d” each independently represent an integer from 0 to 4 and “m” represents an integer from 0 to 20; where in formula (I) R 1 and R 2Each independently represents a halogen atom or a group selected from the group consisting of: an alkyl group with 1 to 18 carbon atoms; an alkoxy group with 1 to 18 carbon atoms; a cycloalkyl group with 3 to 20 carbon atoms; a cycloalkoxy group with 3 to 20 carbon atoms; an alkenyl group with 2 to 10 carbon atoms; an aryl group with 6 to 14 carbon atoms; an aryloxy group with 6 to 14 carbon atoms; an aralkyl group with 7 to 20 carbon atoms; an aralkyloxy group with 7 to 20 carbon atoms; a nitro group; an aldehyde group; a cyano group; and a carboxyl group. X represents a single bond, an alkylene group with 1 to 8 carbon atoms, an alkylidene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 15 carbon atoms, a cycloalkylidene group with 5 to 15 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, -S-, -SO-, -SO2-, -O- or -CO-, and “a” and “b” each independently represent an integer from 0 to 4; where in formula (III) R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms or an aryl group with 6 to 12 carbon atoms. [2] Polycarbonate-based resin composition according to claim 1, wherein R 14represents an alkyl group with 1 to 18 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group with 3 to 12 carbon atoms, or a 3- to 12-membered saturated or unsaturated heterocyclic group. [3] Polycarbonate-based resin composition according to claim 2, wherein R 14 represents a methyl group, a cyclopentyl group, or a cyclohexyl group. [4] Polycarbonate-based resin composition according to any one of claims 1 to 3, wherein ‘m’ represents an integer from 0 to 4. [5] Polycarbonate-based resin composition according to any one of claims 1 to 4, wherein the aromatic polycarbonate-based resin (A-2) further comprises a polyorganosiloxane block comprising the repeating unit represented by formula (III). [6] Polycarbonate-based resin composition according to claim 5, wherein the repeating unit represented by formula (III) is included as a structural unit represented by any of the following general formulas (III-I) to (III-III): where in formulas (III-I) to (III-III) R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or an aryl group with 6 to 12 carbon atoms, and several R 3 to R 6 may be identical or different from each other, Y-R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R 9 -O- or -R 7 OR 10 -O- represents, where several Y-groups can be the same or different from each other, R 7a single bond, a linear, branched or cyclic alkylene group with 1 to 12 carbon atoms, -R 71 R 72 -, represents a substituted or unsubstituted arylene group or a diarylene group, R 71 represents a linear, branched, or cyclic alkylene group, R 72 represents a substituted or unsubstituted arylene group, R 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, R 9 represents a diarylene group, R 10 β represents a linear, branched or cyclic alkylene group or a diarylene group, β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide, 'n' represents an integer of 31 or greater and less than 91, and 'p' represents an integer of 1 or more and n-2 or less. [7] Polycarbonate-based resin composition according to any one of claims 1 to 6, wherein the content of the repeating unit represented by formula (III) in the total content of the repeating unit represented by formula (I), the repeating unit represented by formula (II) and the repeating unit represented by formula (III) is 0.1 wt% to 3.2 wt%. [8] Polycarbonate-based resin composition according to any one of claims 1 to 7, wherein the aromatic polycarbonate-based resin (A-1) further comprises the repeating unit represented by formula (I). [9] Polycarbonate-based resin composition according to any one of claims 1 to 8, wherein the content of the structural unit represented by formula (II) in the total content of the repeating unit represented by formula (I), the repeating unit represented by formula (II) and the repeating unit represented by formula (III) is 1.0 to 25% by mass. [10] Polycarbonate-based resin composition according to any one of claims 1 to 9, wherein the aromatic polycarbonate-based resin (A-1) has a viscosity-averaged molecular weight (Mv) of 10,000 to 100,000. [11] Polycarbonate-based resin composition according to any one of claims 1 to 10, wherein the aromatic polycarbonate-based resin (A-2) has a viscosity-averaged molecular weight (Mv) of 15,000 to 25,000. [12] Polycarbonate-based resin composition according to any one of claims 1 to 11, wherein a molded article made from the polycarbonate-based resin composition has a scratch resistance of HB or greater, as tested according to JIS K5600-5-4. [13] Molded articles made from the polycarbonate-based resin composition according to any one of claims 1 to 12.

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