Polycarbonate-polysiloxane resin and molded articles obtained from it

Abstract

To provide a polycarbonate-polysiloxane resin which is excellent in transparency, low specific gravity, heat resistance and impact resistance.SOLUTION: A polycarbonate-polysiloxane resin contains a polycarbonate block (A-1) and a polysiloxane block (A-2), and has specific gravity of more than 1.10 and less than 1.20, and a glass transition temperature of 145-200°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate-polysiloxane resin and a molded article obtained by molding the same. [Background technology]

[0002] Polycarbonate resins are widely used in the optical, electrical and electronic equipment, automotive, and infrastructure fields, taking advantage of their high transparency, heat resistance, and impact resistance. In the automotive field, there is a need to reduce vehicle weight in order to reduce environmental impact and improve driving range, and this has led to a demand for polycarbonate resins with even lower specific gravity while maintaining the excellent properties of conventional polycarbonate resins. Furthermore, polycarbonate resins with a higher glass transition temperature than general polycarbonate resins are being used in components that require high heat resistance, such as headlamps and fog lamp covers.

[0003] When designing polycarbonate resins with high glass transition temperatures, bisphenols, which have a chemical structure with high rigidity and low molecular mobility, are commonly used (Patent Document 1). However, in this case, impact resistance is sacrificed, and impact resistance is insufficient, particularly at low temperatures, so sufficient impact resistance may not be exhibited in cold regions such as high latitudes and mountainous areas. Resin modifiers are used to improve impact resistance, but these generally reduce transparency and glass transition temperature, thereby impairing the inherent properties of the polycarbonate resin. As described above, a polycarbonate resin that combines high levels of transparency, low specific gravity, heat resistance, and impact resistance has yet to be provided. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2010 / 105769 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a polycarbonate-polysiloxane resin that is excellent in transparency, low specific gravity, heat resistance, and impact resistance. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that polycarbonate-polysiloxane resins containing polycarbonate blocks and polysiloxane blocks, each containing a specific structural unit, are excellent in transparency, low specific gravity, heat resistance, and impact resistance, and have thus completed the present invention.

[0007] That is, according to the present invention, the object of the invention is achieved as follows.

[0008] 1. A polycarbonate-polysiloxane resin comprising a polycarbonate block (A-1) and a polysiloxane block (A-2), characterized in that the specific gravity of the resin is greater than 1.10 and less than 1.20, and the glass transition temperature of the resin is 145 to 200°C.

[0009] 2. The polycarbonate-polysiloxane resin according to item 1 above, wherein the polycarbonate block (A-1) contains a structural unit represented by the following formula (1):

[0010] [ka]

[0011] (In the above formula (1), R 1 and R 2each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from the group consisting of groups represented by the following formula (2):

[0012] [ka]

[0013] (In the above formula (2), R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 19 and R 20 each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; when there are a plurality of groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7.

[0014] 3. The polycarbonate-polysiloxane resin according to item 1 or 2 above, wherein the polysiloxane block (A-2) contains a structural unit represented by the following formula (3):

[0015] [ka]

[0016] (In the above formula (3), R 23 , R 24 , R 25 and R 26 are each independently at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; R 21 and R 22 are each independently at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, p is a natural number from 1 to 150, and X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0017] 4. The polycarbonate-polysiloxane resin according to any one of items 1 to 3 above, wherein the polycarbonate block (A-1) contains a structural unit represented by the following formula (4):

[0018] [ka]

[0019] (In the above formula (4), R 27 , R 28 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are a plurality of each, they may be the same or different, i and j each represent an integer of 1 to 4, and Y represents at least one group selected from the group consisting of groups represented by the following formula (5):

[0020] [ka]

[0021] (In the above formula (5), R 29 , R 30 ,R 31 , R 32 , R 33 each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and when there are a plurality of each, they may be the same or different, and k is an integer of 1 to 3.

[0022] 5. The structural units of the polycarbonate block (A-1) include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl) 5. The polycarbonate-polysiloxane resin according to any one of items 1 to 4 above, which contains units derived from at least one of 1,1-bis(3-methyl-4-hydroxyphenyl)-1-phenylethane and 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

[0023] 6. The polycarbonate-polysiloxane resin according to any one of items 1 to 5 above, wherein the content of the polysiloxane block (A-2) is 5 to 50% by weight based on the entire polycarbonate-polysiloxane resin.

[0024] 7. The polycarbonate-polysiloxane resin according to any one of items 1 to 6 above, wherein the average number of siloxane repeating units in the polysiloxane block (A-2) is 1 to 150.

[0025] 8. The polycarbonate-polysiloxane resin according to any one of items 1 to 7 above, wherein the average size of the polysiloxane domains of the polycarbonate-polysiloxane resin is 1 to 20 nm.

[0026] 9. The polycarbonate-polysiloxane resin according to any one of items 1 to 8 above, wherein a molded article obtained by molding the resin into a thickness of 2 mm has a total light transmittance of 80% or more.

[0027] 10. A molded article obtained by molding the polycarbonate-polysiloxane resin according to any one of items 1 to 9 above.

[0028] 11. A film or sheet obtained by molding the polycarbonate-polysiloxane resin according to any one of items 1 to 9 above.

[0029] 12. An automobile lamp lens or an automobile interior / exterior component made of the polycarbonate-polysiloxane resin according to any one of items 1 to 9 above.

[0030] 13. A lighting cover, resin window, or front panel made of the polycarbonate-polysiloxane resin according to any one of items 1 to 9 above. [Effects of the Invention]

[0031] The polycarbonate-polysiloxane resin of the present invention combines excellent properties such as transparency, low specific gravity, heat resistance, and impact resistance, and therefore has exceptional industrial effects. DETAILED DESCRIPTION OF THE INVENTION

[0032] The present invention will be described in detail below.

[0033] <Polycarbonate-polysiloxane resin> In the present invention, the polycarbonate-polysiloxane resin contains a polycarbonate block (A-1) and a polysiloxane block (A-2).

[0034] The polycarbonate-polysiloxane resin of the present invention is characterized by having a specific gravity of more than 1.10 and less than 1.20, and a glass transition temperature of 145 to 200°C.

[0035] (specific gravity) The specific gravity of the polycarbonate-polysiloxane resin of the present invention is greater than 1.10 and less than 1.20, preferably 1.105 or greater and 1.195 or less, and more preferably 1.11 or greater and 1.19 or less. A specific gravity within this range is lower than that of typical bisphenol A-type polycarbonate resins, which is preferable from the perspective of weight reduction. The specific gravity is measured in accordance with JIS K7112, Method for Measuring Density and Specific Gravity of Plastics - Non-Foamed Plastics (Method C, Float-Sink Method).

[0036] (glass transition temperature) The glass transition temperature of the polycarbonate-polysiloxane resin of the present invention is in the range of 145 to 200°C, preferably 146 to 195°C, more preferably 148 to 190°C, particularly preferably 150 to 180°C, and most preferably 152 to 170°C. A temperature above the lower limit of this range is preferred because it provides good heat resistance stability when used as a molded product. A temperature below the upper limit is preferred because it provides an appropriate melt viscosity during molding, making it easy to mold thin-walled components and large-area components such as resin windows, and suppressing problems such as thermal degradation. The glass transition temperature is measured using a 2910 DSC manufactured by TA Instruments Japan, Inc., at a heating rate of 20°C / min.

[0037] <Polycarbonate block (A-1)> In the present invention, the polycarbonate block (A-1) is a portion of the polycarbonate polymer contained in the polycarbonate-polysiloxane resin. For example, the polycarbonate block (A-1) preferably contains a structural unit represented by the following formula (1).

[0038] [ka]

[0039] In the above formula (1), R 1 and R 2R each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. 1 and R 2 When there are a plurality of each of the above, they may be the same or different.

[0040] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0041] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tetradecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0042] Examples of the alkoxy group having 1 to 18 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, an octoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0043] Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0044] The cycloalkoxy group having 6 to 20 carbon atoms is preferably a cyclohexyloxy group. and cyclooctyloxy groups. A cycloalkoxy group having 6 to 12 carbon atoms is preferred.

[0045] Examples of the alkenyl group having 2 to 10 carbon atoms include a methenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc. An alkenyl group having 2 to 6 carbon atoms is preferred.

[0046] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, etc. Examples of the aryloxy group having 6 to 14 carbon atoms include a phenyloxy group, a naphthyloxy group, etc.

[0047] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenylethyl group, etc. Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group, a phenylethyloxy group, etc.

[0048] e and f each independently represent an integer of 1 to 4.

[0049] W is a single bond or at least one group selected from the group consisting of groups represented by the following formula (2):

[0050] [ka]

[0051] In the above formula (2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

[0052] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0053] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group. These may be substituted. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group.

[0054] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

[0055] R 19 and R 20 are each independently a hydrogen atom, a halogen atom, or a group having 1 to 18 carbon atoms. It represents at least one group selected from the group consisting of an alkyl group, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are multiple groups, they may be the same or different.

[0056] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0057] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tetradecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0058] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0059] Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0060] Examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group, a cyclooctyl group, etc. A cycloalkoxy group having 6 to 12 carbon atoms is preferred.

[0061] Examples of the alkenyl group having 2 to 10 carbon atoms include a methenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc. An alkenyl group having 2 to 6 carbon atoms is preferred.

[0062] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, etc. Examples of the aryloxy group having 6 to 14 carbon atoms include a phenyloxy group, a naphthyloxy group, etc.

[0063] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenylethyl group, etc. Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group, a phenylethyloxy group, etc.

[0064] g is an integer of 1 to 10, preferably an integer of 1 to 6. h is an integer of 4 to 7, preferably an integer of 4 to 5.

[0065] The polycarbonate block (A-1) is particularly preferably one containing a structural unit represented by the following formula (4).

[0066] [ka]

[0067] In the above formula (4), R 27 , R 28 R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 27 , R 28When there are a plurality of each of these, they may be the same or different.

[0068] i and j are integers of 1 to 4, respectively.

[0069] Y is at least one group selected from the group consisting of groups represented by the following formula (5):

[0070] [ka]

[0071] In the above formula (5), R 29 , R 30 , R 31 , R 32 , R 33 R each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 14 carbon atoms. 29 , R 30 , R 31 , R 32 , R 33 When there are a plurality of each of these, they may be the same or different.

[0072] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0073] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

[0074] k is an integer of 1 to 3.

[0075] <Polysiloxane block (A-2)> In the present invention, the polysiloxane block (A-2) is a polysiloxane-based moiety contained in the polycarbonate-polysiloxane resin, and the type thereof is not particularly limited.

[0076] Specifically, the polysiloxane block preferably contains a structural unit represented by the following formula (3).

[0077] [ka]

[0078] In the above formula (3), R 23 , R 24 , R 25 and R 26 are each independently at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

[0079] Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. Preferred is an alkyl group having 1 to 6 carbon atoms.

[0080] Examples of the substituted or unsubstituted aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, etc. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

[0081] R 23 , R 24 , R 25 and R 26 is preferably a methyl group.

[0082] R 21 and R 22 are each independently at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms.

[0083] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0084] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, etc. Preferred are alkyl groups having 1 to 6 carbon atoms.

[0085] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0086] R 21 and R 22 is particularly preferably a hydrogen atom or a methoxy group.

[0087] X is a divalent aliphatic group having 2 to 8 carbon atoms. Examples of the divalent aliphatic group include alkylene groups having 2 to 8 carbon atoms. Examples of the alkylene group include an ethylene group, a trimethylene group, and a tetramethylene group.

[0088] p is a natural number from 1 to 150, preferably a natural number from 5 to 100, more preferably a natural number from 10 to 80, and particularly preferably a natural number from 20 to 50. The average chain length p is calculated by nuclear magnetic resonance (NMR) measurement.

[0089] The repeating unit of p is R 23 , R 24 For example, as shown in the following formula (6), there may be repeating units of p1 and p2, in which case the sum of the repeating units of p1 and p2 is p, and the repeating units of p1 and p2 in this case may be random.

[0090] [ka]

[0091] In order to satisfy such a specific chain length range, the polysiloxane raw material may be prepared by mixing two or more different hydroxyaryl-terminated polysiloxane raw materials having different average chain lengths p. The polysiloxane raw material may be prepared by mixing appropriate polysiloxane raw materials whose ends have been hydroxyaryl-modified together, or by mixing appropriate polysiloxane raw materials whose ends have not yet been hydroxyaryl-modified. Either method may be used, in which polysiloxane precursors having different average chain lengths are mixed together in advance, and then the terminals are modified with hydroxyaryl groups.

[0092] <Other resins> The polycarbonate-polysiloxane resin of the present invention may contain other resins as long as the effects of the present invention are not impaired. Among these, polycarbonate resins are particularly preferred from the viewpoint of compatibility with the polycarbonate-polysiloxane resin of the present invention.

[0093] <Method for producing polycarbonate-polysiloxane resin> The polycarbonate-polysiloxane resin of the present invention can be produced by steps (I) and (II).

[0094] (Process (I)) Step (I) is a step of reacting a dihydric phenol represented by the following formula (7) with phosgene in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution to prepare a solution containing a carbonate oligomer having a terminal chloroformate group.

[0095] [ka]

[0096] (In the formula, R 1 , R 2 , e, f and W are the same as in formula (1).

[0097] Examples of the dihydric phenol represented by the above formula (7) include 4,4'-biphenol, 3,3',5,5'-tetrafluoro-4,4'-biphenol, α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (hereinafter sometimes abbreviated as "BPM"), α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, and α,α'-bis(4-hydroxyphenyl)-m-bis(1,1,1,3,3,3-hexafluoroisopropyl)benzene. , 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter sometimes abbreviated as "BPZ"), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "BPTMC"), 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "BPOCTMC"), 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1- Bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(3-fluoro-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)perfluorocyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-diphenyl sulfide, 4,4'-dihydroxy-3,3'-diphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyl sulfone, 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as "BPA"), 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter sometimes abbreviated as "BPC"), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane (hereinafter sometimes abbreviated as "BP26XA"), 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis (4-hydroxyphenyl)butane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(3-methyl-4-hydroxyphenyl)decane, 1,1-bis(2,3-dimethyl-4-hydroxyphenyl)decane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 2,2-bis(4-hydroxyphenyl) (4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (hereinafter sometimes abbreviated as "BPAF"), 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (hereinafter sometimes abbreviated as "SBI"), 7,7'-dimethyl-6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane, 7,7'-diphenyl-6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane, 2,2-bis(4-hydroxy-3-methylphenyl)-1,1 ,1,3,3,3-hexafluoropropane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3-fluoro-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis(3,5-difluoro-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,Examples include 2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-phenylethane (hereinafter sometimes abbreviated as "BPAP"), bis(4-hydroxyphenyl)diphenylmethane (hereinafter sometimes abbreviated as "BPTP"), 9,9-bis(4-hydroxyphenyl)fluorene (hereinafter sometimes abbreviated as "BPF"), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF"), and 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene (hereinafter sometimes abbreviated as "BPPF").

[0098] Among the above, BPA, SBI, BPAF, BPZ, BPOCZ, BPTMC, BPOCTMC, BPC, BCF, BPAP, and BPTP are preferred. From the viewpoints of impact resistance, heat resistance, low specific gravity, and availability, BPA, BPAF, BPZ, BPTMC, BPOCTMC, BPC, BCF, BPAP, and BPTP are more preferred, and BPA, BPZ, BPTMC, BPOCTMC, BPC, BCF, and BPAP are particularly preferred. These dihydric phenols may be used alone or in combination of two or more.

[0099] (Step (II)) Step (II) is a step of interfacially polymerizing a hydroxyaryl-terminated polysiloxane represented by the following formula (8) with the carbonate oligomer prepared in step (I) to obtain the polycarbonate-polysiloxane resin of the present invention.

[0100] [ka]

[0101] (R in the formula 21 ~R 26 , X, and p are the same as in the formula (3). As the hydroxyaryl-terminated polysiloxane represented by the above formula (8), for example, the following compounds are preferably used.

[0102] [ka]

[0103] Hydroxyaryl-terminated polysiloxanes can be easily produced by hydrosilylation of a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, with the end of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polysiloxane and (2-methoxy-4-allylphenol)-terminated polysiloxane are preferred, with (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxane being particularly preferred. The hydroxyaryl-terminated polysiloxanes may be used alone or in combination of two or more.

[0104] To achieve high transparency, the average siloxane repeat number p of the hydroxyaryl-terminated polysiloxane is preferably 1 to 150, more preferably 5 to 100, even more preferably 10 to 80, and particularly preferably 20 to 50. At or above the lower limit of this preferred range, excellent impact resistance is achieved, while at or below the upper limit of this preferred range, excellent transparency is achieved. The average chain length p can be calculated by H-NMR measurement.

[0105] Resins above the lower limit exhibit a high rheological property modification effect due to the introduction of polysiloxane moieties with low cohesive strength, making it easy to increase the structural viscosity index. As a result, they maintain high fluidity during shear flow and have good moldability. Resins below the upper limit tend to reduce the average size of polysiloxane domains. As a result, resin molded products with excellent transparency can be obtained even under molding conditions where the resin is retained in a cylinder at high temperatures for long periods of time. Polysiloxane units below the upper limit increase the number of moles per unit weight, making it easier for the units to be incorporated evenly into the polycarbonate. A large number of siloxane repeats leads to uneven incorporation of polysiloxane units into the polycarbonate and an increase in the proportion of polysiloxane units in the polymer molecule, making it easier for polycarbonates containing and not containing these units to be produced, and reducing mutual compatibility. As a result, large polysiloxane domains are more likely to be produced. On the other hand, from the viewpoint of moldability and impact resistance, it is advantageous for the polysiloxane domain to be large to some extent, and therefore there is a preferred range of the number of repetitions as described above.

[0106] In the present invention, the polysiloxane domain refers to a domain mainly composed of polysiloxane dispersed in a polycarbonate matrix, and may contain other components. As described above, the polysiloxane domain does not necessarily consist of a single component because its structure is formed by phase separation from the polycarbonate matrix.

[0107] In the polycarbonate-polysiloxane resin of the present invention, the polysiloxane component content relative to the total weight of the resin is preferably 1 to 70% by weight. The polysiloxane component content is more preferably 3 to 60% by weight, and even more preferably 5 to 50% by weight. At or above the lower limit of this preferred range, excellent impact resistance is achieved, while at or below the upper limit of this preferred range, stable transparency that is less susceptible to the effects of molding conditions is likely to be achieved. The polysiloxane content can be calculated by 1H-NMR measurement.

[0108] Comonomers other than the dihydric phenol and hydroxyaryl-terminated polysiloxane may also be used in combination, provided that they do not interfere with the production process of the present invention.

[0109] The polycarbonate-polysiloxane resin of the present invention can be made into a branched polycarbonate resin by using a branching agent in combination with the above-mentioned dihydric phenol compound. Examples of tri- or higher functional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1,1-bis(4- Examples of the 4-hydroxyphenyl ether include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0110] The method for producing such a branched polycarbonate resin may be a method in which a branching agent is contained in the mixed solution during the production reaction of a chloroformate compound, or a method in which a branching agent is added during the interfacial polycondensation reaction after the completion of the production reaction. The proportion of carbonate constituent units derived from the branching agent in the total amount of carbonate constituent units constituting the resin is preferably 0.005 to 1.005. The branched structure content is preferably 1.5 mol %, more preferably 0.01 to 1.2 mol %, and particularly preferably 0.05 to 1.0 mol %. The branched structure content can be calculated by 1H-NMR measurement.

[0111] In step (I), a mixed solution containing an oligomer of a dihydric phenol having terminal chloroformate groups is obtained, and then the mixed solution is stirred while adding a hydroxyaryl-terminated polysiloxane of the above formula (8) at a rate of 0.004 molar equivalents / min or less relative to the amount of dihydric phenol charged, and the hydroxyaryl-terminated polysiloxane and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polysiloxane resin.

[0112] In the production of the present invention, the solvent may be any of various reaction-inert solvents, such as those used in the production of known polycarbonates, used alone or in combination. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred. The dihydric phenol concentration is preferably 500 g / L or less, more preferably 450 g / L or less, and even more preferably 300 g / L or less. From the viewpoint of production efficiency, the lower limit of the dihydric phenol concentration is preferably 150 g / L or more.

[0113] During the interfacial polycondensation reaction, an acid binder may be added as needed, taking into account the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polysiloxane that yields formula (3) above, or a portion of the dihydric phenol as described above, is added as an additional monomer to this reaction stage, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the dihydric phenol and hydroxyaryl-terminated polysiloxane added later (usually 1 mole corresponds to 2 equivalents).

[0114] The polycondensation by interfacial polycondensation reaction between the dihydric phenol oligomer and the hydroxyaryl-terminated polysiloxane is carried out by vigorously stirring the above mixture.

[0115] In such polymerization reactions, a terminal terminator or a molecular weight modifier is usually used. Examples of terminal terminators include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of the total dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

[0116] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0117] The reaction time for this polymerization reaction must be relatively long to reduce the amount of unreacted polysiloxane components, preferably 30 minutes or more, more preferably 50 minutes or more. On the other hand, since stirring the reaction solution for a long period of time can cause polymer precipitation, the reaction time is preferably 180 minutes or less, more preferably 90 minutes or less.

[0118] The reaction pressure may be reduced, normal pressure, or increased pressure, but is usually preferably normal pressure or the natural pressure of the reaction system.

[0119] The reaction temperature is selected from the range of -20 to 50°C, and in many cases, since heat is generated during polymerization, it is desirable to cool the reaction mixture with water or ice.

[0120] If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0121] (viscosity average molecular weight) The viscosity-average molecular weight of the polycarbonate-polysiloxane resin of the present invention is preferably in the range of 12,000 to 40,000, more preferably 13,000 to 30,000, and even more preferably 14,000 to 25,000. Within the above range, practical mechanical strength is readily attained in many fields, and the resin has an appropriate melt viscosity during molding, suppressing problems such as thermal degradation. Furthermore, the difference in melt viscosity from the polycarbonate resin to be mixed as needed is small, resulting in good kneadability. Furthermore, the water-washing step during resin production is efficient, resulting in excellent productivity.

[0122] The viscosity average molecular weight of the polycarbonate-polysiloxane resin in the present invention can be calculated by first determining the specific viscosity (η SP ) was determined using an Ostwald viscometer from a solution of 0.7 g of resin dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and the viscosity average molecular weight Mv was calculated using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7

[0123] (shock resistance) The polycarbonate-polysiloxane resin of the present invention preferably undergoes ductile fracture in a high-speed surface impact test carried out in accordance with JIS K7211-2.

[0124] (Total light transmittance) The total light transmittance of the polycarbonate-polysiloxane resin of the present invention is preferably 80% or more, more preferably 85% or more, and even more preferably 88% or more. The haze value is preferably 5.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less. By achieving these values, the appearance and light transmittance of the molded product are excellent, which is preferable. The total light transmittance and haze can be measured in a 2.0 mm thick section of the obtained resin plate using a Haze Meter NDH 2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with ASTM D1003.

[0125] (Domain size) In the polycarbonate-polysiloxane resin of the present invention, the average size of the polysiloxane domains is preferably in the range of 1 to 20 nm, more preferably in the range of 2 to 15 nm. At or above the lower limit of this range, sufficient impact resistance is exhibited, and at or below the upper limit of this range, excellent transparency is achieved.

[0126] (Pencil hardness) The pencil hardness of the polycarbonate-polysiloxane resin of the present invention is preferably 2B or higher, which is equal to or higher than that of ordinary polycarbonate resins. In terms of excellent scratch resistance, it is preferably B or higher, more preferably HB or higher, and even more preferably F or higher. Preferably, the resin has a hardness of 1H or more, and particularly preferably 1H or more. A pencil hardness of 4H or less provides sufficient functionality. In the present invention, pencil hardness refers to a hardness at which no scratches remain when the resin of the present invention is rubbed with a pencil having a specific pencil hardness. It is preferable to use the pencil hardness used in the surface hardness test of a coating film, which can be measured according to JIS K-5600, as an index. Pencil hardness decreases in the following order: 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, and 6B, with the hardest being 9H and the softest being 6B.

[0127] <Other ingredients> The polycarbonate-polysiloxane resin of the present invention may contain various flame retardants, reinforcing fillers, and additives that are usually added to polycarbonate resins, provided that the effects of the present invention are not impaired.

[0128] In the present invention, the polycarbonate-polysiloxane resin can be pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. When producing such pellets, various flame retardants, reinforcing fillers, and additives can also be blended.

[0129] Flame retardants include various compounds known as flame retardants for thermoplastic resins, particularly aromatic polycarbonate resins. More preferred are organometallic salt-based flame retardants (e.g., organic alkali (earth) metal sulfonates, metal borate-based flame retardants, and metal stannate-based flame retardants), organophosphorus-based flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazenes), silicone-based flame retardants made from silicone compounds, and fibrillated PTFE. Among these, organometallic salt-based flame retardants and organophosphorus-based flame retardants are particularly preferred. The incorporation of such compounds not only improves flame retardancy, but also improves other properties, such as antistatic properties, fluidity, rigidity, and thermal stability, depending on the properties of each compound.

[0130] <Molded products> In the present invention, various products can be produced from the polycarbonate-polysiloxane resin by injection molding the pellets produced as described above. Furthermore, it is also possible to directly form the resin melt-kneaded in an extruder into sheets, films, profile extrusion molded products, direct blow molded products, and injection molded products without going through the pelletizing process.

[0131] Injection molding can be performed using not only conventional molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluids), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these various molding methods are already widely known. Molding can be performed using either a cold runner system or a hot runner system.

[0132] In the present invention, the polycarbonate-polysiloxane resin can also be used in the form of various profile extrusion molded products, sheets, films, etc. by extrusion molding. Sheets and films can also be molded using methods such as inflation, calendaring, and casting. Furthermore, by subjecting the resin to a specific stretching operation, it can also be molded into heat-shrinkable tubing. The polycarbonate-polysiloxane resin of the present invention can also be molded into molded articles by rotational molding, blow molding, etc.

[0133] Furthermore, in the present invention, molded articles made of polycarbonate-polysiloxane resin can be subjected to various surface treatments. Surface treatments here refer to the formation of a new layer on the surface of a molded resin article, such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, and printing, and methods commonly used for polycarbonate resins can be applied. Specific examples of surface treatments include hard coating, water-repellent and oil-repellent coating, ultraviolet-absorbing coating, infrared-absorbing coating, and metallizing (vapor deposition, etc.).

[0134] The polycarbonate-polysiloxane resin of the present invention has excellent transparency, impact resistance, heat resistance, moldability, pencil hardness, and low specific gravity, and can be widely used in the fields of optical parts, electrical and electronic equipment, and mobility. In particular, it is suitable for use in automobile lamp lenses and automobile interior and exterior components molded mainly by injection molding, and in lighting covers, resin windows, and front panels molded mainly by extrusion molding. [Example]

[0135] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the scope of the present invention. Unless otherwise specified, parts in the examples are parts by weight. Evaluations were made according to the following methods.

[0136] (1) Polymer composition ratio Each repeating unit was measured by proton NMR using JNM-AL400 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated.

[0137] (2) Polysiloxane component content and average siloxane repeat number The H-NMR spectrum of the resulting resin was measured using a JEOL JNM-AL400 proton NMR, and the polysiloxane content was calculated from the integral ratio calculated from the integral curve of the dihydric phenol-derived peak (e.g., 1.4 to 1.8 ppm for BPA) and the integral curve of the polysiloxane-derived peak (-0.2 to 0.3 ppm). Similarly, the average polysiloxane repeat number was calculated by comparing the integral ratio calculated from the integral curve of the hydroxyaryl terminal-derived peak and the integral curve of the polysiloxane-derived peak.

[0138] (3) Viscosity average molecular weight (Mv) The specific viscosity (η SP ) was measured using an Ostwald viscometer from a solution of 0.7 g of sample dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and the viscosity average molecular weight Mv was calculated using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7

[0139] (4) Glass transition temperature Using 8 mg of sample, measurements were performed using a thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd. in accordance with JIS K7121 under conditions of a nitrogen atmosphere (nitrogen flow rate: 40 ml / min) and a heating rate of 20°C / min.

[0140] (5) Specific gravity The resin was molded using an injection molding machine (Japan Steel Works, J-75E3) under conditions of a cylinder temperature of 300-360°C, a mold temperature of 80-120°C, a dwell time of 20 seconds, and a cooling time of 20 seconds to form a three-tiered resin plate with a width of 50 mm, a length of 90 mm, and thicknesses of 3 mm (20 mm), 2 mm (45 mm), and 1 mm (25 mm) from the gate side. The density and specific gravity of the resulting resin plate were measured in accordance with JIS K7112, Measurement Method for Density and Specific Gravity of Plastics - Non-Foamed Plastics (Method C, Float-Sink Method).

[0141] (6) Total light transmittance and haze The total light transmittance (%) and haze (%) at a 2 mm thick portion of the three-stage resin plate obtained in (5) above were measured using a Haze Meter NDH 2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with ASTM D1003.

[0142] (7) Impact resistance Using a Shimadzu HYDROSHOTHITS-P10 high-speed impact tester (Shimadzu Corporation), the impact resistance of the 2 mm thick part of the three-stage resin plate obtained in (5) above was evaluated under the following conditions: test temperature 23°C or -30°C, test speed 7 m / sec, striker diameter 1 / 2 inch, and receiving diameter 1 inch. The test was carried out five times, and the fracture morphology was visually observed and judged according to the criteria described below. "Good": Ductile fracture was observed 3 or more times out of 5. "×": Ductile fracture was observed 2 or less times out of 5.

[0143] (8) Domain size The three-tiered resin plate was cut perpendicular to the resin flow direction using a microtome (Leica Microsystems EM UC6) to prepare ultrathin sections, which were attached to grids (JEOL EM FINE GRID No. 2632 F-200-CU 100PC / CA) and observed using a JEOL TEM JEM-2100 transmission electron microscope at an accelerating voltage of 200 kV and a magnification of 20,000x.

[0144] The obtained micrographs were subjected to particle analysis using the image analysis software WinROOF Ver. 6.6 (Mitani Corporation), and the average size and particle size distribution (frequency distribution) of the polysiloxane domains in the sample slices were obtained. Here, the maximum major axis (the length between any two points on the outer contour of the particle selected so that the distance between them is the maximum) was used as the size of each domain. Similar analysis was performed on five sample slices, and the average value was used as the value for each sample.

[0145] (9)Pencil hardness Based on JIS K5600, a line was drawn on the surface of a resin plate in a thermostatic chamber at an ambient temperature of 23°C with a pencil held at a 45° angle and a load of 750 g applied, and the surface condition was visually evaluated. Load: 750g Measurement speed: 50mm / min Measurement distance: 7mm Pencil: Mitsubishi Pencil Hi-uni

[0146] [Examples 1 to 9] <Resin manufacturing> (Production Example 1) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 13,993 parts of ion-exchanged water and 6,315 parts of a 25% aqueous solution of sodium hydroxide, and 3,441 parts of BPAP as a dihydric phenol and 6.88 parts of hydrosulfite were dissolved therein. Then, 10,166 parts of methylene chloride was added, and 1,480 parts of phosgene (hereinafter sometimes abbreviated as "FH") was blown in over 70 minutes at 16 to 24°C with stirring. 1,339 parts of a 25% aqueous solution of sodium hydroxide was added, and p-tert-butyl ether was further added. A solution of 80.85 parts of methylphenol dissolved in 720 parts of methylene chloride was added, and while stirring, a solution of 334 parts of polydimethylsiloxane (hereinafter sometimes abbreviated as "PDMS") KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a hydroxyaryl-terminated polysiloxane was prepared by dissolving in 5083 parts of methylene chloride. This solution was added to form an emulsion, and then the mixture was stirred vigorously again. With stirring, 6.0 parts of triethylamine was added while the reaction solution was kept at 28°C, and the mixture was heated to a temperature of 26 to 31°C. The reaction was completed by continuing stirring at 100°C for 1 hour. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with water. When the washings became neutral, the organic phase was washed with acidic hydrochloric acid water. After that, the organic phase was repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water. The aqueous phase was then placed in a kneader filled with warm water, and the methylene chloride was evaporated while stirring to obtain a resin powder. After dehydration, the mixture was dried in a hot air circulating dryer at 100°C for 12 hours. The properties of the resulting resin are shown in Table 1.

[0147] (Production Example 2) This was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 3,417 parts of BPAP and the hydroxyaryl-terminated polysiloxane was changed to 593 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 1.

[0148] (Production Example 3) This was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 3,184 parts of BPZ and the hydroxyaryl-terminated polysiloxane was changed to 297 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 1.

[0149] (Production Example 4) This was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 3,158 parts of BPZ and the hydroxyaryl-terminated polysiloxane was changed to 593 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 1.

[0150] (Production Example 5) This was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 4,427 parts of BCF and the hydroxyaryl-terminated polysiloxane was changed to 816 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 1.

[0151] (Production Example 6) This was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 4286 parts of BCF and the hydroxyaryl-terminated polysiloxane was changed to 1965 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 1.

[0152] (Production Example 7) This was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 1,876 parts of BPTMC and 1,479 parts of BPC, and the hydroxyaryl-terminated polysiloxane was changed to 408 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 1.

[0153] (Production Example 8) This was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 1205 parts of BPTMC and 1811 parts of BPA, and the hydroxyaryl-terminated polysiloxane was changed to 408 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 1.

[0154] (Production Example 9) This was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 1835 parts of BPOCTMC and 1644 parts of BPC, and the hydroxyaryl-terminated polysiloxane was changed to 334 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 1.

[0155] [Comparative Examples 1 to 13] <Resin manufacturing> (Production Example 10) This resin was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 3,473 parts of BPAP and 70.07 parts of p-tert-butylphenol, and no hydroxyaryl-terminated polysiloxane was used. The properties of the resulting resin are shown in Table 2.

[0156] (Production Example 11) This was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 3,358 parts of BPAP, 70.07 parts of p-tert-butylphenol, and the hydroxyaryl-terminated polysiloxane was changed to 1,223 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 2.

[0157] (Manufacturing Example 12) This resin was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 3,209 parts of BPZ and 70.07 parts of p-tert-butylphenol, and no hydroxyaryl-terminated polysiloxane was used. The properties of the resulting resin are shown in Table 2.

[0158] (Manufacturing Example 13) This was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 4006 parts of BCF, 70.07 parts of p-tert-butylphenol, and the hydroxyaryl-terminated polysiloxane was changed to 4264 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 2.

[0159] (Manufacturing Example 14) This resin was produced in the same manner as in Production Example 1, except that the dihydric phenols were changed to 1854 parts of BPTMC and 1531 parts of BPC, and p-tert-butylphenol was changed to 70.07 parts, and no hydroxyaryl-terminated polysiloxane was used. The properties of the resulting resin are shown in Table 2.

[0160] (Manufacturing Example 15) This resin was produced in the same manner as in Production Example 1, except that the dihydric phenols were changed to 1,298 parts of BPTMC, 1,772 parts of BPA, and 70.07 parts of p-tert-butylphenol, and no hydroxyaryl-terminated polysiloxane was used. The properties of the resulting resin are shown in Table 2.

[0161] (Manufacturing Example 16) This resin was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 4042 parts of BPOCTMC and 70.07 parts of p-tert-butylphenol, and no hydroxyaryl-terminated polysiloxane was used. The properties of the resulting resin are shown in Table 2.

[0162] (Manufacturing Example 17) This resin was produced in the same manner as in Production Example 1, except that the dihydric phenols were changed to 1,415 parts of BPOCTMC and 1,990 parts of BPC, and p-tert-butylphenol was changed to 70.07 parts, and no hydroxyaryl-terminated polysiloxane was used. The properties of the resulting resin are shown in Table 2.

[0163] (Manufacturing Example 18) This was produced in the same manner as in Production Example 1, except that the dihydric phenols were changed to 1,427 parts of BPC and 2,086 parts of BPOCTMC, and the hydroxyaryl-terminated polysiloxane was changed to 667 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 2.

[0164] (Manufacturing Example 19) This resin was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 2727 parts of BPA and 57.49 parts of p-tert-butylphenol, and no hydroxyaryl-terminated polysiloxane was used. The properties of the resulting resin are shown in Table 2.

[0165] (Manufacturing Example 20) This resin was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 2930 parts of BPA and 70.07 parts of p-tert-butylphenol, and the hydroxyaryl-terminated polysiloxane was changed to 160 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 2.

[0166] (Manufacturing Example 21) This resin was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 2904 parts BPA and 70.07 parts p-tert-butylphenol, and the hydroxyaryl-terminated polysiloxane was changed to 519 parts PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 2.

[0167] (Manufacturing Example 22) This resin was produced in the same manner as in Production Example 1, except that the dihydric phenol was changed to 2889 parts of BPA and 70.07 parts of p-tert-butylphenol, and the hydroxyaryl-terminated polysiloxane was changed to 719 parts of PDMS KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)). The properties of the resulting resin are shown in Table 2.

[0168] [Table 1]

[0169] [Table 2]

[0170] The polycarbonate-polysiloxane resin of the present invention has transparency, low specific gravity, heat resistance, and impact resistance. It is recognized that there is a high degree of compatibility between gender. [Industrial Applicability]

[0171] The polycarbonate-polysiloxane resin of the present invention has excellent transparency, low specific gravity, heat resistance, and impact resistance, and can be used in a wide range of fields, including optical components, electrical and electronic equipment, and mobility.

Claims

1. A polycarbonate-polysiloxane resin comprising a polycarbonate block (A-1) and a polysiloxane block (A-2), wherein the polycarbonate block (A-1) contains, as a structural unit, a unit derived from at least one of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, the specific gravity of the resin being greater than 1.10 and less than 1.20, and the glass transition temperature of the resin being 145 to 200°C.

2. 2. The polycarbonate-polysiloxane resin according to claim 1, wherein the polysiloxane block (A-2) contains a structural unit represented by the following formula (3): 【Chemistry 1】 (In the above formula (3), R ２３ , R ２４ , R ２５ and R ２６ each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; R ２１ and R ２２ each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, p is a natural number from 1 to 150, and X is a divalent aliphatic group having 2 to 8 carbon atoms.

3. 3. The polycarbonate-polysiloxane resin according to claim 1, wherein the content of the polysiloxane block (A-2) is 5 to 50% by weight, based on the entire polycarbonate-polysiloxane resin.

4. 4. The polycarbonate-polysiloxane resin according to claim 1, wherein the average number of siloxane repeating units in the polysiloxane block (A-2) is 1 to 150.

5. 5. The polycarbonate-polysiloxane resin according to claim 1, wherein the polysiloxane domains of the polycarbonate-polysiloxane resin have an average size of 1 to 20 nm.

6. 6. The polycarbonate-polysiloxane resin according to claim 1, wherein a molded article of the resin having a thickness of 2 mm has a total light transmittance of 80% or more.

7. A molded article obtained by molding the polycarbonate-polysiloxane resin according to any one of claims 1 to 6.

8. A film or sheet obtained by molding the polycarbonate-polysiloxane resin according to any one of claims 1 to 6.

9. An automobile lamp lens or an automobile interior or exterior member made of the polycarbonate-polysiloxane resin according to any one of claims 1 to 6.

10. A lighting cover, a resin window or a front panel made of the polycarbonate-polysiloxane resin according to any one of claims 1 to 6.

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