Resin composition and molded articles obtained therefrom

Abstract

To provide a resin composition having excellent wear test resistance and a molding obtained by molding the same.SOLUTION: A resin composition has a flexural modulus of 1,000-2,000 MPa and a coefficient of kinetic friction of 0.05-0.30.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition and a molded product obtained by molding the same.

Background Art

[0002] Conventionally, films, sheets, and resin plates used as molded products made of polycarbonate are excellent in transparency, impact resistance, heat resistance, flame retardancy, etc., are lighter than glass, have excellent moldability, and have a high degree of design freedom. Therefore, they are used as lightweight plastic windows instead of window glass for vehicles such as automobiles. When a resin member is used as a substitute member for glass, it is necessary to prevent the occurrence of abrasion marks because light is scattered when abrasion marks occur. Abrasion marks occur, for example, when wiping a resin member with a cloth or a car wash brush, the resin member is indented under a wide range of stress, and dust intervening between the cloth or car wash brush and the resin member acts as an abrasive to scrape off the surface of the resin member. Compared with glass, polycarbonate is inferior in surface characteristics such as surface hardness and scratch resistance, so it may be used with a coating layer such as a hard coat (Patent Document 1).

[0003] However, coating a hard coat on a resin material has problems such as generally lengthening the manufacturing process and impairing the impact resistance, which is an inherent characteristic of polycarbonate resin. Against such a background, there is a demand for a resin material that can improve a car wash test, which is a kind of abrasion resistance test, without coating a hard coat, but a resin material that can improve abrasion resistance with a single resin has not been provided yet.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The object of the present invention is to provide a resin composition having excellent wear resistance and a molded article obtained by molding therefrom. [Means for solving the problem]

[0006] As a result of diligent research, the inventors of this invention discovered that a resin composition having a specific range of elastic modulus and low dynamic friction exhibits excellent wear resistance, thus completing the present invention. In other words, the objectives of the present invention are achieved by the following items 1 to 18.

[0007] 1. A resin composition characterized by having a flexural modulus of 1,000 MPa to 2,000 MPa and a coefficient of dynamic friction of 0.05 to 0.30. 2. The resin composition according to item 1 above, comprising a polycarbonate resin. 3. The resin composition according to item 1 or 2 above, which contains a sliding modifier. 4. The resin composition according to item 3 above, wherein the sliding modifier is a fatty acid amide-based sliding modifier. 5. The resin composition according to item 3 or 4 above, wherein the content of the sliding modifier is 0.1 to 5 parts by weight per 100 parts by weight of the resin. 6. The resin composition according to any one of paragraphs 2 to 5 above, wherein the polycarbonate resin comprises a polycarbonate block (A-1) and a polysiloxane block (A-2). 7. The resin composition according to paragraph 6, wherein the polycarbonate block (A-1) contains a structural unit represented by the following formula (1).

[0008] [ka]

[0009] (In the above equation (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 a plurality of them, they may be the same or different. e and f are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following formula (2).)

[0010] [Chemical formula]

[0011] (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 them, they may be the same or different. g is an integer of 1 to 10, and h is an integer of 4 to 7.)

[0012] 8. The resin composition according to item 6 or 7, wherein the polysiloxane block (A-2) contains a structural unit represented by the following formula (3).

[0013] [ka]

[0014] (In the above equation (3), R 23 , R 24 , R 25 and R 26 Each of these is 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 Each of these groups is 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.

[0015] 9. The resin composition according to any one of paragraphs 6 to 8 above, wherein the polycarbonate block (A-1) contains a structural unit represented by the following formula (4).

[0016] [ka]

[0017] (In the above equation (4), R 27 , R 28 Each of the following independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. If there are multiple such groups, they may be the same or different. i and j are integers from 1 to 4, and Y is at least one group selected from the group represented by the following formula (5).

[0018] [ka]

[0019] (In the above equation (5), R 29 , R 30 ,R 31 , R 32 , R 33 Each of these independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, and an aryl group with 6 to 14 carbon atoms. If there are multiple such groups, they may be the same or different, and k is an integer from 1 to 3.

[0020] 10. The resin composition according to any one of paragraphs 6 to 9 above, wherein the structural unit of the polycarbonate block (A-1) includes a unit derived from at least one of 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)-1-phenylethane, and 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

[0021] 11. The resin composition according to any one of paragraphs 6 to 10 above, wherein the content of the polysiloxane block (A-2) is 5 to 50% by weight based on the total weight of the resin. 12. The resin composition according to any one of items 6 to 11 above, wherein the average siloxane repeat number (p) of the polysiloxane block (A-2) is 5 to 100. 13. The resin composition according to any one of paragraphs 1 to 12 above, wherein a molded product formed from the resin composition to a thickness of 2 mm has a total light transmittance of 80% or more and a haze value of 5.0 or less. 14.1. A resin composition according to any of items 1 to 13 above, wherein the temperature of deflection under load conditions of 8 MPa is 80°C or higher. 15. A resin composition according to any of items 1 to 14 above, wherein the Charpy impact value is 4 kJ / m2 or higher. 16. A molded article obtained by molding any of the resin compositions described in item 1 to 15 above. 17. A film or sheet obtained by molding any of the resin compositions described in item 1 to 15 above. 18. A vehicle exterior component comprising the resin composition according to any one of claims 1 to 15. [Effects of the Invention]

[0022] The resin composition of the present invention has excellent abrasion resistance and is therefore suitable for use in vehicle exterior components and the like, and the industrial effects it provides are exceptional. [Modes for carrying out the invention]

[0023] The present invention will be described in detail below. The resin composition of the present invention is characterized by having an elastic modulus within a specific range and low dynamic friction. Preferably, the resin composition of the present invention contains a polycarbonate resin as a resin component. Furthermore, preferably, the resin composition of the present invention contains a sliding modifier.

[0024] <Polycarbonate resin> The polycarbonate resin preferably contains a polycarbonate block (A-1) and a polysiloxane block (A-2).

[0025] (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).

[0026] [ka]

[0027] In the above equation (1), R 1 and R 2Each of these groups is independently 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 If there are multiple instances of each, they may be identical or different.

[0028] Examples of halogen atoms include fluorine, chlorine, and bromine atoms. Examples of alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl groups. Preferably, alkyl groups having 1 to 6 carbon atoms are used.

[0029] Examples of alkoxy groups having 1 to 18 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and octoxy groups. Alkoxy groups having 1 to 6 carbon atoms are preferred.

[0030] Examples of cycloalkyl groups having 6 to 20 carbon atoms include cyclohexyl groups and cyclooctyl groups. Cycloalkyl groups having 6 to 12 carbon atoms are preferred.

[0031] Preferred cycloalkoxy groups with 6 to 20 carbon atoms include cyclohexyloxy groups and cyclooctyloxy groups. Cycloalkoxy groups with 6 to 12 carbon atoms are preferred.

[0032] Examples of alkenyl groups having 2 to 10 carbon atoms include methenyl, ethenyl, propenyl, butenyl, and pentenyl groups. Alkenyl groups having 2 to 6 carbon atoms are preferred.

[0033] Examples of aryl groups with 6 to 14 carbon atoms include the phenyl group and the naphthyl group. Examples of aryloxy groups with 6 to 14 carbon atoms include the phenyloxy group and the naphthyloxy group.

[0034] Examples of aralkyl groups with 7 to 20 carbon atoms include the benzyl group and the phenylethyl group. Examples of aralkyloxy groups with 7 to 20 carbon atoms include the benzyloxy group and the phenylethyloxy group. e and f are each independent integers between 1 and 4. W is at least one group selected from the group consisting of single bonds or groups represented by the following formula (2).

[0035] [ka]

[0036] In equation (2) above, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 Each of these 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.

[0037] Examples of alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups. Preferably, alkyl groups having 1 to 6 carbon atoms are used.

[0038] Examples of aryl groups having 6 to 14 carbon atoms include phenyl groups and naphthyl groups. These may be substituted. Examples of substituents include alkyl groups having 1 to 6 carbon atoms, such as methyl groups, ethyl groups, propyl groups, and butyl groups.

[0039] Examples of aralkyl groups with 7 to 20 carbon atoms include the benzyl group and the phenylethyl group.

[0040] R 19 and R 20 Each of these 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. If there are multiple groups, they may be the same or different.

[0041] Examples of halogen atoms include fluorine, chlorine, and bromine atoms. Examples of alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl groups. Preferably, alkyl groups having 1 to 6 carbon atoms are used.

[0042] Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. Alkoxy groups having 1 to 6 carbon atoms are preferred.

[0043] Examples of cycloalkyl groups having 6 to 20 carbon atoms include cyclohexyl groups and cyclooctyl groups. Cycloalkyl groups having 6 to 12 carbon atoms are preferred.

[0044] Examples of cycloalkoxy groups having 6 to 20 carbon atoms include cyclohexyloxy groups and cyclooctyl groups. Cycloalkoxy groups having 6 to 12 carbon atoms are preferred.

[0045] Examples of alkenyl groups having 2 to 10 carbon atoms include methenyl, ethenyl, propenyl, butenyl, and pentenyl groups. Alkenyl groups having 2 to 6 carbon atoms are preferred.

[0046] Examples of aryl groups with 6 to 14 carbon atoms include the phenyl group and the naphthyl group. Examples of aryloxy groups with 6 to 14 carbon atoms include the phenyloxy group and the naphthyloxy group.

[0047] Examples of aralkyl groups with 7 to 20 carbon atoms include the benzyl group and the phenylethyl group. Examples of aralkyloxy groups with 7 to 20 carbon atoms include the benzyloxy group and the phenylethyloxy group.

[0048] g is an integer between 1 and 10, preferably between 1 and 6. h is an integer between 4 and 7, preferably between 4 and 5.

[0049] The polycarbonate block (A-1) is preferably one that includes a structural unit represented by the following formula (4).

[0050] [ka]

[0051] In equation (4) above, R 27 , R 28 Each of these independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. 27 , R 28 If there are multiple instances of each, they may be identical or different. i and j are integers between 1 and 4, respectively. Y is at least one group selected from the group consisting of groups represented by the following formula (5).

[0052] [ka]

[0053] In equation (5) above, R 29 , R 30 , R 31 , R 32 , R 33 Each of these 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 If there are multiple instances of each, they may be identical or different.

[0054] Examples of alkyl groups having 1 to 4 carbon atoms include the methyl group, ethyl group, propyl group, and butyl group. Examples of aryl groups with 6 to 14 carbon atoms include the phenyl group and the naphthyl group. k is an integer between 1 and 3.

[0055] Preferably, the structural unit of the polycarbonate block (A-1) includes a unit derived from at least one of the following: 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)-1-phenylethane, and 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

[0056] (Polysiloxane block (A-2)) In the present invention, the polysiloxane block (A-2) preferably contains a structural unit represented by the following formula (3).

[0057] [ka]

[0058] In equation (3) above, R 23 , R 24 , R 25 and R 26 Each of these is independently at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

[0059] Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups. Preferably, alkyl groups having 1 to 6 carbon atoms are used.

[0060] Examples of substituted or unsubstituted aryl groups having 6 to 12 carbon atoms include phenyl groups and naphthyl groups. Examples of substituents include alkyl groups having 1 to 6 carbon atoms, such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, and hexyl groups. R 23 , R 24 , R 25 and R 26 It is preferable that it be a methyl group.

[0061] R 21 and R 22 Each of these is 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.

[0062] Examples of halogen atoms include fluorine, chlorine, and bromine atoms. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups. Preferably, alkyl groups having 1 to 6 carbon atoms are used.

[0063] Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, and octoxy groups. Preferably, the alkoxy group has 1 to 6 carbon atoms.

[0064] R 21 and R 22 However, it is particularly preferable that the atoms be hydrogen atoms or methoxy groups. X is a divalent aliphatic group having 2 to 8 carbon atoms. Examples of divalent aliphatic groups include alkylene groups having 2 to 8 carbon atoms. Examples of alkylene groups include ethylene, trimethylene, and tetramethylene groups.

[0065] p is a natural number between 1 and 150, preferably between 5 and 100, more preferably between 10 and 80, and particularly preferably between 20 and 50. The average chain length p is calculated by nuclear magnetic resonance (NMR) measurement.

[0066] The repeating unit of p is R 23 , R 24 It may contain multiple different units. For example, as in equation (6) below, there may be repeating units of p1 and p2, in which case the sum of the repeating units of p1 and p2 will be p, and the repeating units of p1 and p2 in this case may be random.

[0067] [ka]

[0068] To satisfy such a specific chain length range, two or more different hydroxyaryl-terminated polysiloxane raw materials having average chain lengths p may be mixed to prepare the product. The method for mixing and preparing the polysiloxane raw materials may be either by mixing suitable polysiloxane raw materials whose ends have been modified with hydroxyaryl, or by first mixing polysiloxane precursors having suitable average chain lengths before modifying their ends with hydroxyaryl, and then modifying their ends with hydroxyaryl.

[0069] The polysiloxane block (A-2) component content relative to the total weight of the resin is preferably 5 to 50% by weight. More preferably, the polysiloxane component content is 7 to 45% by weight, and even more preferably 10 to 40% by weight. Above the lower limit of this preferred range, excellent impact resistance is obtained, and below the upper limit of this preferred range, stable transparency that is less affected by molding conditions is easily obtained. This polysiloxane content can be calculated by 1H-NMR measurement.

[0070] (Method of manufacturing polycarbonate resin) The polycarbonate resin in this invention can be manufactured by process (I) and process (II).

[0071] (Process (I)) Step (I) is a step in which a divalent phenol represented by the following formula (7) and phosgene are reacted in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution to prepare a solution containing a carbonate oligomer having terminal chloroformate groups.

[0072] [ka]

[0073] (In the formula, R 1 , R 2 e, f, and W are the same as in equation (1) above.

[0074] Examples of divalent phenols represented by formula (7) above 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 (sometimes abbreviated as "BPZ"), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (sometimes abbreviated as "BPTMC"), 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (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'-dimeth 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-diphenylsulfide, 4,4'-dihydroxy-3,3'-diphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenylsulfone, 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 (sometimes abbreviated as "BPC"), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane (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) Roxyphenyl)-1,1,1,3,3,3-Hexafluoropropane (hereinafter sometimes abbreviated as "BPAF"), 6,6'-Dihydroxy-3,3,3',3'-Tetramethyl-1,1'-Spirobindan (hereinafter sometimes abbreviated as "SBI"), 7,7'-Dimethyl-6,6'-Dihydroxy-3,3,3',3'-Tetramethyl-1,1'-Spirobindan, 7,7'-Diphenyl-6,6'-Dihydroxy-3,3,3',3'-Tetramethyl-1,1'-Spirobindan, 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 (sometimes abbreviated as "BPAP"), bis(4-hydroxyphenyl)diphenylmethane (sometimes abbreviated as "BPTP"), 9,9-bis(4-hydroxyphenyl)fluorene (sometimes abbreviated as "BPF"), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (sometimes abbreviated as "BCF"), and 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene (sometimes abbreviated as "BPPF").

[0075] Among the above, BPA, SBI, BPAF, BPZ, BPOCZ, BPTMC, BPOCTMC, BPC, BCF, BPAP, and BPTP are preferred. From the viewpoint 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 divalent phenols may be used individually or in combination of two or more.

[0076] (Step (II)) Step (II) is a step in which a hydroxyaryl-terminated polysiloxane represented by the following formula (8) is interfacially polymerized with the carbonate oligomer prepared in step (I) to obtain the polycarbonate-polysiloxane resin of the present invention.

[0077] [ka]

[0078] (R in the formula 21 ~R 26 X and p are the same as in equation (3) above. As the hydroxyaryl-terminated polysiloxane represented by the above formula (8), the following compounds are preferably used, for example.

[0079] [ka]

[0080] Hydroxyaryl-terminated polysiloxanes can be easily produced by hydrosilylation reactions of olefinic unsaturated carbon-carbon bonded phenols, preferably vinylphenol, 2-allylphenol, isopropenylphenol, and 2-methoxy-4-allylphenol, to the ends of polysiloxane chains having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polysiloxanes and (2-methoxy-4-allylphenol)-terminated polysiloxanes are preferred, and (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes are particularly preferred. Hydroxyaryl-terminated polysiloxanes may be used alone or in combination of two or more types.

[0081] Furthermore, 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. Above the lower limit of this preferred range, the impact resistance is excellent, and below the upper limit of this preferred range, the transparency is excellent. The average chain length p can be calculated by 1H-NMR measurement.

[0082] Resins above the lower limit mentioned above exhibit a high effect in modifying rheological properties through the introduction of polysiloxane moieties with low cohesive force, making it easier to achieve a high structural viscosity index. As a result, they maintain high fluidity during shear flow and have good moldability. Resins below this upper limit tend to have a smaller average size of polysiloxane domains. As a result, resin molded products with excellent transparency can be obtained even under molding conditions where the material is kept in the cylinder for a long time at high temperatures. Polysiloxane units below the upper limit increase in the number of moles per unit weight, making it easier for these units to be evenly incorporated into the polycarbonate. When the number of siloxane repeats is large, the incorporation of polysiloxane units into the polycarbonate becomes uneven, and the proportion of polysiloxane units in the polymer molecule increases, making it easier for polycarbonates containing these units and those not to be produced, and reducing their mutual compatibility. As a result, large polysiloxane domains tend to form. On the other hand, from the standpoint of moldability and impact resistance, it is advantageous for the polysiloxane domains to be somewhat larger, and therefore, as mentioned above, there is a preferred range of repeating numbers.

[0083] In this invention, a polysiloxane domain refers to a domain mainly composed of polysiloxane dispersed in a polycarbonate matrix, and may contain other components. As described above, since the structure of a polysiloxane domain is formed by phase separation from the polycarbonate matrix, it is not necessarily composed of a single component.

[0084] Furthermore, other comonomers other than the divalent phenol and hydroxyaryl-terminated polysiloxane can be used in combination, as long as they do not interfere with the manufacturing method of the present invention.

[0085] The polycarbonate resin of the present invention can be made into a branched polycarbonate resin by using a branching agent in combination with the above-mentioned divalent phenolic compound. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucid, or 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 include trisphenols such as hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 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.

[0086] The method for producing such branched polycarbonate resin may involve including the branching agent in the mixed solution during the chloroformate compound formation reaction, or adding the branching agent during the interfacial polycondensation reaction after the formation reaction is complete. The proportion of carbonate constituent units derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, and particularly preferably 0.05 to 1.0 mol%, of the total amount of carbonate constituent units constituting the resin. The amount of branched structure can be calculated by 1H-NMR measurement.

[0087] In step (I), a mixed solution containing an oligomer of divalent phenol having terminal chloroformate groups is obtained. Then, while stirring the mixed solution, the hydroxyaryl-terminated polysiloxane of formula (8) is added at a rate of 0.004 molar equivalents / min or less relative to the amount of divalent phenol charged, and the hydroxyaryl-terminated polysiloxane and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate resin.

[0088] In the production of the present invention, various reaction-inert solvents, such as those used in the production of known polycarbonates, may be used as solvents, either alone or in mixtures. 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 concentration of divalent phenol 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 divalent phenol concentration is preferably 150 g / L or more.

[0089] In interfacial polycondensation reactions, an acid binder may be added as appropriate, taking into account the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders 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, or mixtures thereof. Specifically, when adding a hydroxyaryl-terminated polysiloxane to derive formula (3) above, or a portion of a divalent phenol as an additive monomer in this reaction step, it is preferable to use 2 equivalents or an excess amount of alkali relative to the total number of moles of the later-added divalent phenol and hydroxyaryl-terminated polysiloxane (usually 1 mole corresponds to 2 equivalents).

[0090] The polycondensation reaction between the divalent phenol oligomer and the hydroxyaryl-terminated polysiloxane is carried out by vigorously stirring the above mixture.

[0091] In such polymerization reactions, end-terminating agents or molecular weight modifiers are commonly used. Examples of end-terminating agents include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenols, p-tert-butylphenol, p-cumylphenol, and tribromophenol, as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, alkyl hydroxybenzoates, hydroxyphenylalkylates, and alkyl etherphenols. The amount used is in the range of 100 to 0.5 moles, preferably 50 to 2 moles, per 100 moles of all divalent phenolic compounds used, and it is naturally possible to use two or more compounds in combination.

[0092] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine like triethylamine or a quaternary ammonium salt may be added.

[0093] The reaction time for such polymerization reactions needs to be relatively long in order to reduce unreacted polysiloxane components. Preferably, it is 30 minutes or more, and more preferably 50 minutes or more. On the other hand, since polymer precipitation may occur due to prolonged stirring of the reaction solution, it is preferably 180 minutes or less, and more preferably 90 minutes or less.

[0094] The reaction pressure can be reduced, atmospheric, or pressurized, but it is usually preferable to use atmospheric pressure or the self-pressure of the reaction system.

[0095] The reaction temperature is selected from the range of -20 to 50°C, and since polymerization often generates heat, water cooling or ice cooling is desirable.

[0096] If desired, small amounts of antioxidants such as sodium sulfite or hydrosulfide may be added.

[0097] (viscosity average molecular weight) In the present invention, the viscosity-average molecular weight of the polycarbonate-polysiloxane resin 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 can be easily obtained in many fields, and during molding, it has an appropriate melt viscosity, which suppresses problems such as thermal degradation, and the difference in melt viscosity with the polycarbonate resin that is mixed as needed is small, resulting in good kneadability. Furthermore, the efficiency of the water washing process during resin manufacturing is good, and productivity is excellent.

[0098] The viscosity-average molecular weight of the polycarbonate-polysiloxane resin in this invention is first calculated using the following formula: the specific viscosity (η SP The viscosity was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of resin in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP ) = (t-t0) / t0 [t0 is the number of seconds for the methylene chloride to fall, and t is the number of seconds for the sample solution to fall.] The specific viscosity (η) SP The viscosity-average molecular weight Mv was calculated from 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

[0099] <Sliding modifier> The sliding modifier suitable for use in the resin composition of the present invention is not particularly limited as long as it has a sliding modifying effect, but fatty acid amides are preferred from the viewpoint of compatibility. Furthermore, the content of the sliding modifier per 100 parts by weight of the resin composition is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 4.5 parts by weight, and even more preferably 1 to 4 parts by weight, from the viewpoint of improving wear resistance and suppressing white haze caused by gas generation.

[0100] (Fatty acid amide) From the viewpoint of improving abrasion resistance, the fatty acid amide suitable for use in the resin composition of the present invention preferably has 10 or more carbon atoms in the terminal alkyl group, more preferably 12 or more, even more preferably 14 or more, and most preferably 16 or more. On the other hand, from the viewpoint of improving the appearance of the molded product, the fatty acid amide preferably has 30 or fewer carbon atoms in the terminal alkyl group, more preferably 25 or fewer, even more preferably 20 or fewer, and most preferably 18 or fewer.

[0101] Specific examples of fatty acid amides include stearate amide (e.g., Aamide AP-1, manufactured by Mitsubishi Chemical Corporation), methylenebisstearate amide (e.g., Bis-Aamide LA, manufactured by Mitsubishi Chemical Corporation), ethylenebishydroxystearate amide (e.g., Slipax H, manufactured by Nippon Kasei Co., Ltd.), hexamethylenebishydroxystearate amide (e.g., Slipax ZHH, manufactured by Nippon Kasei Co., Ltd.), and m-xylylenebishydroxystearate amide (e.g., Slipax PXH, manufactured by Nippon Kasei Co., Ltd.).

[0102] <Resin composition> (Method for manufacturing resin compositions) In the present invention, the resin composition is preferably a blend of polycarbonate resin and a sliding modifier in a molten state. As a method of blending in a molten state, an extruder is generally used, and the mixture is kneaded and pelletized at a molten resin temperature of 200 to 320°C, preferably 220 to 300°C, more preferably 230 to 290°C. This yields pellets of a resin composition in which both resins are uniformly blended. The configuration of the extruder, the screw configuration, etc., are not particularly limited. If the molten resin temperature in the extruder exceeds 320°C, the resin may become discolored or undergo thermal decomposition. On the other hand, if the resin temperature falls below 200°C, the resin viscosity may be too high, overloading the extruder.

[0103] (modulus of elasticity) The resin composition of the present invention has a flexural modulus of 1,000 MPa to 2,000 MPa as measured according to ISO 178. Preferably, the flexural modulus is 1,200 MPa to 1,900 MPa, more preferably 1,300 MPa to 1,850 MPa, and even more preferably 1,500 MPa to 1,800 MPa. Within this range, the stress applied to the resin surface during car wash tests can be reduced, resulting in excellent abrasion resistance, which is therefore preferable.

[0104] (Coefficient of kinetic friction) The resin composition of the present invention has a dynamic friction coefficient of 0.05 to 0.30, as measured by the friction coefficient measurement test described in the measurement method below. Preferably, this dynamic friction coefficient is 0.06 to 0.25, and more preferably 0.07 to 0.20. Within this range, the stress applied to the resin surface during the car wash test can be reduced, resulting in excellent abrasion resistance, which is therefore preferable. Measurement Method: The coefficient of dynamic friction between the resin plate surface and the sapphire needle was measured using a surface properties measuring instrument manufactured by Shinto Scientific (HEIDON) under conditions of 23°C and 50% RH. A sapphire needle with a tip shape of R0.7Φ was used, and the average value of three measurements under a load of 100g was taken as the measured value.

[0105] (Temperature of deflection under load) The resin composition of the present invention preferably has a load deflection temperature of 80°C or higher under high load (1.8 MPa) as defined by ISO 75. More preferably, this load deflection temperature is 85°C or higher, even more preferably 90°C or higher, and particularly preferably 100°C or higher. Within this range, thermal deformation in real-world environments is reduced, making it particularly useful for applications such as automotive parts. There is no particular upper limit, but 150°C or lower is preferred.

[0106] (Charpy impact value) The resin composition of the present invention has a notched Charpy impact strength of 4 kJ / m² as measured according to ISO 179. 2 Preferably, it is 8 kJ / m³ or higher. 2 It is more preferable that it be greater than or equal to 10 kJ / m 2 It is even more preferable that the concentration be 15 kJ / m³ or higher. 2The above is particularly preferable. The notched Charpy impact strength is 100 kJ / m². 2 The following provides sufficient functionality.

[0107] (Total light transmittance) The total light transmittance of the resin composition of the present invention is preferably 80% or more, more preferably 85% or more, and even more preferably 87% or more. The haze value is preferably 5.0 or less, more preferably 3.0 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less. The above values ​​are preferable as they result in excellent appearance and light transmittance when molded into a product. The total light transmittance and haze can be measured in accordance with ASTM D1003 using a Haze Meter NDH 2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. at a thickness of 2.0 mm of the obtained resin plate.

[0108] <Other ingredients> The polycarbonate-polysiloxane resin of the present invention can be blended with various flame retardants, reinforcing fillers, and additives that are commonly used in polycarbonate resins, as long as they do not impair the effects of the present invention.

[0109] As flame retardants, various compounds conventionally known as flame retardants for thermoplastic resins, particularly aromatic polycarbonate resins, can be applied. More preferably, organometallic salt flame retardants (e.g., alkali (earth) metal salts of organosulfonic acid, metal borate salt flame retardants, and metal stainate salt flame retardants), organophosphorus flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazenes), silicone flame retardants consisting of silicone compounds, fibrillated PTFE, etc. Among these, organometallic salt flame retardants and organophosphorus flame retardants are particularly preferred. Furthermore, while the incorporation of such compounds improves flame retardancy, it also brings about improvements in other properties, such as antistatic properties, fluidity, rigidity, and thermal stability, depending on the properties of each compound.

[0110] <Molded products> In the present invention, the resin composition can be used to manufacture various products by injection molding pellets that are typically produced as described above. Furthermore, it is also possible to directly form sheets, films, shaped extruded products, direct blow molded products, and injection molded products from a resin that has been melt-kneaded in an extruder, without going through the pellet stage.

[0111] In such injection molding, molded products can be obtained not only using conventional molding methods, but also using injection molding techniques such as injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those using supercritical fluid injection), insert molding, in-mold coating molding, insulated 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. Furthermore, molding can be performed using either a cold runner system or a hot runner system.

[0112] Furthermore, in the present invention, the resin composition can be used in the form of various irregularly shaped extruded products, sheets, and films by extrusion molding. Inflation molding, calendering, and casting methods can also be used for forming sheets and films. It is also possible to form it as a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can also be molded into products by rotational molding or blow molding.

[0113] Furthermore, in the present invention, molded articles made of resin compositions can be subjected to various surface treatments. Surface treatments referred to here involve forming a new layer on the surface of the resin molded 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 coatings, water-repellent and oil-repellent coatings, ultraviolet-absorbing coatings, infrared-absorbing coatings, and metallizing (vapor deposition, etc.).

[0114] The resin composition of the present invention achieves a high degree of compatibility between transparency, impact resistance, heat resistance, and abrasion resistance, and can be widely used in the fields of optical components, electrical and electronic equipment, and mobility. It is suitably used for vehicle interior and exterior components, resin windows, or front panels, and is particularly suitable for use as a vehicle exterior component. [Examples]

[0115] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the present invention. Unless otherwise specified, parts in the examples refer to parts by weight. The evaluation was carried out according to the following method.

[0116] (1) Polymer composition ratio Each repeating unit was measured using a JEOL JNM-AL400 proton NMR spectrometer, and the polymer composition ratio (molar ratio) was calculated. (2) Polysiloxane content and average siloxane repeat count Using a JEOL Ltd. JNM-AL400 proton NMR spectrometer, the 1H-NMR spectrum of the obtained resin was measured. The polysiloxane content was calculated from the integral ratio obtained from the integral curves of the divalent phenol-derived peak (e.g., 1.4-1.8 ppm in the case of BPA) and the polysiloxane-derived peak (-0.2-0.3 ppm). Similarly, the average polysiloxane repeat count was calculated by comparing the integral ratio obtained from the integral curves of the hydroxyaryl-terminated peak and the polysiloxane-derived peak. (3) Total light transmittance and haze The total light transmittance (%) and haze (%) of a 2mm thick section of the resin plate were measured using a Haze Meter NDH 2000 manufactured by Nippon Denshoku Kogyo Co., Ltd., in accordance with ASTM D1003. (4) Temperature of deflection under load (HDT) The temperature of deflection under a high load of 1.80 MPa was measured according to ISO 75. (5) Notched Charpy impact strength A notched Charpy impact test was performed according to ISO 179. (6) Flexural modulus The flexural modulus was measured according to ISO 178. (7) Coefficient of kinetic friction The coefficient of dynamic friction between the resin plate surface and a sapphire needle was measured using a surface texture measuring instrument manufactured by Shinto Scientific (HEIDON) under conditions of 23°C and 50% RH. A sapphire needle with a tip shape of R0.7Φ was used, and the average of three measurements under a load of 100g was used as the measured value. (8) Car wash test Measurements were performed using a 100mm square, 2mm thick resin plate in accordance with ISO 20556. For samples before and after measurement, the haze change (ΔHaze) at three similar points was used as an indicator of car wash resistance. The evaluation was performed according to the criteria described below. "◎": 0 < ΔHaze ≦ 3 "〇": 3 < ΔHaze ≤ 6 "△": 6 < ΔHaze ≤ 9 "×": 9<ΔHaze

[0117] [Example 1] <Resin manufacturing> In a reactor equipped with a thermometer, stirrer, and reflux condenser, 13,993 parts of deionized water and 6,315 parts of 25% sodium hydroxide aqueous solution were added. 1,112 parts of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC), 2,082 parts of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC), and 5.28 parts of hydrosulfite were dissolved as divalent phenols. Then, 10,166 parts of methylene chloride were added, and 1,480 parts of phosgene (hereinafter sometimes abbreviated as "FH") were blown in over 70 minutes at 16-24°C under stirring. 1339 parts of a 25% sodium hydroxide aqueous solution were added, and then a solution of 70.01 parts of p-tert-butylphenol dissolved in 720 parts of methylene chloride was added. While stirring, a solution was prepared by dissolving 741 parts of polydimethylsiloxane (hereinafter sometimes abbreviated as "PDMS") KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)) as a hydroxyaryl-terminated polysiloxane in 5083 parts of methylene chloride. This solution was added to the mixture to create an emulsified state, and then the mixture was stirred vigorously again. Under this stirring, the reaction mixture reached a temperature of 28°C. 6.0 parts of triethylamine were added to the mixture and the reaction was completed by stirring for 1 hour at a temperature of 26-31°C. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, and washed repeatedly with water. Once the washing solution became neutral, it was washed with hydrochloric acid-acidified water. Subsequently, it was washed repeatedly with deionized water until the conductivity of the aqueous phase was almost the same as that of the deionized water. It 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, it was dried in a hot air circulating dryer at 100°C for 12 hours.

[0118] <Manufacturing of resin compositions> To 100 parts by weight of the obtained resin powder, 1.5 parts by weight of bisamide LA (hereinafter referred to as bisLA) manufactured by Mitsubishi Chemical Corporation was added. Subsequently, the mixture was melt-kneaded in a vented twin-screw extruder [(Technovel Co., Ltd. KZW15-25MG)] at 270°C in both the cylinder and die to obtain a resin composition. A portion of the obtained resin composition was dried at 80°C for 12 hours or more, and then test pieces for various evaluations were molded using an injection molding machine. The evaluation results are shown in Table 1.

[0119] [Example 2] <Resin manufacturing> It was manufactured using the same method as in Example 1. <Manufacturing of resin compositions> The same method as in Example 1 was used, except that 3 parts by weight of bis LA was used. The evaluation results are shown in Table 1.

[0120] [Example 3] <Resin manufacturing> It was manufactured using the same method as in Example 1. <Manufacturing of resin compositions> The product was manufactured in the same manner as in Example 1, except that 3 parts by weight of Amid AP-1 (hereinafter referred to as AP-1), manufactured by Mitsubishi Chemical Corporation, was used as a sliding modifier. The evaluation results are shown in Table 1.

[0121] [Example 4] <Resin manufacturing> In a reactor equipped with a thermometer, stirrer, and reflux condenser, 13,993 parts of deionized water and 6,315 parts of 25% sodium hydroxide aqueous solution were added. 1,112 parts of BPTMC, 1,800 parts of 2,2-bis(4-hydroxyphenyl)propane (BPA), and 4.02 parts of hydrosulfite were dissolved as divalent phenols. Then, 10,166 parts of methylene chloride were added, and 1,480 parts of phosgene (hereinafter sometimes abbreviated as "FH") were blown in over 70 minutes at 16-24°C under stirring. 1339 parts of a 25% sodium hydroxide aqueous solution were added, and then a solution of 70.01 parts of p-tert-butylphenol dissolved in 720 parts of methylene chloride was added. While stirring, a solution was prepared by dissolving 1483 parts of polydimethylsiloxane (hereinafter sometimes abbreviated as "PDMS") KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)) as a hydroxyaryl-terminated polysiloxane in 5083 parts of methylene chloride. This solution was added to the mixture to create an emulsified state, and then the mixture was stirred vigorously again. Under this stirring, the reaction mixture was heated to 28°C. In this state, 6.0 parts of triethylamine were added and the reaction was completed by stirring for 1 hour at a temperature of 26-31°C. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, and washed repeatedly with water. When the washing solution became neutral, it was washed with hydrochloric acid-acidified water. Then, it was washed repeatedly with deionized water until the conductivity of the aqueous phase was almost the same as that of the deionized water. It was then placed in a kneader filled with hot water, and the methylene chloride was evaporated while stirring to obtain resin powder. After dehydration, it was dried in a hot air circulating dryer at 90°C for 12 hours.

[0122] <Manufacturing of resin compositions> To 100 parts by weight of the obtained resin powder, 1.5 parts by weight of bisLA was added. Then, the mixture was melt-kneaded in a vented twin-screw extruder [(Technovel Co., Ltd. KZW15-25MG)] at 260°C in both the cylinder and die to obtain a resin composition. A portion of the obtained resin composition was dried at 80°C for 12 hours or more, and then test pieces for various evaluations were molded using an injection molding machine. The evaluation results are shown in Table 1.

[0123] [Example 5] <Resin manufacturing> In a reactor equipped with a thermometer, stirrer, and reflux condenser, 13,993 parts of deionized water and 6,315 parts of 25% sodium hydroxide aqueous solution were added. 362 parts of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BCF), 12,755 parts of BPC, and 3.48 parts of hydrosulfite were dissolved as divalent phenols. Then, 10,166 parts of methylene chloride were added, and 1,480 parts of phosgene (hereinafter sometimes abbreviated as "FH") were blown in over 70 minutes at 16-24°C under stirring. 1339 parts of a 25% sodium hydroxide aqueous solution were added, and then a solution of 70.01 parts of p-tert-butylphenol dissolved in 720 parts of methylene chloride was added. While stirring, a solution was prepared by dissolving 741 parts of polydimethylsiloxane (hereinafter sometimes abbreviated as "PDMS") KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)) as a hydroxyaryl-terminated polysiloxane in 5083 parts of methylene chloride. This solution was added to the mixture to create an emulsified state, and then the mixture was stirred vigorously again. Under this stirring, the reaction mixture was heated to 28°C. In this state, 6.0 parts of triethylamine were added and the reaction was completed by stirring for 1 hour at a temperature of 26-31°C. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, and washed repeatedly with water. When the washing solution became neutral, it was washed with hydrochloric acid-acidified water. Then, it was washed repeatedly with deionized water until the conductivity of the aqueous phase was almost the same as that of the deionized water. It was then placed in a kneader filled with hot water, and the methylene chloride was evaporated while stirring to obtain resin powder. After dehydration, it was dried in a hot air circulating dryer at 90°C for 12 hours.

[0124] <Manufacturing of resin compositions> To 100 parts by weight of the obtained resin powder, 1.5 parts by weight of bisLA was added. Then, the mixture was melt-kneaded in a vented twin-screw extruder [(Technovel Co., Ltd. KZW15-25MG)] at 260°C in both the cylinder and die to obtain a resin composition. A portion of the obtained resin composition was dried at 80°C for 12 hours or more, and then test pieces for various evaluations were molded using an injection molding machine. The evaluation results are shown in Table 1.

[0125] [Comparative Example 1] <Resin manufacturing> It was manufactured using the same method as in Example 1. <Manufacturing of resin compositions> The product was manufactured in the same manner as in Example 1, except that a sliding modifier was not used. The evaluation results are shown in Table 2.

[0126] [Comparative Example 2] <Resin manufacturing> It was manufactured using the same method as in Example 4. <Manufacturing of resin compositions> The product was manufactured in the same manner as in Example 4, except that a sliding modifier was not used. The evaluation results are shown in Table 2.

[0127] [Comparative Example 3] <Resin manufacturing> In a reactor equipped with a thermometer, stirrer, and reflux condenser, 13,993 parts of deionized water and 6,315 parts of 25% sodium hydroxide aqueous solution were added. After dissolving 3,485 parts of BPTMC and 6.97 parts of hydrosulfite as divalent phenol, 10,166 parts of methylene chloride were added, and 1,480 parts of phosgene (hereinafter sometimes abbreviated as "FH") were blown in over 70 minutes at 16-24°C under stirring. 1339 parts of a 25% sodium hydroxide aqueous solution were added, and then a solution of 70.01 parts of p-tert-butylphenol dissolved in 720 parts of methylene chloride was added. While stirring, a solution was prepared by dissolving 741 parts of polydimethylsiloxane (hereinafter sometimes abbreviated as "PDMS") KF-2201 (p=35 (manufactured by Shin-Etsu Chemical Co., Ltd.)) as a hydroxyaryl-terminated polysiloxane in 2224 parts of methylene chloride. After adding this solution and emulsifying it, the mixture was stirred vigorously again. Under this stirring, the reaction mixture was heated to 28°C. In this state, 6.0 parts of triethylamine were added and the reaction was completed by stirring for 1 hour at a temperature of 26-31°C. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, and washed repeatedly with water. When the washing solution became neutral, it was washed with hydrochloric acid-acidified water. Then, it was washed repeatedly with deionized water until the conductivity of the aqueous phase was almost the same as that of the deionized water. It was then placed in a kneader filled with hot water, and the methylene chloride was evaporated while stirring to obtain resin powder. After dehydration, it was dried in a hot air circulating dryer at 90°C for 12 hours.

[0128] <Manufacturing of resin compositions> The obtained resin powder was melt-kneaded in a vented twin-screw extruder [(Technovel Co., Ltd. KZW15-25MG)] at 260°C for both the cylinder and die to obtain a resin composition. A portion of the obtained resin composition was dried at 80°C for 12 hours or more, and then test pieces for various evaluations were molded using an injection molding machine. The evaluation results are shown in Table 2.

[0129] [Comparative Example 4] Various evaluations were conducted using Teijin's polycarbonate L-1225. The evaluation results are shown in Table 2.

[0130] [Table 1]

[0131] [Table 2] [Industrial applicability]

[0132] The resin composition of the present invention has excellent wear resistance and can be widely used in optical components, electrical and electronic equipment, and mobility applications.

Claims

1. A resin composition containing polycarbonate resin and a sliding modifier, The polycarbonate resin is a polycarbonate resin containing a polycarbonate block (A-1) and a polysiloxane block (A-2). The sliding modifier is a fatty acid amide-based sliding modifier. A resin composition characterized by having a flexural modulus of 1,000 MPa to 2,000 MPa and a coefficient of dynamic friction of 0.05 to 0.

30.

2. The resin composition according to claim 1, wherein the content of the sliding modifier is 0.1 to 5 parts by weight per 100 parts by weight of the resin.

3. The resin composition according to claim 1 or 2, wherein the polycarbonate block (A-1) comprises a structural unit represented by the following formula (1). 【Chemistry 1】 (In the above formula (1), R １ and R ２ Each of these 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. If there are multiple groups, they may be the same or different. e and f are integers from 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following formula (2). 【Chemistry 2】 (In the above formula (2), R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ each independently represent 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, and R １９ and R ２０ each independently represent 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 them, they may be the same or different, g is an integer from 1 to 10, and h is an integer from 4 to 7.).

4. The resin composition according to any one of claims 1 to 3, wherein the polysiloxane block (A-2) includes a structural unit represented by the following formula (3). 【Transformation 3】 (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 of these 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, where p is a natural number from 1 to 150, and X is a divalent aliphatic group having 2 to 8 carbon atoms.

5. The resin composition according to any one of claims 1 to 4, wherein the polycarbonate block (A-1) comprises a structural unit represented by the following formula (4). 【Chemistry 4】 (In the above formula (4), R ２７ , R ２８ Each of the following independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. If there are multiple such groups, they may be the same or different. i and j are integers from 1 to 4, and Y is at least one group selected from the group represented by the following formula (5). 【Transformation 5】 (In the above formula (5), R ２９ , R ３０ , R ３１ , R ３２ , R ３３ Each of these 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. If there are multiple such groups, they may be the same or different, and k is an integer from 1 to 3.

6. The resin composition according to any one of claims 1 to 5, wherein the structural unit of the polycarbonate block (A-1) includes a unit derived from at least one of 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)-1-phenylethane, and 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

7. The resin composition according to any one of claims 1 to 6, wherein the content of the polysiloxane block (A-2) is 5 to 50% by weight based on the total weight of the resin.

8. The resin composition according to any one of claims 4 to 7, wherein the average siloxane repeat number (p) of the polysiloxane block (A-2) is 5 to 100.

9. The resin composition according to any one of claims 1 to 8, wherein a molded product formed from the resin composition to a thickness of 2 mm has a total light transmittance of 80% or more and a haze value of 5.0 or less.

10. A resin composition according to any one of claims 1 to 9, wherein the temperature of deflection under load conditions of 1.8 MPa is 80°C or higher.

11. Charpy impact value is 4 kJ / m ２ The resin composition according to any one of claims 1 to 10.

12. A molded article obtained by molding the resin composition according to any one of claims 1 to 11.

13. A film or sheet obtained by molding the resin composition according to any one of claims 1 to 11.

14. A vehicle exterior member comprising the resin composition according to any one of claims 1 to 11.

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