TW200808869A - Polycarbonate-hydrogenated polybutadiene copolymer, method for producing the same, and polycarbonate resin composition using the same - Google Patents

Abstract

Disclosed is a polycarbonate-hydrogenated polybutadiene copolymer containing repeating units (I) and (II) having specific structures. Also disclosed is a polycarbonate resin composition obtained by melt-mixing a blend which is obtained by blending the polycarbonate-hydrogenated polybutadiene copolymer (iii) into a mixture of 45-99% by mass of a polycarbonate resin (I) and 55-1% by mass of a polyolefin resin (ii) in an amount of 0.1-30 parts by mass per 100 parts by mass of the resin mixture. The polycarbonate resin composition is improved in compatibility between the polycarbonate resin and the polyolefin resin, while having impact resistance, fluidity and chemical resistance without suffering from lamellar separation.

Description

200808869 (1) IX. Description of the Invention [Technical Field] The present invention relates to a polycarbonate-hydrogenated polybutadiene copolymer, and a process for producing the same, using the polycarbonate resin composition thereof, especially A polycarbonate resin composition which is excellent in low-temperature impact resistance, fluidity, and chemical resistance, which does not exhibit lamellar peeling after molding. [Prior Art] Polycarbonate resin is an engineering plastic excellent in heat resistance, impact resistance, transparency, and the like. When it is doped with a polycarbonate resin and a polyolefin resin, further characteristics (impact resistance at low temperature, fluidity, and chemical resistance) can be imparted. However, polycarbonate resins and polyolefin resins have a problem of poor compatibility, and mechanical strength is greatly lowered. In order to improve the rigidity at high temperature and the impact resistance at low temperature, Patent Document 1 proposes to blend 4,4f-dioxydiphenylalkane polycarbonate resin in 100 parts by mass of a polypropylene resin. ~100 parts by mass of a rigid polypropylene resin composition improved at high temperatures. However, when this resin composition is used, a layered peeling of the injection molded article occurs in a stripe-like appearance on the surface, which has a problem of impairing the appearance. Further, in Patent Document 2, in order to improve moldability and chemical resistance, it is proposed to contain 70 to 99% by mass of the aromatic polycarbonate resin, and the maximum peak of the melt index, density, and differential scanning calorimetry (DSC) measurement method. The temperature and the boiling-insoluble component are each a thermoplastic resin composition of 1 to 30% by mass of the B-olefin copolymer of the specified range. However, in the case of 200808869 (2), the layered peeling occurred on the injection molded article, and a striped pattern was formed on the surface, which caused a problem of damage to the appearance. Further, in Patent Document 3 and Patent Document 4, in order to solve the problem of the above-mentioned layer peeling, that is, surface peeling, and in order to have a chemical interaction with the polycarbonate resin, an unsaturated carboxylic acid-modified polyolefin resin is also proposed. Composition with polycarbonate resin. However, the general polycarbonate was sealed at the terminal and did not have a functional group, so no significant effect was observed. # Further, in Patent Document 5, a saturated rubbery polymer partially and completely crosslinked is proposed, a polyolefin resin, a polystyrene resin, a polyamide resin, a polyurethane resin, and a poly A high-impact property and high-performance thermoplastic resin composition made of a thermoplastic resin other than a polyolefin resin such as a carbonate resin. More specifically, (A) a thermoplastic elastomer composed of a partially or completely crosslinked saturated rubbery polymer and a polyolefin resin: 95 to 5 parts by mass, (B) a thermoplastic resin (excluding a polyolefin system) Resin): 5 to 95 parts by mass and (C) a compatibilizing agent: a composition of 0.1 parts by mass to 50 parts by mass based on 100 parts by mass of the component (A) and the component (B), and the composition The saturated rubbery polymer is a high impact resistance thermoplastic resin composition characterized by 1 to 40% by mass. Regarding the case where the thermoplastic resin is a polycarbonate, the sweat is disclosed in Example 18: 'First, an ethylene octene-1 copolymer (TPE-) was used using a biaxial extruder (40 ιηιηφ, L/D = 47). 1) / Syndiotactic polypropylene (pp) / free radical bow hair (POX) / cross-linking aid (DVB) = 6/44.4 / 0.3 8 / 0.74 (mass ratio) mixed with a cylinder temperature of 220. (: is melted and extruded to produce a crosslinked thermoplastic elastomer. Among them, acrylonitrile-styrene grafted styrene/propylene/conjugated diene copolymer will be used as a compatibilizing agent-5-8200808869 (3) The hydrogenated styrene-butadiene segmented copolymer and polycarbonate can be produced by melting, kneading, extruding, and pelletizing in a twin-axis extruder. Thus, it is necessary to melt and extrude twice, which is prone to heat deterioration. Moreover, recently, the use of a modified polycarbonate having a functional group to react with a polyolefin in a kneading machine has been reported in the Society, etc., but it has to be kneaded for a long time, and it cannot be applied to a general continuous kneading machine, and PCT Patent Document 1: JP-A-59-22374 (Patent Document No. 5) JP-A-59-223749 Patent Document 5: JP-A-20001 - 1 4 6 5 3 3 SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art described above, and to improve Polycarbonate resin compatible with polyolefin resin, resistant A polycarbonate resin composition having properties such as impact properties, fluidity, and chemical resistance, a polycarbonate polymer suitable as a compatibilizing agent, and a method for producing the same are aimed at the purpose of the present invention. As a result of the investigation, it was found that the polycarbonate-hydrogenated polybutadiene copolymer having a specific structure is effective for the dissolution of the polycarbonate resin and the polyolefin resin, and the polyolefin functional region can be reduced, so that the copolymer is melted by mixing. The resin composition obtained by kneading is not peeled off at the time of molding, and the above-mentioned problem can be solved. -6 - 200808869 (4) Further, it has been found that a hydrogenated polybutyl group having a phenolic hydroxyl group as a terminal of the polycarbonate-hydrogen material is used. In other words, the present invention provides (1) a polycarbonate-hydrogenated polybutadiene having a repeating unit (π) represented by a repeating unit (Π) represented by the following formula (Ϊ), The hepta-butadiene copolymer Μ ' is a novel polymer characterized by (1) and the following formula

[Chemical 1]

[wherein R1 and R2 each have a halogen atom (for example, iodine), an alkoxy group, an ester group, a carboxyl group, a hydroxyl group, and an aromatic group having an alkyl group at the carbon number of 6 to 20, m-position Any one of R1 and R2 may be the same or different from each other, and, in addition, a number of 1 to 20 polymethyl, alkyl, alkylene, 兀, -S - ^ -SO- ' -S〇2* Λ -Ο- χ -CO - , chloro, bromo, fluoro, 1~8 alkyl or all 'which can be bonded to 〇 - since most, each X is Single bond, carbocyclic alkyl, ring or general formula 200808869 (5) [Chemical 2]

3 3 Η I Η CICIC

?H3?-i

The whole number of 4 ο is shown as the η m basis residue and the base of the table 1

Ο [wherein R3 is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and a fluorene is a single bond, a polymethyl group having a carbon number of 1 to 10, an alkyl group, and an alkylene group, r For 〇~4 integers, p is a number from 0.00 to 1.00, q is an integer from 1 to 500; when R3 is a majority, most of R3 may be the same or different from each other]. (2) The polycarbonate-hydrogenated polybutadiene copolymer according to the above (1), wherein the content of the hydrogenated polybutadiene portion is from 0.1 to 50% by mass 〇(3) as described in the above (1) or 2) The polycarbonate-hydrogenated polybutadiene copolymer described in which the viscosity average molecular weight is 1 Å, 〇〇〇 50,000. (4) A method for producing a polycarbonate-hydrogen-8-200808869 (6) polybutylene copolymer according to any one of the above (1) to (3), characterized in that the lower (m) The aromatic di-based compound (A) is reacted with an iron source such as diphenyl photoacrylate to produce a polycarbonate oligomer oligomer and an aromatic represented by the following formula (w) A method in which a monomer (B) and the above aromatic mono-based compound (A)' are reacted in a mixed solution with an aqueous alkali solution. Gas, carbon, carbon-based compounding machine solvent

0 h2 h2 h2 h2> _C—C—G— [wherein R1 and R2, m and η, X are the same as the above formula (I)] [Chemical 5] ch3 ]Ό〇η 0 [wherein, R3, Y, r, p, and q are of the same general formula (Π); when R3, most of R3 may be the same or different from each other]. (5) A polycarbonate resin composition characterized in that the mixture of the 'acid ester resin (i) 45 to 99% by mass and the polyolefin resin (ii) 55- is added per 100 parts by mass of the above (1) ~(3) of the polycarbonate-hydrogenated polybutadiene copolymer (iii) 0.1~30 (IV) is mostly in the mass% of the polycarbon mass - 9 - 200808869 (7), after melt-kneading Got it. (6) A polycarbonate resin composition characterized in that it is a mixture of 45 to 99% by mass of the polycarbonate resin (i) and 55 to 1% by mass of the polyolefin resin (ii). The polycarbonate-hydrogenated polybutadiene copolymer (iii) of any one of the above (1) to (3) is added in an amount of 0.1 to 30 parts by mass and the styrene-ethylene/butylene-styrene segmental copolymer is added. The obtained solubilization auxiliary (iv) is 0.5 to 10 parts by mass, and is obtained by melt kneading. (7) A molded article obtained by melt molding the polycarbonate resin composition according to (5) or (6) above. (8) A hydrogenated polybutadiene characterized by having a phenolic hydroxyl group at the terminal represented by the above formula (IV). [Embodiment] The polycarbonate-hydrogenated polybutadiene copolymer having the repeating unit represented by the formula (I) and the repeating unit (Π) represented by the formula (I) of the present invention is effective for polycarbonate. When the resin is compatible with the polyolefin resin and is blended in the polycarbonate resin composition containing the polyolefin resin, the polyolefin functional region can be reduced, so that the composition does not exhibit lamellar peeling after molding, and Improve the impact resistance at low temperatures. The effect of the melter of the polycarbonate-hydrogenated polybutadiene copolymer acts as a surfactant type and exists at the interface between the polyolefin resin and the polycarbonate resin to reduce the polyolefin functional region. Polycarbonate-hydrogenated polybutadiene copolymer-10-200808869 (8) The polycarbonate/hydrogenated polybutadiene polymer is a repeating unit (1) having the following general formula (1), and a lower formula (n) Polycarbonate-hydrogenated polybutylene oxide copolymer of the repeating unit (Π) indicated. [Chemical 6]

(I) In the formula (I), each of R1 and R2 is a halogen atom (e.g., chlorine, bromine, fluorine, iodine), an alkoxy group, an ester group, a thiol group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms. Or a ring having 6 to 20 carbon atoms may have an aromatic group of an alkyl group, which may be bonded to any of the 〇-position and the m-position. When each of R1 and R2 is a plurality, each of R1 and r2 may be the same or different from each other. Further, X is a single bond, a polymethyl group having 1 to 20 carbon atoms, an alkylene group, an alkylene group, a cycloalkyl group, a cycloalkylene group, _8-, -80-, -802-, - 0-, -C Ο - bond or general formula

-11 - 200808869 (9) The base and the hydrazine residue shown, m and η are integers representing 〇~4. W匕8]

(Π) In the formula (Π), 3 is an alkyl group having 1 to 20 carbon atoms, an aryl group, a aryl group, a fluorene group, a polymethyl group having a carbon number of 1 to 10, and a stretching base. And the sub-family base, r is an integer of G~4, Ρ is 〇·〇〇~1〇〇, ^ is an integer of i~. When R3 is a majority, most of R2 may be the same or different from each other. In the polycarbonate-hydrogenated polybutadiene copolymer of the present invention, the content of the hydrogenated polybutadiene portion is preferably from 0.1 to 50% by mass. When the content of the hydrogenated polybutadiene portion is in the range of from 0.1 to 50% by mass, compatibility can be exhibited. The more preferable content of the hydrogenated polybutadiene moiety is from 0.5 to 40% by mass, particularly preferably from 1 to 30% by mass. Further, the polycarbonate-hydrogenated polybutadiene copolymer of the present invention has a viscosity average molecular weight of from 10,000 to 50,000. When the viscosity average molecular weight is in the range of 10,000 to 50,000, when it is melt-kneaded in the form of a compatibilizing agent, the kneading of the polyolefin resin and the polycarbonate resin is facilitated, the polyolefin functional region is reduced, and the molded article is suppressed. Layered peeling improves mechanical properties. A more preferred viscosity average molecular weight is from 1 1,000 to 40,000, particularly preferably from 13,000 to 30,000. -12- 200808869 do) Method for producing polycarbonate-hydrogenated polybutadiene copolymer The method for producing polycarbonate-hydrogenated polybutadiene copolymer of the present invention is known as the following formula (week) The aromatic di-based compound (A) represented by the reaction with a carbonyl source to produce a polycarbonate oligomer having an aromatic dihydroxy compound represented by the following formula (IV) (B) The reaction is carried out with the aromatic dihydroxy compound (A) in a mixed solution of an organic solvent and an aqueous alkali solution. Further, the polycarbonate-hydrogenated polybutadiene copolymer of the present invention can be produced by a transesterification method or an oxidative carbonylation method in addition to the above-mentioned interfacial polycondensation method. Hereinafter, the materials used in the production of the polycarbonate-hydrogenated polybutadiene copolymer and the polycarbonate resin composition of the present invention will be described. 1·Aromatic Dihydroxy Compound (A) The aromatic dihydroxy compound (A) used in the present invention can be used in the formula (m).

(In the formula, R1, R2, X, m and η are the same as the above-mentioned aromatic dihydroxy compounds having a carbon number of 12 to 37. Here, the aromatic dihydroxy compound shown in the above general formula ( melon) • 13- 200808869 (11) can be a wide variety of substances, especially 2,2-bis(4-hydroxyphenyl)propane [bisphenol A] is better. Examples of the divalent phenol other than bisphenol a include 1,1-bis(4-hydroxyphenyl)methane;;,, bis-(4-hydroxyphenyl)ethane; 9,9-bis(4-hydroxyphenyl) 9,9-bis(3-methyl-4-hydroxyphenyl)anthracene; bis(4-hydroxyphenyl)cycloalkane; bis(4-hydroxyphenyl)sulfide; bis(4-hydroxyl) Phenyl) maple; bis(4-hydroxyphenyl)hydrazine; bis(4-hydroxyphenyl)ether; bis(4-hydroxyphenyl) other than bisphenol A such as bis(4-hydroxyphenyl) ketone a compound or a halogenated bisphenol such as 2,2-bis(3,dibromo-enhydroxyphenyl)propane or 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane. When these phenols have an alkyl group as a substituent, the group is preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably a fluorenyl group having 1 to 4. Further, these aromatic dihydroxy compounds may be used alone or in combination of two or more. Hydrogenated polybutadiene (B) of the formula (IV)

[化10]

(IV) (wherein R3, Y, p, q and Γ are the same as defined above) The phenol terminal hydrogenated polybutadiene (B) represented by the formula (V) -14- (V) 200808869 (12) [11]

(wherein, Y, p, and q are the same as defined above) the hydroxy terminal hydrogenated polybutadiene (C) represented by the formula and the benzoic acid ester derivative (D) represented by the formula (V!) Obtained by transesterification

(wherein R5 is a lower alkyl group, and R3 and r are the same as defined above.) The hydroxy terminal hydrogenated polybutadiene (C) represented by the formula (V) is obtained by hydrogenation of polybutadiene, so that a small amount of double bonds are present. There is a possibility that the phenol terminal hydrogenated polybutadiene (B) represented by the passage of VI) is used in the range which does not affect the physical properties. Further, the polymerization of butadiene is 1,4- or 1,2-bonded, and its tt is limited, and can be used in the range of 〇 p S p S 1.00. Y is a single bond, a polymethyl group having a carbon number of 1 to 1 Å, an alkyl group, a group, and an ethyl group and a propyl group [(HO) - [CH (CH3) -CH 2 ] - are preferred. The formula (may be in the absence of alkylene (C)] -15- 200808869 (13) q is 1 to 500, preferably 1 to 200, more preferably 5 to 150. Hydroxybenzoate derivative ( D) R1 2 is preferably methyl, ethyl, n-propyl or n-butyl. Commercially available hydroxy terminal hydrogenated polybutadiene (c) is KRASOL HLBP-P300 manufactured by Satomer (Y: Base, p: 0 · 6 5, q: 6 6) The polybutadiene is terminated with ethylene oxide and then hydrogenated. In the present example, KRASOL HLBP-P3 00 is also used. The transesterification reaction of a hydroxyl terminated hydrogenated polybutadiene with a hydroxybenzoate derivative to obtain a phenol-terminated hydrogenated polybutadiene, and the terminal reaction rate is not necessarily 100%. The reaction rate may be 50% or more. The present invention also provides a hydrogenated polybutadiene having a phenolic hydroxyl group represented by the above formula (IV). 3. A carbonyl source · The carbonyl source of the polycarbonate used in the present invention is a general polycarbonate # Phosphorus used for interfacial polycondensation is used, and triphosgene, bromine phosgene, etc. can be used. In addition, in the case of transesterification, diallyl carbonate can be used. In the case of the carbonylation method, carbon monoxide or the like can be used. -16-1 End-stopping agent 2 The terminal stopper of the polycarbonate used in the present invention is not particularly limited, and examples thereof include phenol, hydrazine, m-, and p-cresol. , p-tert-butylphenol, ρ·tripentylphenol, P-third octylphenol, p-pentylphenol, P-methoxyphenol, p-phenylphenol, etc. Third butyl phenol, P-pentyl phenol 200808869 (14), p-t-octyl phenol, and phenol are preferred. 5. Polycarbonate-hydrogenated polybutadiene copolymer copolymer molecular and copolymer ratio, etc. It is not particularly specified that the viscosity average molecular weight (Mv) is preferably from 10,000 to 50,000, and preferably from 11, 〇〇〇 to 4 〇, 〇〇〇, as a viscosity of the compatibilizing agent. It is more preferably from 1 3,000 to 30,000. Further, the content of the hydrogenated polybutadiene is preferably from 11 to 5 〇 mass% from the viewpoint of the performance of the compatibilizing agent and the physical property balance of the resin composition. 'and preferably 0.5 to 40% by mass, more preferably 1 to 3 % by mass. 6. Solvent, alkaline aqueous solution in the production of the present invention In the interfacial polycondensation method of the method, the solvent is various inert organic solvents, and examples thereof include dichloromethane; chloroform, carbon tetrachloride; 1, 1-methyl chloroacetate, 1,2-methyl chloride, 1 , 1,1-dichloroethane; 1,1,2-trichloroethane; 1,1,1,2-tetrachloroethane; 1,1,1,2-tetrachloroethane; pentachloroethane Alkane; a chlorinated hydrocarbon such as chlorobenzene, toluene, acetonitrile, etc. These organic solvents may be used alone or in combination of two or more. Among them, methylene chloride is particularly suitable. The base to be used in the preparation of the aqueous alkali solution may, for example, be sodium hydroxide, potassium hydroxide or barium hydroxide. Among them, sodium hydroxide and potassium hydroxide are preferred, and sodium hydroxide is particularly suitable. When manufactured by transesterification, no solvent is required. 17-200808869 (15) Further, in the case of the oxidative carbonylation method, examples of the solvent include dichloromethane, chloroform, 1,2-dichloroethane, acetophenone, r-butyrolactone, and tetrahydrofuran. Further, a solvent having a carbonate bond is also useful. For example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethyl carbonate, propyl carbonate, diallyl carbonate, allyl methyl carbonate, bis(2-methoxyphenyl) Carbonate, vinyl carbonate, dibenzyl carbonate, di(o-methoxyphenyl) carbonate, methyl ethyl carbonate, and the like. The preferred one is propionate carbonate. 7. Catalyst In the interfacial condensation method of the production method of the present invention, the catalyst is an interphase shift catalyst. For example, a tertiary amine or a salt thereof, a quaternary ammonium salt, a quaternary phosphonium salt or the like is preferably used. Examples of the tertiary amine include triethylamine, tributylamine, N,N-dimethylcyclohexylamine, pyridine, and dimethylaniline. Further, the tertiary amine salt may, for example, be a salt of such tertiary amine. Acid salts, bromates, and the like. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, and tetrabutylammonium bromide. Examples of the fourth-order iron salt include chlorination. Tetrabutyl iron, tetrabutyl bromide scale, and the like. These catalysts may be used singly or in combination of two or more. Among the above catalysts, a tertiary amine is preferred, and particularly triethylamine is suitable. Examples of the transesterification catalyst in the transesterification method include various materials, and examples thereof include an alkali metal (for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), an alkaline earth metal compound, an amine, and a quaternary ammonium salt. Nitrogen-containing basics such as -18 - 200808869 (16) Compounds or boron compounds. The above nitrogen-containing basic compound is preferably used in the form of trihexylamine, tetramethyl hydroxide hydroxide, tetrabutylammonium hydroxide or dimethylox. Further, examples of the boron compound include boric acid, trimethyl borate, triethyl borate, tributyl borate, triheptyl borate, triphenyl borate, and trinaphthyl borate. The catalyst in the oxidative carbonylation method may use a catalyst in which various palladium compounds are combined with a reducing oxidizing agent. Examples of the palladium compound include palladium chloride (ruthenium), carbonyl chloride, palladium, palladium acetate, and the like, and examples thereof include dichlorobis(acetonitrile)palladium (ruthenium), dichlorobis(benzonitrile)palladium (ruthenium), and the like. . These palladium compounds may be used singly or in combination of two or more. Examples of the reducing oxidizing agent include a lanthanoid element, a transition metal of Groups 5 to 7 of the periodic table, chromium, manganese, iron, cobalt, nickel, and copper, and among them, cobalt is preferred. The cobalt compound is suitably cobalt chloride (ruthenium), cobalt acetate (ruthenium) or the like. Among them, chlorination (Π) is preferred. In the polycarbonate-hydrogenated polybutadiene copolymer produced by the interfacial polycondensation method of the present invention, first, the aromatic dihydroxy compound (A) [hereinafter, referred to as divalent phenol (A)] and phosgene are used. The carbonyl source reacts to produce a polycarbonate oligomer. In this reaction, a polycarbonate aqueous solution is prepared by preparing an alkali aqueous solution containing a divalent phenol (A) as a raw material and reacting it with phosgene or the like in the presence of an inert organic solvent. In this case, the aqueous alkali solution is usually preferably used in a concentration of from 1 to 15% by mass. Further, the content of the divalent phenol (A) in the aqueous alkali solution is usually selected in the range of 〇 5 to 20% by mass. Further, the amount of the inert organic solvent to be used is expected to be -19-200808869 (17) The volume ratio of the organic phase to the aqueous phase is 5/1 to 7/1, preferably 2/1 to 4/1. The reaction temperature is usually in the range of 0 to 50 ° C, preferably 5 to 40 ° C. In the reaction, after the reaction of phosgene or the like, an aqueous solution containing the alkali of di(A) and a part of the terminal stopper are added. React as desired. After the reaction, the aqueous phase is separated from the organic phase containing the acid ester oligomer by an operation such as standing or centrifugation. The organic phase can be used not only in the polycarbon oligomer but also in the next step. Next, in the presence of the residual terminal stopper, the polycarbonate obtained as described above and the aforementioned phenol terminal hydrogenated polybutadiene (B) and divalent phenol, in the presence of an aqueous solution of the catalyst and an inert organic solvent to be used. The polycondensation is usually carried out at a temperature in the range of 〇50 ° C, preferably 5 to 4 〇 ° C. The base, the inert organic solvent and the catalyst to be used at this time may be the same as those described for the production of the polycarbonate oligomer. Further, the capacity ratio of the organic phase to the aqueous phase in the interfacial polycondensation is the same as described above. After the reaction, the mixture is appropriately diluted with an inert organic solvent, and then the aqueous phase is separated from the organic phase containing the polycarbonate-hydrogenated polybutadiene by a static or the like. Finally, the polycarbonate-hydrogenated polybutadiene solution thus obtained is washed successively with an aqueous alkali solution, an aqueous acid solution and water, and then the carbonate-hydrogenated polybutadiene copolymer is isolated and recovered. Next, the polycarbonate resin composition of the present invention will be described. Selecting the selected phenolic medium into the polycarbonate, testing. The ester is low (A). The above-mentioned, or the copolymerization is agglomerated. Poly-20-200808869 (18) The polycarbonate resin composition of the present invention is a polycarbonate. In the mixture of 45 to 99% by mass of the resin (i) and 55 to 1% by mass of the polyolefin resin (π), the above-mentioned polycarbonate-hydrogenated polybutadiene copolymer (iii) is blended per 100 parts by mass. 1 to 30 parts by mass, and melt-kneaded. 8. Polycarbonate Resin The polycarbonate resin used in the polycarbonate resin composition of the present invention has a viscosity average molecular weight (Mv) of preferably 10,000 to 50,000, preferably 1 15,000 to 40,000, and preferably 1 3,000 to 3 0,000 is better. Viscosity The average molecular weight (Mv) is 1 〇, and in the range of 〇〇〇~5 0,000, the mechanical strength of the resin composition is satisfactory, and it can be injection molded. 9. Polyolefin resin The polyolefin resin (Π) used in the polycarbonate resin composition of the present invention is not particularly limited, and examples thereof include ethylene, propylene, butene-1, 4-® methyl-pentene-1. a monopolymer or a copolymer of ethylene and an α-olefin such as propylene, butene-1, hexene-1, heptene-1, octene-1, 4-methyl-pentene-1, or the like, Copolymer of propylene with ethylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, 4-methyl-pentene-1, etc., butene- A copolymer of 1, and an α-olefin such as ethylene, propylene, pentene-1, hexene-1, heptene-1, octene-1, and 4-methyl-pentene-1. The copolymer may be a random copolymer' and may also be a segmented copolymer. Further, the polyaniline resin (i i) may be used in combination of two or more kinds.

The melt index (MI) of the polyolefin resin (ii) is preferably from 0.1 to 100 g/10 min, more preferably from 0.4 to 80 g, in the measurement method according to JIS-21-200808869 (19) K721 0:99. /10 minutes. In the polycarbonate resin composition of the present invention, the mixing ratio of the polycarbonate resin (i) and the polyolefin resin (Π) is 45 to 99% by mass in the former and 55 to 1% by mass in the latter. A preferred mixing ratio is 50 to 98% by mass in the former and 50 to 2% by mass in the latter. Further, the polycarbonate-hydrogenated polybutadiene copolymer (iii) is a mixture of the above-mentioned poly-carbonate resin (i) and the polycarbonate resin (i) and the polyolefin resin (ii) per 1 part by mass. The ratio of ol to 30 parts by mass is matched. When the amount is 0.1 part by mass or more, the compatibility of the polycarbonate resin and the polyolefin resin is effective, and since the polycarbonate resin composition can reduce the polyolefin functional region, laminar peeling after molding can be suppressed. The mechanical properties such as low-temperature impact resistance can be improved. On the other hand, when it is 30 parts by mass or less, the polycarbonate resin composition can suppress other physical properties such as mechanical properties. Further, in the present invention, by using the compatibility aid as (iv), the mechanical properties such as impact resistance can be further improved. The type of the compatibility aid which is used as the component of the compatibility aid (iv) in the present invention is not particularly limited, but a styrene-ethylene/butylene-styrene segmental copolymer (hereinafter referred to as "SEBS") is used. For the most appropriate. Further, a segmented copolymer represented by the following formula (W) or (VBI) X-(YX) n···(观)(Χ-Υ) η (Vffl) is also suitably used as a compatibilizing aid. . Formula - 22- 200808869 (20) X in (w) and (Vi) is a styrene polymerized segment, and the degree of polymerization of the two terminals of the molecular chain in the formula (VI) is the same or different. γ is selected from at least one of an isoprene polymerization segment, a hydrogenated butadiene polymer segment, and a hydrogenated isoprene polymer segment. Further, η is an integer of 1 or more. The content of the X component in the above segmented copolymer is desirably 20 to 80% by mass, preferably 30 to 70% by mass. When the amount is less than 20% by mass, the rigidity of the resin composition of the tree Φ is lowered. When the amount is more than 80% by mass, the moldability and the impact strength tend to be lowered, which are all undesirable. Further, the number average molecular weight per single segment of the X component is in the range of 5,000 to 200,000, and the number average molecular weight per segment of the bismuth component is desirably in the range of 5,000 to 200,000, and the number of each single segment of the X component. When the average molecular weight is less than 5,000 and the number average molecular weight of each segment of the bismuth component is less than 5,000, the mechanical properties of the resin composition tend to be insufficient, and each single segment of the X component When the number average molecular weight is more than 200,000 and the number average molecular weight of each of the ® and the bismuth components is more than 200,000, the moldability of the resin composition tends to be lowered, which is not preferable. Moreover, the number average molecular weight of the segmented copolymer is 1 〇, 〇〇〇~4 〇〇, and the range of 〇〇〇 is good, the average molecular weight of the number is less than 1 〇, and the mechanical properties of 〇〇〇 are poor. If it exceeds 40,000, the moldability tends to decrease and it is not preferable. By adding a compatibility aid, the impact resistance can be further improved. Specific examples of such a segmented copolymer include styrene-hydrogenated butadiene-styrene three-stage polymer, styrene-isoprene-styrene three-stage polymer, styrene-hydrogenated isoprene Alkene-styrene three-stage polymer, phenylethylene-23- 200808869 (21) ene-hydrogenated isoprene two-stage polymer, styrene-isoprene two-stage polymer, styrene-hydrogenated Diene two-stage polymer and the like. Further, other compatibility solubilizing agents include acid-modified EPR, epoxy-modified EPR, acid-modified polyolefin, epoxy-modified polyolefin, amine-modified EPR, amine-modified polyolefin, and acid-modified EPR or acid modified polyolefin / epoxy resin, etc. (iv) The blending amount of the component is 0.5 to 10 parts by mass, preferably 100 parts by mass, based on the total of the polyolefin resin (i) and the polyolefin resin (Π), that is, the [(i) + (ii)] component. It is 1 to 8 parts by mass, particularly preferably 2 to 6 parts by mass. If it is 10 parts by mass or more, the rigidity is insufficient. When the amount is 0.5 parts by mass or less, no improvement in the impact resistance is observed. Further, in the present invention, the compatibility aid may be used singly or in combination of two or more. 10. Others In the polycarbonate resin composition of the present invention, various additives may be blended to the extent that the properties are not impaired. Examples of the additives include antioxidants such as hindered phenol-based and ester-based antioxidants, light stabilizers such as hindered amines, flame retardants, flame retardant adjuvants, colorants, antistatic agents, anti-sticking agents, weathering agents, and mold release agents. Agents, slip agents, etc. Further, as the additive, a fibrous filler such as glass fiber, carbon fiber or linaloamide fiber, a metal fiber such as copper or brass, or a whisker such as potassium titanate, magnesium hydroxysulfate or aluminum borate may be added as appropriate. A powdery inorganic filler such as talc, calcium carbonate, magnesium carbonate, cerium oxide, carbon black, titanium oxide, clay, mica, magnesium hydroxide, and aluminum hydroxide. The polycarbonate resin composition of the present invention can be obtained by blending and kneading the above-mentioned respective components in accordance with -24-200808869 (22). The compounding and melt-kneading can be carried out by a usual method such as a bow-tie blender, a Hanschel mixer, a Banbury mixer, a drum mill, a single-axis screw extruder, a twin-screw extruder, and the like. A kneader, a multi-axis screw extruder, etc. can be carried out. The heating temperature at the time of melt kneading is usually 210 to 260 °C. The present invention also provides a molded body obtained by melt-molding the polycarbonate resin composition of the present invention. • According to the present invention, a polycarbonate-hydrogenated polybutadiene copolymer having a specific structure is effective for the mutual dissolution of a polycarbonate resin and a polyolefin resin, and is blended with the polycarbonate-hydrogenated polybutadiene copolymer. Since the polycarbonate resin composition of the present invention can reduce the polyolefin functional region, it does not exhibit lamellar peeling after molding, and the mechanical properties of low-temperature impact resistance and the like are excellent. Second, further details are given according to examples. The invention is illustrated, but the invention is not limited by such examples. Production Example 1 (Production of Polycarbonate Oligomer) 60 kg of bisphenol A (BPA) was dissolved in 400 liters of a 5% by mass aqueous sodium hydroxide solution to prepare a sodium hydroxide aqueous solution of bisphenol A. Next, the aqueous sodium hydroxide solution of bisphenol A kept at room temperature was flowed at a rate of 138 liters/hour, and the flow rate of methylene chloride was 6 9 liters/hour to a tube having an inner diameter of 10 mm and a length of 10 m. The reactor was introduced through an orifice plate and phosgene was blown in its -25-200808869 (23) and blown at a flow rate of 1 〇·7 kg/hr for 3 hours. The tubular reactor used here was a double tube, and the discharge temperature of the reaction liquid was maintained at 25 ° C by cooling water in the sleeve portion. Further, the pH of the discharge liquid was adjusted to 10 to 1 1 . The reaction solution thus obtained was allowed to stand, the aqueous phase was separated and removed, and a dichloromethane phase (220 liters) was collected, and 170 liters of dichloromethane was further added thereto, and the mixture was sufficiently stirred as a PC oligomer (concentration 3). 17 g / liter). The degree of polymerization of the PC oligomer obtained here was 3 to 4 gins, and the concentration of the chloroformate group was 0.73 mol/liter. Production Example 2 (Production of Phenol Terminal Hydrogenated Polybutadiene) KRASOL HLBP-P300 manufactured by Satomer Co., Ltd. as a hydroxyl terminated hydrogenated polybutadiene was placed in a autoclave with 500 g of methyl p-hydroxybenzoate 40. 0.25 g of gram and dibutyltin oxide were stirred under a nitrogen atmosphere at 220 ° C for 6 hours under normal pressure, and methanol was distilled off. Thereafter, the pressure was reduced to remove unreacted methyl p-hydroxybenzoate. Cold ® However, the desired phenol terminal hydrogenated polybutadiene. It is a viscous liquid at room temperature. The terminal fraction was calculated by iH-NMR measurement, and the calculated terminal reaction rate was 95%. Example 1 (Production of Polycarbonate-Hydrogenated Polybutadiene Copolymer A) Polycarbonate oligomerization obtained in Production Example 1 To 10 liters, 6 liters of j chloromethane was added and diluted, and 178 g of the phenol terminal hydrogenated polybutadiene obtained in Production Example 2 and 68 g of p-tert-butylphenol were dissolved. Aqueous sodium hydroxide solution (NaOH: 60 g, water: 350 ml) -26-200808869 (24) and triethylamine 6·3 ml were added thereto, and stirred at 300 rpm for 1 hour. Thereafter, an alkaline aqueous solution of bisphenol A (bisphenol A: 712 g, sodium hydroxide: 416 g, water: 5 liters) was added, and stirred at 500 rpm for 1 hour. After stirring for 1 hour, add 1 liter of liters of water, 10 liters of water, and stir for 15 minutes, then let stand and separate the dichloromethane phase. The methylene chloride phase was washed in the order of 0. 0 3 mol/liter sodium hydroxide aqueous solution, 0.2 mol/liter hydrochloric acid, and water (2 times). Thereafter, the methylene chloride phase was concentrated, and acetone was added thereto to crystallize it, and then the solvent was removed to obtain a sheet-like polymer. Dry at 1 20 °C for 1 2 hours. The obtained polycarbonate-hydrogenated polybutadiene copolymer A had a viscosity average molecular weight (Mv) of 22,000, and the hydrogenated polybutadiene content was 4.5% by mass based on ιΗ-NMR. The viscosity average molecular weight (Mv) was determined by using a Uber-type Dessert viscosity tube and measuring the ultimate viscosity at 20 ° C in dichloromethane, and calculating according to the following formula.

[η ] = 1.23xl〇·5 · Μν° 83 Example 2 (Production of Polycarbonate-Hydrogenated Polybutadiene Copolymer Β) In Example 1, except that the phenol terminal hydrogenated polybutadiene 1 78 g The same procedure as in Example 1 was carried out except that the amount was changed to 356 g, and the polycarbonate-hydrogenated polybutadiene copolymer B was obtained. The viscosity average molecular weight (Mv): 22, 40 Å, and the hydrogenated polybutadiene content was 8.9% by mass based on 1 Η-NMR. Examples 3 to 9 and Comparative Examples 1 to 2 27 - 200808869 (25) A biaxial kneading machine (manufactured by Toshiba Machine Co., Ltd., TEM-35B) was used in the composition and temperature conditions shown in Table 1, and the number of screw revolutions was used. Melt-kneading was carried out at 30,000 rPm at 260 ° C to produce nine objects. The raw material is made of polycarbonate: Tafuron FN 1 700 (Mv: 1,7,400) manufactured by Idemitsu Kosan Co., Ltd. as polycarbonate resin (i), segmented polypropylene: Prime Polymer Co., Ltd. 卩1^11^ 〇1711161*1-78 5 Η (MI: 11 g/10 min), and high-density polyethylene: Asahi Kasei Co., Ltd. Suntech J-300 (ΜΙ: 41 g/10 min) as a polyolefin resin (ii) Tafutech H-1050 manufactured by Asahi Kasei Co., Ltd. as a solubilizing auxiliary (iv) SEBS, copolymer A and copolymer B obtained in Example 1 and Example 2 as a polycarbonate-hydrogenated polybutadiene copolymer (iii) ), and matched in the mass% shown in Table 1. Further, the mixing ratio of the polycarbonate resin (i) to the polyolefin resin (Π) was that the examples 3, 5, 7, 8, and 9 were 79% by mass of the polycarbonate resin (i), and the polyolefin resin (ii) was 21% by mass, and Examples 4 and 6 are a polycarbonate resin (i) of 78% by mass and a polyolefin resin (Π) of 22% by mass. In Table 1, the copolymer (iii) and the compatibilizing auxiliary (iv) Also marked with the total mass%. The nine examples of the obtained examples and comparative examples were evaluated by a 100-m injection molding machine (model name: IS-100EN, manufactured by Toshiba Machine Co., Ltd.) at a molding temperature of 270 ° C and a mold temperature of 80 °. (: conditions, the test piece was prepared, and the following measurement was performed. -28- 200808869 (26) (1) Melt fluidity MFR (solution flow rate) 7210, and 1 mm at a pressure of 280 T:, 15.7 MPa, Amount of molten resin flowing out of a nozzle having a length of 10 mm (2) Tensile breaking strength: measured according to JIS K 7133 (3) IZOD (cantilever beam impact strength), (taste thickness: ASTM D256, measured at 0 ° C. (4 Chemical resistance: According to the evaluation method (in 1/4 ellipsoid Q, as shown in Fig. 1 (oblique view), the 1/4 ellipse will be = 3 mm), and the test piece is coated with toluene/isooctane. Hold for 48 hours. Read the minimum length of the crack (1) to find the limit skew (%). [Number 1] 1 Limit skew (%) · —- C1 - (----- ) X2 ) 3 /2 · t X 1 0 0 2 aaa ... φ (t: test piece flesh thickness) These results are shown in Table 1. : According to ns K , measured by diameter (m 1 / sec) ° 〇 3 · 2 m m) skewed according to the limit of E) Sample (thickness = 4/6 mixture (X), and by -29-200808869 (27)

Comparative Example m 〇ITi v〇00 (N (N c5 (Μ § Os rH vo 〇〇 ON o ! i § r - 4 m CN 卜 o Example ON Os Ι / Ί mi-1 ON (N (N 00 o 00 jn m 芝-1—H v〇ON o 卜VQ 1-H <N ro jn 〇VO o ο t—H: $ (N (N oo o W"> rH CO § o inch 〇〇rH mma \ irj 00 om et al l-H <N m VO o unit (mass%) o (D a <N ^-H cd 丨KJ/m2 limit skew (%) FN1700 J-785HT J-300 copolymer AI copolymerization Η 50-1050 (1) Flow 値 (2) Tensile breaking strength <tpf steal a M fr Q 〇O °u M 〇/^-N <>/ C Ο 擀S- S〇#1 T Ng遁E ts post g ss chain sniper -30- 200808869 (28) As exemplified by the results of the examples in Table 1, each of the examples using the acid ester resin composition was melt-kneaded with the single-carbonated hydrocarbon system. In Comparative Example 1 of the resin composition, the tensile strength and the IZOD impact strength were improved, and the layered peeling did not occur in the observation of the stretched test piece. Further, the comparative example composed only of the polycarbonate resin was at a low temperature of 0 °C. Under the impact of IZOD The degree is also improved, and the degree of refinement is also improved. Moreover, it is excellent in a mixed solution of toluene/isooctane = 4/6. From these results, it is considered that the polycarbonate-hydrogenated polybutane acts as a compatibilizing agent type, and the polycondensation is reduced. An olefin functional zone, and an increase in mechanical properties and chemical resistance. Industrial Applicability The polycarbonate resin composition of the present invention is a polycarbonate-hydrogenated polybutadiene copolymer and a polyalkylene Since the resin is melted, the polyolefin functional region can be reduced, and the layered layer is peeled off, which is a low-temperature impact resistance, fluidity, and a polycarbonate resin composition, and is suitable for use in the demand of the product. Further, the polycarbonate of the present invention. In the manufacture of the ester-hydrogenated polybutadiene carbonate resin composition, the hydrogenated polybutadiene of the present invention can be effectively utilized. The polycarbonate resin of the present invention can be used in comparison with the polyene, 2, in the test. In the comparison of the three after the fracture, it is understood that the chemical resistance of the flow and the diene copolymer are various copolymers which inhibit the layered peeling of the acid ester resin having a specific structure and the properties which are not excellent in drug properties after the polyforming. Poly is a compatibilizing agent, a polycarbonate - 200 808 869 Manufacturing (29) of polybutadiene copolymers - hydrogenated -31. Further, the method for producing a polycarbonate-hydrogenated polybutadiene copolymer of the present invention is a method which is excellent in reproducibility and can be efficiently produced, and can be used in the production of the above-mentioned polycarbonate-hydrogenated polybutadiene copolymer. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view of a test piece mounting tool for evaluating the chemical resistance of the resin composition of the present invention.

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Claims (1)

200808869 (1) X. Patent Application No. 1. A polycarbonate-hydrogenated polybutadiene copolymer characterized by having the repeating unit (1) represented by the following formula (1) and the following formula ( n ) the repeated unit (π ), [Chemical 1] (I) wherein R1 and R2 each are a halogen atom (e.g., chlorine, bromine, fluorine, iodine), an alkoxy group, an ester group, a carboxyl group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, or a total carbon number of 6 The ring of -20 may have an aromatic group of an alkyl group, which may be bonded to any of the 0-position and the m-position; when each of R1 and r2 is a plurality, each of Ri and R2 may be identical to each other. Or X. is a single bond, a polymethyl group having a carbon number of 1 to 20, an alkylene group, an alkylene group, a cycloalkylene group, a cycloalkylene group, _S__, -S Ο -, - S Ο 2 ·, - Ο ·, · C 0 -bond or general formula -33- 200808869 (2) The base and the 荀 residue, m and η are integers representing 〇~4] [Chemical 3] Γ0 0 0 Hz H2 ΗίΝ C-C-G-〇Η -Y 0—C• E -a, 0-c— I! 0 (Π) [wherein R is a yard, aryl, and aryl group with a carbon number of 1 to 20, γ is a single bond, carbon number 1 〜1 聚的聚伸methyl, alkylene, and alkylene, r is 〇~4 integer, p is 〇· 00~1.00, q is an integer from 1 to 5 ;; when r3 is a majority, Most R3s can be the same or different from each other]. 2. The polycarbonate-hydrogenated polybutadiene copolymer according to claim 1, wherein the hydrogenated polybutadiene portion has a content of 〇·1 to 50% by mass 〇3. The polycarbonate-hydrogenated polybutadiene copolymer according to item 1 or 2, wherein the viscosity average molecular weight is 1 Å, 〇〇〇 50,000. A method for producing a polycarbonate-hydrogenated polybutadiene copolymer according to any one of claims 1 to 3, which is characterized in that the aromatic compound represented by the following formula (m) is used. The hydroxy compound (A) is reacted with a carbonyl source to produce a polycarbonate oligomer having an aromatic dihydroxy compound (B) represented by the following formula (IV) and the aforementioned aromatic diol Method for carrying out a reaction of a hydroxy compound (A) in a mixed solution of an organic solvent and an aqueous alkali solution, -34- 200808869 (3) [Chemical 4] [wherein, R1 and R2 each are a halogen atom (for example, chlorine, bromine, fluorine, iodine), an alkoxy group, an ester group, a carboxyl group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms or a total carbon number of 6 to 20 The ring may have an aromatic group of an alkyl group, which may be bonded to any of the 〇-position and the m-position; when each of R1 and R2 is a plurality, each of R1 and R2 may be the same or different from each other. Further, X is a single bond, a polymethyl group having a carbon number of 1 to 20, an alkyl group, an alkylene group, a cycloalkyl group, a cycloalkylene group, -S-, -SO-, -S 〇2·, -〇-, -CO-bonding or general formula [5] The base and the residue represented by m, η are integers representing 0 to 4] -35- (IV) (IV) 200808869 (4) [Chem. 6] [wherein, R3 is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and Y is a single bond, a polymethyl group having a carbon number of 1 to 1 Å, an alkylene group, an alkylene group, and 1 is 〇~4 integer, :? The number is from 0.00 to 1.00, and 9 is an integer from 1 to 500. When 113 is a majority, most of R3 may be the same or different from each other]. A polycarbonate resin composition characterized in that it is a mixture of 45 to 99% by mass of the polycarbonate resin (i) and 55 to 1% by mass of the polyolefin resin (ii). The polycarbonate-hydrogenated polybutylene diene copolymer (iii) of any one of the above claims 1 to 3 is added in an amount of from 0.1 to 30 parts by mass, and is obtained by melt-kneading. 6 - a polycarbonate resin composition characterized by being a mixture of 45 to 99% by mass of the polycarbonate resin (i) and 55 to 1% by mass of the polyolefin resin (ii) Addition of the polycarbonate-hydrogenated polybutadiene copolymer (iii) according to any one of claims 1 to 3, 〇·1 to 30 parts by mass, and styrene-ethylene•butylene-styrene block The solubilization auxiliary (W) obtained by the copolymer is 0.5 to 10 parts by mass, and is obtained by melt-kneading. A molded article obtained by melt molding of a polycarbonate resin composition of claim 5 or 6. A hydrogenated polybutadiene characterized by having a phenolic hydroxyl group at the terminal represented by the above formula (ly). -36-