Polycarbonate resin composition and molded article thereof

Abstract

To provide a polycarbonate resin composition that, even when containing a plant-derived filler as biomass, does not cause decomposition of polycarbonate, and maintains excellent impact resistance and heat resistance, which are inherent characteristics of polycarbonate, as well as a molded article thereof.SOLUTION: A polycarbonate resin composition comprises 0.2 to 50 pts.mass of a plant-derived filler (B) relative to 100 pts.mass of a polycarbonate resin (A).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polycarbonate resin composition and a molded article thereof. [Background technology]

[0002] Polycarbonate resin is a thermoplastic resin that has excellent mechanical strength, heat resistance, thermal stability, and the like, and is therefore widely used industrially in fields such as electrical and electronics and automotive.

[0003] In recent years, due to the growing awareness of resource circulation and the environment and waste reduction, attention has been focused on bio-derived materials. Patent documents 1 to 3 describe resin compositions containing plant-derived fillers. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2018-119048 A [Patent Document 2] JP 2001-081338 A [Patent Document 3] Special Publication No. 2003-528963 Summary of the Invention [Problem to be solved by the invention]

[0005] However, because plant-derived fillers have low heat resistance and are prone to burning and decomposition when processed at high temperatures, polyolefins such as polyethylene resin and polypropylene resin, which have low processing temperatures, have mainly been used as matrix resins, and they have rarely been composited with engineering plastics such as polycarbonate resin. Composite materials using polyolefin as the matrix resin have poor impact strength and heat resistance, making them difficult to apply to fields such as electrical and electronics and automobiles.

[0006] The present invention aims to provide a polycarbonate resin composition and a molded article thereof, which, despite containing a plant-derived filler, which is biomass, is resistant to decomposition and has excellent impact strength and heat resistance, which are inherent characteristics of polycarbonate resin. [Means for solving the problem]

[0007] Means for Solving the Problems The present inventors conducted intensive research to solve the above problems, and as a result discovered that by blending a specific amount of a plant-derived filler with a polycarbonate resin, it is possible to obtain a polycarbonate resin composition that is resistant to decomposition even when it contains a plant-derived filler, and that has excellent impact strength and heat resistance, which are traditional characteristics of polycarbonate, and thus completed the present invention.

[0008] That is, the present invention (1) is a polycarbonate resin composition characterized by containing 0.2 to 50 parts by mass of a plant-derived filler (B) based on 100 parts by mass of a polycarbonate resin (A).

[0009] The present invention (2) is the polycarbonate resin composition according to the present invention (1), in which the polycarbonate resin (A) contains a recycled polycarbonate resin.

[0010] The present invention (3) is the polycarbonate resin composition according to the present invention (1) or (2), in which the plant-derived filler (B) is made from at least one plant selected from wood, wheat, tea, bamboo, and rice.

[0011] The present invention (4) is the polycarbonate resin composition according to any one of the present inventions (1) to (3), which contains 0.3 to 10 parts by mass of a dispersibility improver (C) per 100 parts by mass of the polycarbonate resin (A).

[0012] The present invention (5) is the polycarbonate resin composition according to the present invention (4), wherein the dispersibility improver (C) has at least one functional group selected from a maleic anhydride group, an amino group, and a glycidyl group.

[0013] The present invention (6) is the polycarbonate resin composition according to any one of the present inventions (1) to (5), which contains 1 to 10 parts by mass of the elastomer (D) per 100 parts by mass of the polycarbonate resin (A).

[0014] The present invention (7) is the polycarbonate resin composition according to the present invention (6), in which the elastomer (D) is a core / shell type graft copolymer.

[0015] The present invention (8) is the polycarbonate resin composition according to the present invention (7), in which the elastomer (D) is a methyl methacrylate-butadiene graft copolymer.

[0016] The present invention (9) is a polycarbonate resin composition containing one or more additives selected from the group consisting of antioxidants, colorants, release agents, softeners, spreading agents, antistatic agents, and impact modifiers.

[0017] The present invention (10) is a molded article comprising the polycarbonate resin composition according to any one of the present inventions (1) to (9).

[0018] The present invention (11) is the molded article according to the present invention (10), which is an interior product, a smartphone cover, a vehicle interior part, or an insert molded article.

[0019] The present invention (12) is the molded article according to the present invention (10) or (11), which is a decorative film. Effect of the Invention

[0020] The polycarbonate resin composition of the present invention contains a plant-derived filler, yet the composite material is resistant to decomposition, and can be made into a resin material having excellent impact strength and heat resistance, which are characteristics of polycarbonate. This allows the amount of fossil fuel used to be reduced, and addresses issues related to resource circulation and the environment and waste reduction, making the composition extremely valuable in industrial applications. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be modified and implemented as desired without departing from the gist of the present invention.

[0022] The polycarbonate resin composition of the present invention is characterized by containing 0.2 to 100 parts by mass of a plant-derived filler (B) based on 100 parts by mass of a polycarbonate resin (A).

[0023] The polycarbonate resin (A) used in the present invention is a polymer obtained by the phosgene process in which various dihydroxydiaryl compounds are reacted with phosgene, or the ester exchange process in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate, and a representative example is a polycarbonate resin produced from 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A).

[0024] Examples of the dihydroxydiaryl compounds include, in addition to bisphenol A, bis(hydroxyaryl)alkanes such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclohexane, dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, and dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.

[0025] These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidylhydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, etc. may also be used in combination.

[0026] Furthermore, the above dihydroxyaryl compounds may be used in combination with the following trivalent or higher phenol compounds: Trivalent or higher phenol compounds include phloroglucin, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene, 2,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, and 2,2-bis-[4,4-(4,4'-dihydroxydiphenyl)-cyclohexyl]-propane.

[0027] The viscosity average molecular weight of the polycarbonate resin (A) is not particularly limited, but from the viewpoints of moldability and strength, it is usually in the range of 10,000 to 100,000, more preferably 16,000 to 30,000, and even more preferably 19,000 to 26,000. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst, etc. may be used as necessary.

[0028] The amount of the polycarbonate resin (A) in the polycarbonate resin composition is preferably 25 to 95% by mass. If the amount of the polycarbonate resin (A) exceeds 95% by mass, the processability may be poor, and if it is less than 25% by mass, the heat resistance may be poor, which is not preferable.

[0029] The polycarbonate resin (A) may be unused or recycled (regenerated). The blending ratio of unused and regenerated resins can be appropriately adjusted. Preferable examples of regenerated resins include those used in transport containers, automobile headlamps, optical disks, building materials such as plate materials, etc. (post-consumer recycling), and sprues, runners, scraps, etc. generated during injection molding or extrusion molding (post-industrial recycling). Commercially available products include, for example, R-PC170AS manufactured by Aida Shokai Co., Ltd., which is a recycled polycarbonate resin derived from transport containers.

[0030] When a recycled polycarbonate resin is contained, its content is not particularly limited, but is preferably from 10 to 90% by mass, and more preferably from 20 to 80% by mass, in the polycarbonate resin (A).

[0031] The plant-derived filler (B) used in the present invention refers to a filler made from wood, wheat, tea, bamboo, rice, and other plants that are processing residues generated during the manufacture of products in various fields and cannot be used as products. Examples include wood powder generated during the processing of wood and wooden products, loss materials generated during the malt manufacturing process in beer factories, fine powders such as cuttings generated during the tea manufacturing process, bamboo powder crushed from abandoned bamboo forests, rice bran and powdered rice generated during rice polishing, etc.

[0032] The plant-derived filler may be used in the form of a powder, a pellet, or a masterbatch pellet with a resin. The method for obtaining the powder is not particularly limited. Examples of the crushing device include a hammer mill, a jet mill, and a roller mill. Pretreatment may also be performed using a coarse crushing device such as a jaw crusher, a cone crusher, and a hammer crusher. The powder obtained by crushing may be adjusted in particle size distribution by dry classification or wet classification. The method for obtaining the pellet is not particularly limited. The pellet shape is molded by a ring die method, a flat die method, or the like. The method for obtaining the masterbatch pellet with a resin is not particularly limited. It is produced by a single-screw extruder or a twin-screw extruder used for producing resin pellets.

[0033] The average particle size of the plant-derived filler (B) is not particularly limited, but is preferably from 1 to 2000 μm, more preferably from 5 to 1000 μm.

[0034] Plant-derived fillers are available from Hiroshima Tanka Kogyo Co., Ltd., Biopoly Joetsu Co., Ltd., Nissin FULFIL Co., Ltd., and the like.

[0035] The amount of plant-derived filler (B) is 0.2 to 50 parts by mass, preferably 0.3 to 40 parts by mass, and more preferably 0.4 to 30 parts by mass, relative to 100 parts by mass of polycarbonate resin. If the amount of plant-derived filler (B) exceeds 50 parts by mass, the productivity decreases, and if it is less than 0.2 parts by mass, the waste reduction effect is lost.

[0036] The polycarbonate resin composition according to the present invention may contain a decomposition improver (C). The dispersion improver (C) is a component that improves the dispersibility of the plant-derived filler (B) in the polycarbonate resin (A). Examples of the dispersion improver (C) include compounds having at least one functional group selected from a maleic anhydride group, an amino group, and a glycidyl group.

[0037] As the compound containing maleic anhydride groups, maleic anhydride-modified styrene-ethylene / butylene-styrene block copolymer (maleic anhydride-modified SEBS) and α-olefin-maleic anhydride copolymer are preferred. Maleic anhydride-modified SEBS is an unsaturated carboxylic acid modified product of styrene-ethylene / butylene-styrene block copolymer, which is a styrene-based rubber polymer, and has excellent heat resistance, impact resistance, and compatibility with plant-derived fillers. Maleic anhydride-modified SEBS is not limited in its manufacturing method, and can be obtained by known methods, such as emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, or a combination of these methods. Commercially available products include Tuftec (registered trademark) M1913 manufactured by Asahi Kasei Corporation, KRATON (registered trademark) FG1901 and KRATON FG1924 manufactured by KRATON, and TAIPOL SEBS-7131 manufactured by TSRC in Taiwan.

[0038] The α-olefin-maleic anhydride copolymer is a copolymer of maleic anhydride and α-olefin, a copolymer of maleic anhydride and a conjugated diene monomer, or a copolymer of conjugated diene and aromatic vinyl monomer, and has excellent heat resistance, impact resistance, and compatibility with plant-derived fillers. The α-olefin-maleic anhydride copolymer is obtained by grafting maleic anhydride onto the above-mentioned olefin polymer, and a known method can be used for the graft modification. For example, it can be obtained by mixing a predetermined amount of unsaturated carboxylic acids with a molten olefin polymer using an extruder and reacting them. Commercially available products include Diacarna (registered trademark) 30M manufactured by Mitsubishi Chemical Corporation.

[0039] As the compound containing an amino group, an amine-modified styrene-ethylene / butylene-styrene block copolymer (amine-modified SEBS) is preferred. The amine-modified SEBS is an amine-modified product of a styrene-ethylene / butylene-styrene block copolymer, which is a styrene-based rubber polymer, and has excellent heat resistance, impact resistance, and compatibility with plant-derived fillers. The method of producing the amine-modified SEBS is not limited in any way, and it can be obtained by a known method, such as an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, a solution polymerization method, or a combination of these methods. An example of a commercially available product is Tuftec MP10 manufactured by Asahi Kasei Corporation.

[0040] As the compound containing a glycidyl group, glycidyl-modified styrene-butadiene-styrene copolymer (glycidyl-modified SBS) and polyglycidyl methacrylate (PGMA) are preferred. Glycidyl-modified SBS is a glycidyl-modified product of styrene-butadiene-styrene copolymer, which is a styrene-based rubber polymer, and has excellent heat resistance, impact resistance, and compatibility with plant-derived fillers. The method of producing the glycidyl-modified SBS is not limited in any way, and it can be obtained by known methods, such as emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, or a combination of these. Commercially available products include Epofriend (registered trademark) AT501 and Epofriend CT310 manufactured by Daicel Corporation.

[0041] Polyglycidyl methacrylate is a glycidyl-modified acrylic polymer, and has excellent heat resistance, impact resistance, and compatibility with plant-derived fillers. There is no limitation on the method of producing polyglycidyl methacrylate, and it can be obtained by known methods, such as emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, or a combination of these methods. Commercially available products include Metablen (registered trademark) P-1901 manufactured by Mitsubishi Chemical Corporation.

[0042] The blending amount of the dispersion improver (C) is 0.3 to 10 parts by mass, preferably 0.5 to 8 parts by mass, and more preferably 1 to 5 parts by mass, based on 100 parts by mass of the polycarbonate resin (A). When the blending amount is within this range, the impact strength, heat resistance, and dispersibility of the plant-derived filler are improved.

[0043] Furthermore, the polycarbonate resin composition of the present invention may contain an elastomer (D). The elastomer (D) used in the present invention is a component that is blended to maintain the impact strength and heat resistance, which are characteristics of polycarbonate, that are reduced by the plant-derived filler (B).

[0044] Examples of the elastomer (D) include core / shell type graft copolymers. The core / shell type graft copolymer, methyl methacrylate-butadiene graft copolymer (MB), is a core-shell type graft copolymer in which the core is butadiene and the shell is methyl methacrylate. Examples of commercially available products include Kane Ace (registered trademark) M-711 manufactured by Kaneka Corporation and Paraloid (registered trademark) EXL2603 manufactured by Dow Chemical Company.

[0045] The polymerization method for the elastomer (D) can be, for example, known emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, or a combination of these polymerization methods may be used.

[0046] The blending amount of the elastomer (D) is 1 to 10 parts by mass, preferably 1 to 25 parts by mass, and more preferably 3 to 15 parts by mass, based on 100 parts by mass of the polycarbonate resin. If the blending amount is within this range, the impact strength and heat resistance are maintained.

[0047] The polycarbonate resin composition of the present invention preferably further contains one or more additives selected from the group consisting of antioxidants, colorants, release agents, softeners, spreading agents, antistatic agents, and impact modifiers.

[0048] The antioxidant is not particularly limited as long as the aromatic polycarbonate resin composition targeted by the present invention can be obtained, but examples of the antioxidant include phosphorus-based antioxidants, and the phosphorus-based antioxidant preferably contains a phosphite compound having the following phosphite structure: [ka]

[0049] Examples of the phosphorus-based antioxidant include a phosphite compound represented by the following formula (1), a phosphite compound represented by the following formula (2), a phosphite compound represented by the following formula (3), and a phosphite compound represented by the following formula (4).

[0050] Formula (1): [ka] (In the formula, R 1 represents an alkyl group having 1 to 20 carbon atoms, and a represents an integer of 0 to 3.

[0051] In the above formula (1), R 1 is an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

[0052] Examples of the compound represented by formula (1) include triphenyl phosphite, tricresyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, and trisnonylphenyl phosphite. Among these, tris(2,4-di-t-butylphenyl) phosphite is particularly suitable. Examples of commercially available products include Irgafos 168 manufactured by BASF ("Irgafos" is a registered trademark of BASF Societas Europea).

[0053] Formula (2): [ka] (In the formula, R 2 , R 3 , R 5 and R 6 R each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group. 4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; X represents a single bond, a sulfur atom, or a group represented by the formula: -CHR 7 - (where R 7 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. A represents an alkylene group having 1 to 8 carbon atoms or a group represented by the formula: *-COR 8 - (where R 8 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond on the oxygen side. Either Y or Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[0054] In formula (2), R 2 , R 3 , R 5 and R 6each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group.

[0055] Here, examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, t-pentyl, i-octyl, t-octyl, and 2-ethylhexyl groups. Examples of the cycloalkyl group having 5 to 8 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl, 1-methylcyclohexyl, and 1-methyl-4-i-propylcyclohexyl groups. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl, α-methylbenzyl, and α,α-dimethylbenzyl groups.

[0056] Above R 2 , R 3 and R 5 are each preferably independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl group having 6 to 12 carbon atoms. 2 and R 5 are each preferably independently a t-alkyl group such as a t-butyl group, a t-pentyl group, or a t-octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group. 3 is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, or a t-pentyl group, and more preferably a methyl group, a t-butyl group, or a t-pentyl group.

[0057] Above R 6is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms, and more preferably a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, or a t-pentyl group.

[0058] In formula (2), R 4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include the above-mentioned R 2 , R 3 , R 5 and R 6 In particular, R 4 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0059] In formula (2), X is a single bond, a sulfur atom or a group represented by the formula: -CHR 7 -, where the formula is -CHR 7 -R in 7 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms include the above-mentioned R 2 , R 3 , R 5 and R 6 In particular, X is preferably a single bond, a methylene group, or a methylene group substituted with a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or the like, and more preferably a single bond.

[0060] In formula (2), A is an alkylene group having 1 to 8 carbon atoms or a group represented by the formula: 8Examples of the alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a 2,2-dimethyl-1,3-propylene group, and the like, with a propylene group being preferred. 8 -R in 8 R represents a single bond or an alkylene group having 1 to 8 carbon atoms. 8 Examples of the alkylene group having 1 to 8 carbon atoms represented by the formula (I) include the alkylene groups exemplified in the above description of A. 8 is preferably a single bond or an ethylene group. 8 The * in - is a bond on the oxygen side, indicating that the carbonyl group is bonded to the oxygen atom of the phosphite group.

[0061] In formula (2), one of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, and a pentyloxy group. Examples of the aralkyloxy group having 7 to 12 carbon atoms include a benzyloxy group, an α-methylbenzyloxy group, and an α,α-dimethylbenzyloxy group. Examples of the alkyl group having 1 to 8 carbon atoms include the above-mentioned R 2 , R 3 , R 5 and R 6 Examples of the alkyl group include those exemplified in the explanation of the above.

[0062] Examples of the compound represented by formula (2) include 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine, 6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine, 6 -[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, etc. Among these, 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine is preferred when the resulting aromatic polycarbonate resin composition is used in a field where optical properties are particularly required. An example of a commercially available product is Sumilizer GP ("Sumilizer" is a registered trademark) manufactured by Sumitomo Chemical Co., Ltd.

[0063] Formula (3): [ka] (In the formula, R 9 and R 10 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and b and c each independently represent an integer of 0 to 3.

[0064] Examples of the compound represented by formula (3) include bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, etc. As a commercially available product, ADK STAB PEP-36 manufactured by ADEKA CORPORATION ("ADK STAB" is a registered trademark) is commercially available.

[0065] Formula (4): [ka]

[0066] (In the formula, R 11 ~R 18 R each independently represents an alkyl group or an alkenyl group having 1 to 3 carbon atoms. 11 and R 12 , R 13 and R 14 , R 15 and R 16 , R 17 and R 18 may be bonded to each other to form a ring. 19 ~R 22 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. d to g each independently represents an integer of 0 to 5. X 1 ~X 4 Each of X independently represents a single bond or a carbon atom. 1 ~X 4 is a single bond, R 11 ~R 22 Among these, the functional group connected to the single bond is excluded from the general formula (4).

[0067] A specific example of the compound represented by formula (4) is bis(2,4-dicumylphenyl)pentaerythritol diphosphite, for example. A commercially available product is Doverphos (registered trademark) S-9228 manufactured by Dover Chemical Co.

[0068] Further examples of phosphorus-based antioxidants include [1,1'-biphenyl]-4,4'-diylbis[bis(2,4-di-t-butylphenoxy)phosphine], etc. Commercially available products include, for example, Irgaphos P-EPQ (trade name) manufactured by BASF and HOSTANOX P-EPQ (trade name) manufactured by Clariant Chemicals.

[0069] The blending amount of the antioxidant is preferably 1.0 part by mass or less, and more preferably 0.02 to 0.5 parts by mass, based on 100 parts by mass of the polycarbonate resin (A).

[0070] Examples of the release agent include natural beeswax, fatty acid ester, glycerin fatty acid ester, polyol fatty acid ester, etc. The amount of the release agent added is preferably 0.1 to 1.0 part by mass per 100 parts by mass of the polycarbonate resin. If the amount exceeds 1.0 part by mass, the physical properties may decrease, and the thermal stability may become insufficient during retention during molding processing, causing discoloration.

[0071] Examples of the spreading agent include natural epoxidized soybean oil and liquid paraffin. The amount of the spreading agent added is preferably 0.001 to 10 parts by mass relative to 100 parts by mass of the polycarbonate resin. If the amount exceeds 10 parts by mass, the productivity is poor, and if the amount is less than 0.001 part by mass, the spreading property tends to be insufficient.

[0072] The polycarbonate-based resin composition of the present invention can be used to prepare a molded product or a molded film by injection molding or extrusion molding. The uses of the molded product or the molded film are not particularly limited, and examples thereof include interior use, smartphone covers, and insert molded products. The molded film can also be used as a decorative film.

[0073] The polycarbonate-based resin composition of the present invention can also be used as a resin film for insert molding. The resin film for insert molding is a resin film that is inserted into a mold when insert molding a thermoplastic resin such as a polycarbonate resin. Since polycarbonate resin is usually injection molded at a molding temperature of 280°C or higher, a high level of heat resistance is required even for the film inserted into the mold, so the polycarbonate-based resin composition of the present invention, which has high heat resistance, can be preferably used. The thickness of the resin film is preferably 0.05 to 2.0 mm, more preferably 0.1 to 1.5 mm, and even more preferably 0.2 to 0.8 mm.

[0074] The polycarbonate resin composition of the embodiment of the present invention can be produced by mixing a polycarbonate resin (A), a plant-derived filler (B), and if necessary, a dispersion improver (C), an elastomer (D), and further an antioxidant and various additives. As long as the polycarbonate resin composition of the present invention can be obtained, the production method is not particularly limited, and the type and amount of each component can be appropriately adjusted. The method of mixing the components is also not particularly limited, and examples thereof include a method of mixing using a known mixer such as a tumbler or ribbon blender, and a method of melt kneading using an extruder. Pellets of the polycarbonate resin composition can be easily obtained by these methods.

[0075] As described above, the embodiment of the present invention has been described as an example of the present invention. However, the technology of the present invention is not limited to this, and can be applied to the embodiment with appropriate changes, substitutions, additions, omissions, etc. EXAMPLES

[0076] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples, and can be practiced with any changes or modifications within the scope of the present invention. Unless otherwise specified, "%" and "parts" in the examples respectively indicate "% by mass" and "parts by mass" based on mass.

[0077] Details of the raw materials used are as follows: 1. Polycarbonate resin (A) (a1) PC resin: manufactured by Sumika Polycarbonate Co., Ltd. SD Polycarbonate 200-13 (viscosity average molecular weight 21000) (a2) Recycled PC resin: manufactured by Aida Shokai Co., Ltd. R-PC170AS (viscosity average molecular weight 19000)

[0078] 2. Plant-derived filler (B) (b1-1) Hinoki MB: Asahi Yuusu Co., Ltd. Hinoki 55% / PP resin (b1-2) Cypress powder: Yoshino cypress sawdust made by Kita Sawmill, 1mm (b2) Hiba MB: Made by Biopoly Joetsu Co., Ltd. BMP-W51G-10 (51% Japanese cypress / PP resin) (b3) Cedar MB: Made by Plaisir Co., Ltd. WPC-MB65 (65% cedar / PP resin) (b4) Spruce MB: Made by Nissin FULFIL Co., Ltd. W-148 (70% spruce / PP resin) (b5) White Ash MB: Manufactured by Sun Three Co., Ltd. PANDO.WP (White Ash 51% / Biomass PE Resin) (b6) White wood powder: White wood powder manufactured by Hiroshima Carbonization Industry Co., Ltd. (b7) Barley MB: 55% barley / PP resin manufactured by Asahi Yuasa Co., Ltd. (b8) Tea MB: Asahi Yuasu Co., Ltd. Tea 55% / PP resin (b9) Bamboo charcoal MB: Manufactured by Asahi Yuas Co., Ltd. Bamboo charcoal 55% / PP resin (b10) Powdered rice / rice bran MB: Manufactured by Biopoly Joetsu Co., Ltd. SRP70 (70% rice powder or rice bran / PP resin)

[0079] 3. Dispersion improver (c1) m-SEBS (maleic anhydride modified SEBS): Asahi Kasei Corporation Tuftec M1913 (c2) AO-MAn (α-olefin-maleic anhydride copolymer): Mitsubishi Chemical Corporation Diakaruna 30M (c3) a-SEBS (amine-modified SEBS): Asahi Kasei Corporation Tuftec MP10 (c4) g-SBS (glycidyl-modified SBS): Daicel Corporation Epofriend AT501 (c5) PGMA (polyglycidyl methacrylate): Mitsubishi Chemical Corporation Metablen P-1901

[0080] 4. Elastomer component (D): (d1) MB (methyl methacrylate-butadiene copolymer) Kaneka Corporation Kane Ace M-711

[0081] Examples 1 to 31 and Comparative Examples 1 to 2 The raw materials were all charged into a tumbler in the proportions shown in Tables 1 to 3 and dry-mixed for 10 minutes, and then melt-kneaded at a melting temperature of 240°C using a single-screw extruder (VS40 extruder, manufactured by Tanabe Plastics Machinery Co., Ltd.) to obtain pellets of the aromatic polycarbonate resin composition of each of Examples 1 to 31 and Comparative Examples 1 and 2. The obtained pellets were dried at 105°C for 4 hours or more and evaluated by the methods shown below. The results are shown in Tables 1 to 3.

[0082] <Tensile strength> Using an injection molding machine (ROBOSHOT S2000i100A manufactured by Fanuc Corporation), test pieces with a thickness of 4 mm were prepared according to the ISO test method under conditions of a cylinder temperature of 220 to 250°C and a mold temperature of 50°C. The tensile strength of the obtained test pieces was measured according to ISO 527 and evaluated according to the following criteria. ◎: Tensile strength is 55MPa or more ○: Tensile strength is 40 MPa or more ×: Tensile strength is less than 40 MPa

[0083] <Bending strength> Using an injection molding machine (ROBOSHOT S2000i100A manufactured by Fanuc Corporation), test pieces with a thickness of 4 mm were prepared according to the ISO test method under conditions of a cylinder temperature of 220 to 250°C and a mold temperature of 50°C. The bending strength of the obtained test pieces was measured according to ISO 178 and evaluated according to the following criteria. ◎: Bending strength is 80MPa or more ○: Bending strength is 60MPa or more ×: Bending strength is less than 60 MPa

[0084] <Impact strength> Using an injection molding machine (ROBOSHOT S2000i100A manufactured by Fanuc Corporation), test pieces with a thickness of 4 mm were prepared according to the ISO test method at a cylinder temperature of 220 to 250°C and a mold temperature of 50°C. The notched Charpy impact strength of the obtained test pieces was measured according to ISO 179-1 and evaluated according to the following criteria. ◎: Notched Charpy impact strength is 10kJ / cm 2 End ○: Notched Charpy impact strength is 5 kJ / cm 2 End ×: Notched Charpy impact strength is 5 kJ / cm 2 less than

[0085] <Heavy deflection temperature (HDT)> Using an injection molding machine (ROBOSHOT S2000i100A manufactured by FANUC CORPORATION), test pieces with a thickness of 4 mm were prepared according to the ISO test method at a cylinder temperature of 220 to 250°C and a mold temperature of 50°C. The deflection temperature under load of the obtained test pieces was measured under conditions of 1.80 MPa according to ISO75-2, and evaluated according to the following criteria. ◎: Deflection temperature under load is 120℃ or higher ○: Deflection temperature under load is 110℃ or higher ×: Deflection temperature under load is less than 110℃

[0086] <Productivity> During the process from melt kneading in a single screw extruder to producing pellets, the state of the strand emerging from the tip of the extruder was visually observed and evaluated according to the following criteria. ◯: The strands are stable and pellets can be produced. Δ: Although strands were occasionally disturbed or broken, pellets could be produced. ×: Disorders and breakage of strands frequently occur, making it difficult to prepare pellets.

[0087] <Insert moldability judgment> Using an extrusion molding machine (VS40 extruder manufactured by Tanabe Plastics Machinery Co., Ltd.), a film having a thickness of 200 μm to 700 μm was molded at a cylinder temperature of 210°C to 300°C and a die temperature of 210°C to 300°C. The molded film was inserted into a mold, and polycarbonate resin pellets were inserted into the mold using an injection molding machine (ROBOSHOT S2000i100B manufactured by Fanuc Corporation) at a cylinder temperature of 250°C to 310°C. The state of the obtained insert molded product was visually inspected and evaluated according to the following criteria. ◯: No whitening or sink marks occurred on the insert film, and the design was excellent. △: No whitening or sink marks occurred on the insert film, but the design was not sufficient. ×: Whitening or sink marks occurred on the insert film, and the design was poor.

[0088] [Table 1]

[0089] [Table 2]

[0090] [Table 3]

[0091] From Tables 1 to 3, the polycarbonate resin compositions of Comparative Examples 1 and 2 had a large amount of plant-derived filler blended therein and were inferior in productivity. On the other hand, it was confirmed that, within the range in which the polycarbonate resin (A) and the plant-derived filler (B) exhibit the effects of the present invention, the compositions have excellent impact strength and heat resistance, which are conventional characteristics of polycarbonate, and further have excellent insert moldability. [Industrial Applicability]

[0092] The polycarbonate resin composition of the present invention is resistant to decomposition even when it contains plant-derived materials, and can be made into a resin material that has excellent impact strength and heat resistance, which are traditional characteristics of polycarbonate. Therefore, the amount of fossil fuel used can be reduced, and problems related to resource circulation and the environment and waste reduction can be addressed, making the composition extremely valuable in industrial applications.

Claims

1. A polycarbonate resin composition comprising 0.2 to 50 parts by mass of a plant-derived filler (B) per 100 parts by mass of a polycarbonate resin (A).

2. 2. The polycarbonate resin composition of claim 1, wherein the polycarbonate resin (A) comprises a recycled polycarbonate resin.

3. 2. The polycarbonate resin composition according to claim 1, wherein the plant-derived filler (B) is made from at least one plant selected from the group consisting of wood, wheat, tea, bamboo, and rice.

4. The polycarbonate resin composition according to claim 1, further comprising 0.3 to 10 parts by mass of a dispersibility improver (C) per 100 parts by mass of the polycarbonate resin (A).

5. 5. The polycarbonate resin composition according to claim 4, wherein the dispersibility improver (C) has at least one functional group selected from a maleic anhydride group, an amino group, and a glycidyl group.

6. The polycarbonate resin composition according to claim 1, further comprising 1 to 10 parts by mass of an elastomer (D) per 100 parts by mass of the polycarbonate resin (A).

7. The polycarbonate resin composition according to claim 6, wherein the elastomer (D) is a core / shell type graft copolymer.

8. 8. The polycarbonate resin composition according to claim 7, wherein the elastomer (D) is a methyl methacrylate-butadiene graft copolymer.

9. The polycarbonate resin composition according to claim 1, further comprising one or more additives selected from the group consisting of antioxidants, colorants, release agents, softeners, spreading agents, antistatic agents and impact modifiers.

10. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 9.

11. The molded article according to claim 10, which is any one of an interior product, a smartphone cover, a vehicle interior part, and an insert molded article.

12. The molded article according to claim 10, which is a decorative film.

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