Cacao husk-containing polycarbonate resin composition and molded article containing the same

Abstract

To provide a cacao husk-containing polycarbonate resin composition which has a high biomass degree and little environmental loads upon disposal, and is excellent in weld strength characteristics indispensable for molding a molded article having a complicated shape without lowering various characteristics inherent to a polycarbonate resin as much as possible.SOLUTION: A cacao husk-containing polycarbonate resin composition contains, with respect to 100 pts.mass of a polycarbonate resin (A), 1 to 30 pts.mass of a polyester-based resin (B) and 1 to 40 pts.mass of cacao husk (C).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a cocoa husk-containing polycarbonate resin composition and a molded article containing the same. [Background technology]

[0002] In recent years, effective use of food waste has been actively considered from the perspective of resource circulation. Cocoa husk (cocoa bean skin), which is generated during the production of foods made from cocoa beans such as chocolate, has traditionally been used as animal feed, fertilizer, and fuel.

[0003] On the other hand, there are new attempts to develop new and useful bio-derived materials, that is, environmentally friendly materials with a high biomass ratio (plant-based ratio), excellent environmental performance such as reduced carbon dioxide emissions and reduced fossil raw materials, and low environmental impact when disposed of. As effective utilization measures of cacao husk as a biomass material, for example, Patent Documents 1 and 2 disclose electromagnetic wave absorbing materials containing burned cacao husk. Patent Document 2 discloses a thermal conductive material containing burned cacao husk. Patent Document 3 discloses liquid absorbing rubber containing burned cacao husk. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2011 / 118687 [Patent Document 2] WO2012 / 086719 [Patent Document 3] Patent Publication 2014-193935 [Patent Document 4] Patent Publication No. 2014-047266 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the materials described in Patent Documents 1 to 4 are produced by kneading calcined and graphitized cacao husk with rubber raw materials, and then molding and vulcanizing the mixture. Therefore, the shapes of the materials are limited to simple molded products such as sheets, films, and plates.

[0006] Furthermore, in molded products with complex shapes, multiple mold gates exist in the mold due to product design, which results in linear patterns called welds appearing where the molten resin joins in the mold, reducing the strength of the molded product, but Patent Documents 1 to 4 do not disclose any means to solve this problem.

[0007] The present invention aims to provide a resin composition that has a high biomass content, imposes a low environmental impact when disposed of, and yet has excellent weld strength characteristics that are essential for molding molded articles with complex shapes, without reducing the inherent properties of polycarbonate resins as much as possible. [Means for solving the problem]

[0008] The present inventors have conducted intensive research to solve the above problems, and as a result have found that by blending a specific amount of cocoa husk (C) with polycarbonate resin (A) and polyester resin (B), a cocoa husk-containing polycarbonate resin composition can be obtained which has a high biomass content and low environmental impact when disposed of, while minimizing the deterioration of the inherent properties of polycarbonate resin such as heat resistance and impact strength, and which can improve the weld strength essential for molding complex shapes, and thus completed the present invention.

[0009] That is, the present invention (1) is a cocoa husk-containing polycarbonate resin composition characterized by containing 1 to 30 parts by mass of polyester resin (B) and 1 to 40 parts by mass of cocoa husk (C) relative to 100 parts by mass of polycarbonate resin (A).

[0010] The present invention (2) is the cacao husk-containing polycarbonate resin composition according to the present invention (1), wherein the polycarbonate resin (A) is a recycled polycarbonate resin.

[0011] The present invention (3) is the cocoa husk containing polycarbonate resin composition according to the present invention (1) or (2), wherein the polyester resin (B) is one or more polyester resins selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polybutylene adipate-co-terephthalate, and polyester thermoplastic elastomers.

[0012] The present invention (4) is the cocoa husk-containing polycarbonate resin composition according to any one of the present inventions (1) to (3), further comprising a styrene-based resin (D) or a (meth)acrylic resin (E).

[0013] The present invention (5) is the cocoa husk-containing polycarbonate resin composition according to any one of the present inventions (1) to (4), further comprising one or more selected from the group consisting of heat stabilizers, antioxidants, colorants, release agents, softeners, antistatic agents and impact modifiers.

[0014] The present invention (6) is a molded article comprising the cocoa husk-containing polycarbonate resin composition according to any one of the present inventions (1) to (5).

[0015] The present invention (7) is the molded article according to the present invention (6) molded by injection molding or a 3D printer. Effect of the Invention

[0016] The polycarbonate resin composition containing cacao husk of the present invention is an environmentally friendly material with a high biomass content and low environmental impact when disposed of, and has a good appearance when molded, and can be given design characteristics unique to biomass materials. Moreover, it is a material that improves the weld strength characteristic essential for molding complex shapes without reducing the various properties such as heat resistance and impact strength that polycarbonate resin originally has, and can be applied to various production methods such as injection molding, extrusion molding, 3D printers, etc., and can be used suitably for a wide range of applications, so it has extremely high industrial value. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The embodiments will be described in detail below. However, more detailed explanations than necessary may be omitted. For example, detailed explanations of already well-known matters or duplicate explanations of substantially the same configurations may be omitted. This is to avoid the following explanation becoming unnecessarily redundant and to facilitate understanding by those skilled in the art. Note that the inventors provide the following explanations to enable those skilled in the art to fully understand the present invention, and do not intend to limit the subject matter described in the claims.

[0018] The cocoa husk-containing polycarbonate resin composition of the present invention is characterized by containing 1 to 30 parts by mass of a polyester resin (B) and 1 to 40 parts by mass of cocoa husk (C) relative to 100 parts by mass of a polycarbonate resin (A).

[0019] 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 an aromatic polycarbonate resin produced from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).

[0020] Examples of the dihydroxydiaryl compound 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)cyclopentane and 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.

[0021] These can be used alone or in combination of two or more, but those that are not substituted with halogens are preferred from the viewpoint of preventing the emission of gases containing the halogens into the environment during combustion. In addition to these, piperazine, dipiperidylhydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, etc. may also be used in combination.

[0022] Furthermore, the above dihydroxyaryl compounds may be used in combination with the following trivalent or higher phenolic compounds: 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.

[0023] The viscosity average molecular weight of the polycarbonate resin (A) is not particularly limited, but is usually in the range of 10,000 to 100,000, more preferably 15,000 to 30,000, and even more preferably 17,000 to 26,000, from the viewpoints of moldability and strength. In addition, when producing such a polycarbonate resin, a molecular weight regulator, a catalyst, etc. can be used as necessary. The method for measuring the viscosity average molecular weight is to prepare a 0.5 mass% solution of the polycarbonate resin in methylene chloride as a solvent, measure the specific viscosity (ηsp) at a temperature of 20°C using a Cannon-Fenske type viscometer, determine the limiting viscosity [η] by concentration conversion, and calculate using the following Schnell formula. [η] = 1.23 × 10-4 M0.83

[0024] The polycarbonate resin (A) may be unused or recycled (regenerated). Examples of the regenerated resin 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-industry recycling). Available polycarbonate resins include, for example, R-PC170AS manufactured by Aida Shokai Co., Ltd., which is a recycled polycarbonate resin derived from transport containers, and PC-15NP, a recycled polycarbonate resin manufactured by OS TECH Co., Ltd., Korea.

[0025] When a recycled polycarbonate resin is contained, its content is not particularly limited, but is preferably from 10 to 100% by mass, and more preferably from 20 to 100% by mass, in the polycarbonate resin (A).

[0026] The polyester resin (B) used in the present invention is not particularly limited, but examples thereof include polyethylene terephthalate, polybutylene terephthalate, polybutylene adipate-co-terephthalate, and polyester thermoplastic elastomers.

[0027] Polybutylene adipate-co-terephthalate is a petroleum-derived, biodegradable aromatic polyester (hydrolysis type) made from BDO (1.4-BG), terephthalic acid, and adipic acid, and is a material that combines the excellent decomposition performance of aliphatic polyesters with the excellent mechanical properties of aromatic polyesters. For example, PBAT A400 manufactured by WANGO Corporation can be mentioned. The polyester-based thermoplastic elastomer is an ester-ether type or ester-ester type multiblock copolymer having an aromatic polyester as a hard segment and an aliphatic polyether or aliphatic polyester as a soft segment, and examples thereof include Pelprene P-30B, Pelprene P-40B, Pelprene P-55B, Pelprene P-70B, Pelprene P-90B, Pelprene P-40BU, Pelprene P-40U, Pelprene P-48U, Pelprene P-55U, Pelprene P-75M, Pelprene P-150M (all manufactured by Toyobo Co., Ltd.), Hytrel 3046, Hytrel 4047, Hytrel 4767, Hytrel 5557, Hytrel G3548L, Hytrel HTR8171, and Hytrel HTR8206 (all manufactured by DuPont-Toray Co., Ltd.).

[0028] The polyester resin (B) may be used alone, or a plurality of resin components may be copolymerized or mixed to be used in combination.

[0029] The blending amount of the polyester resin (B) is from 1 to 30 parts by mass, preferably from 3 to 25 parts by mass, and more preferably from 5 to 20 parts by mass, based on 100 parts by mass of the polycarbonate resin (A).

[0030] The cacao husk (C) used in the present invention is the outer skin of cacao beans that is generated during the production process of foods made from cacao beans.

[0031] The cacao husk (C) may be in the form of the cacao husk removed from the cacao beans, or may be pulverized and powdered. When pulverized, the particle size is preferably 1 to 200 μm, more preferably 10 to 100 μm, and even more preferably 15 to 35 μm.

[0032] Cocoa husk (C) may be used in combination with optional ingredients that can be mixed and treated with a polymer binder, such as wood chips or powder, calcium carbonate, talc or ceramic powder, metal powders such as aluminum and copper (static charge removers), activated carbon, zeolite particles, and other functional materials.

[0033] The blending amount of the cacao husk (C) is 1 to 40 parts by mass, preferably 2 to 30 parts by mass, more preferably 3 to 20 parts by mass, and further preferably 4 to 15 parts by mass, based on 100 parts by mass of the polycarbonate resin (A).

[0034] In the present invention, the composition may further contain a styrene-based resin (D) or a (meth)acrylic resin (E). Examples of the styrene-based resin include acrylonitrile-butadiene-styrene copolymer (ABS resin), high impact polystyrene resin (HIPS), and styrene-ethylene / butylene-styrene block copolymer (SEBS). A preferred example of the styrene-based resin is SEBS, and more preferably maleic anhydride-modified SEBS. Commercially available products of maleic anhydride-modified SEBS include Tuftec M1913 manufactured by Asahi Kasei Corporation and KRATON FG1901 manufactured by KRATON.

[0035] Examples of (meth)acrylic resins include acrylic block copolymers and acrylic core / shell type graft copolymers. Commercially available acrylic block copolymers include Clarity LA2250 and LA2140, which are triblock copolymers of polyMMA block-polyBA block-polyMMA block manufactured by Kuraray Co., Ltd. Commercially available acrylic core / shell type graft copolymers include Kane Ace M-711 manufactured by Kaneka Corporation and Metablen W-450A manufactured by Mitsubishi Chemical Corporation.

[0036] The amount of the styrene resin (D) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the polycarbonate resin (A). If the amount of the styrene resin (D) exceeds 20 parts by mass per 100 parts by mass of the polycarbonate resin (A), the weld strength may be deteriorated.

[0037] The amount of the (meth)acrylic resin (E) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the polycarbonate resin (A). If the amount of the styrene resin (E) exceeds 20 parts by mass per 100 parts by mass of the polycarbonate resin (A), the weld strength may be deteriorated.

[0038] The cacao husk containing polycarbonate resin composition of the present invention preferably further contains at least one selected from the group consisting of heat stabilizers, antioxidants, colorants, release agents, softeners, antistatic agents and impact modifiers.

[0039] The antioxidant may be a phosphorus-based antioxidant and / or a phenol-based antioxidant, and is preferably a phosphorus-based antioxidant. As the phosphorus-based antioxidant, a phosphite ester compound having the following phosphite ester structure is preferable, and examples thereof include compounds represented by the following general formulas (1), (2), (3) and (4).

[0040] [ka]

[0041] General 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.

[0042] In the general 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.

[0043] Examples of the compound represented by the general 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).

[0044] General 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 7represents 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.

[0045] In the general formula (2), R 2 , R 3 , R 5 and R 6 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.

[0046] 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.

[0047] R 2 , R 3 and R 5 are each independently preferably 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 R5 are each independently preferably 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 As the alkyl group, 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 is preferable, and a methyl group, a t-butyl group, or a t-pentyl group is more preferable.

[0048] R 6 is 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.

[0049] In the general 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.

[0050] In the general 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 6Examples of X include the alkyl and cycloalkyl groups exemplified in the description of 1. 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.

[0051] In the general formula (2), A is an alkylene group having 1 to 8 carbon atoms or a group represented by the formula: 8 Examples 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 description of A above. 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.

[0052] In the general 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.

[0053] Examples of the compound represented by the general 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, Examples of such compounds include 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, when the polycarbonate resin composition is used in a field where optical properties are particularly required, 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. An example of a commercially available product is Sumilizer GP ("Sumilizer" is a registered trademark) manufactured by Sumitomo Chemical Co., Ltd.

[0054] General 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.

[0055] Examples of the compound represented by the general 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. Commercially available products include Adeka STAB PEP-36 manufactured by ADEKA CORPORATION ("Adeka STAB" is a registered trademark).

[0056] General formula (4): [ka]

[0057] (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 The functional group connected to the single bond is excluded from the general formula (4).

[0058] A specific example of the compound represented by the general formula (4) is bis(2,4-dicumylphenyl)pentaerythritol diphosphite. A commercially available product is Dover Chemical's product name "Doverphos (registered trademark) S-9228".

[0059] Moreover, instead of or in addition to any of the compounds represented by the general formulas (1) to (4) above, a compound represented by the following general formula (5) may be used.

[0060] General formula (5): [ka] (In the formula, R 23 ~R 26 represents an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted with an alkyl group.

[0061] Specific examples of the compound represented by the general formula (5) include, for example, [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.

[0062] The blending amount of the antioxidant is preferably 1.0 part by mass or less, and more preferably 0.02 to 0.6 parts by mass, based on 100 parts by mass of the polycarbonate resin (A).

[0063] Moreover, the resin composition according to the present invention may contain a phenol-based antioxidant in place of or in addition to the phosphorus-based antioxidant.

[0064] An example of the phenol-based antioxidant is a compound represented by the following general formula (6).

[0065] General formula (6): [ka] (In the formula, R 23 represents an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted with an alkyl group.

[0066] Other phenolic antioxidants include α-tocopherol, butylated hydroxytoluene, sinapyl alcohol, vitamin E, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methyl 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylenebis(6-α-methyl-benzyl-p-cresol) 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-butylidenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethyl 1,6-Hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl 6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8 ,10-Tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl- Examples include 4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane. All of these are easily available. The above phenol-based antioxidants can be used alone or in combination of two or more.

[0067] Among them, n-octadecyl-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate, which is a compound represented by the above general formula (6), is suitable. An example of a commercially available product is Adeka STAB AO-50 manufactured by ADEKA CORPORATION.

[0068] The amount of the phenol-based antioxidant to be added is preferably 0.5 parts by mass or less based on 100 parts by mass of the polycarbonate resin (A).

[0069] The cacao husk containing polycarbonate resin composition of the present invention may contain additives such as a mold release agent, an ultraviolet absorber, a pigment, a filler, a flow improver, etc. other than the above-mentioned components, within the range that does not impair the effect.

[0070] The polycarbonate resin composition containing cocoa husk of the present invention can be produced by mixing polycarbonate resin (A), polyester resin (B) and cocoa husk (C), and, if necessary, mixing styrene resin (D) or (meth)acrylic resin (E) and the various additives. As long as the polycarbonate resin composition containing cocoa husk 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 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. By these methods, pellets of the polycarbonate resin composition containing cocoa husk can be easily obtained.

[0071] The molded article of the present invention is characterized by containing the above-mentioned cocoa husk-containing polycarbonate resin composition of the present invention. The manufacturing method of the molded article of the present invention is not particularly limited as long as the desired molded article can be obtained, but examples thereof include a method of molding the cocoa husk-containing polycarbonate resin composition by known injection molding, compression molding, 3D printer, etc.

[0072] The use of the polycarbonate resin composition containing cacao husk of the present invention is not particularly limited, but may be used for electric / electronic devices, daily necessities, building materials, etc. Molded articles obtained from the polycarbonate resin composition containing cacao husk of the present invention have high weld strength, so that the composition can be suitably used for molded articles having welds.

[0073] As described above, the embodiments of the present invention have been described as examples of the present invention. However, the technology of the present invention is not limited to the above, and can be applied to embodiments in which appropriate changes, substitutions, additions, omissions, etc. are made. EXAMPLES

[0074] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" are based on mass.

[0075] The following raw materials were used: 1.(A) Polycarbonate resin: (A1) SD Polycarbonate 200-13 manufactured by Sumika Polycarbonate Co., Ltd. (A2) Recycled polycarbonate resin PC-15NP made by OS TECH, Korea 2.(B) Polyester resin: (B1) Polybutylene adipate-co-terephthalate resin A400 manufactured by WANGO (B2) Toyobo Co., Ltd. polyester thermoplastic elastomer Pelprene P-150M 3.(C) Cacao husk: Ground cacao husk generated during the chocolate manufacturing process (median particle size 26μm) 4. (D) Styrene-based resin: (D1) Acrylonitrile-butadiene-styrene (ABS) resin Clalastic AT-05 manufactured by Nippon A&L Co., Ltd. (D2) Maleic anhydride modified styrene-ethylene / butylene-styrene block copolymer Asahi Kasei Corporation Tuftec M1913 5. (E) (Meth)acrylic resin: (E1) PolyMMA block-PolyBA block-PolyMMA triblock copolymer Kuraray Clarity LA2140 (E2) Methyl methacrylate-butadiene core-shell graft copolymer Kane Ace M-711 manufactured by Kaneka Corporation (E3) Polymer containing unsaturated carboxylic acid alkyl ester unit-acrylic core-shell type graft copolymer Mitsubishi Chemical Corporation Metablen W-450A 6. (F) Antioxidants: Tris(2,4-di-t-butylphenyl)phosphite represented by the following formula:

[0076] [ka] BASF Irgafos 168 7.(G) Release agent: Glycerin Monostearate Riken Vitamin Co., Ltd. Rikemal S-100A

[0077] Examples 1 to 14 and Comparative Examples 1 to 3 The raw materials were all charged into a tumbler in the proportions shown in Table 1 or 2 and dry mixed for 10 minutes. The mixture was then melt-kneaded at a melt temperature of 210°C using a single-screw extruder (VS40 extruder, manufactured by Tanabe Plastics Machinery Co., Ltd.) to obtain pellets of the polycarbonate resin composition of each of Examples 1 to 14 and Comparative Examples 1 to 3.

[0078] <Tensile properties> The pellets were dried in a hot air circulation shelf oven at 85°C for at least 4 hours, and then an injection molding machine (ROBOSHOT S2000i100A manufactured by FANUC CORPORATION) was used to fabricate dumbbell-shaped test pieces with a thickness of 4 mm in accordance with the ISO test method at a cylinder temperature of 220°C and a mold temperature of 50°C. Tensile tests were carried out using the test pieces obtained in accordance with ISO 527. The tensile strengths (TS) are shown in Tables 1 and 2.

[0079] <Weld strength> The pellets were dried in a hot air circulation shelf oven at 85°C for more than 4 hours, and an injection molding machine (ROBOSHOT S2000i100A manufactured by FANUC CORPORATION) was used to prepare dumbbell-shaped test pieces with a thickness of 4 mm and a weld near the center in accordance with the ISO test method at a cylinder temperature of 220°C and a mold temperature of 50°C. Using the obtained test pieces, tensile tests were performed in accordance with ISO 527, except that the tensile speed was set to 5 mm / min. Tables 1 and 2 show the tensile strength (TS-weld) and the retention calculated by dividing TS-weld by TS.

[0080] <Productivity> The material was melt-kneaded in a single-screw extruder, and during the process up to pelletization, the state of the strand emerging from the tip of the extruder was visually inspected and evaluated according to the following criteria. The results are shown in Tables 1 and 2. 〇: The strands are stable and pelletization is possible. △: Strands are sometimes distorted or broken, but pellets can be made. ×: Strands are frequently distorted or broken, making it difficult to produce pellets (difficult to granulate)

[0081] [Table 1]

[0082] [Table 2]

[0083] As shown in Tables 1 and 2, it was confirmed that the cocoa husk-containing polycarbonate resin compositions of Examples 1 to 14 were excellent in weld properties and productivity. On the other hand, the resin composition of Comparative Example 1 had no problem in productivity, but was significantly inferior in weld properties. Moreover, the resin compositions of Comparative Examples 2 and 3 were inferior in productivity and could not be granulated. [Industrial Applicability]

[0084] The polycarbonate resin composition containing cacao husk of the present invention is an environmentally friendly material with a high biomass content and low environmental impact when disposed of, and has a good appearance when molded, and can also be given design characteristics unique to biomass materials. Moreover, it is a material that improves the weld strength characteristic that is essential for molding complex shapes without reducing the various properties such as heat resistance and impact strength that polycarbonate resin originally has, and can be applied to various production methods such as injection molding, extrusion molding, 3D printers, etc., and can be used suitably for a wide range of applications, so it has extremely high industrial utility value.

Claims

1. A cocoa husk-containing polycarbonate resin composition, characterized in that it contains 1 to 30 parts by mass of a polyester resin (B) and 1 to 40 parts by mass of cocoa husk (C) relative to 100 parts by mass of a polycarbonate resin (A).

2. 2. The cocoa husk-containing polycarbonate resin composition according to claim 1, wherein said polycarbonate resin (A) is a recycled polycarbonate resin.

3. The cocoa husk containing polycarbonate resin composition according to claim 1 or 2, wherein the polyester resin (B) is one or more polyester resins selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polybutylene adipate-co-terephthalate, and polyester thermoplastic elastomers.

4. 3. The cocoa husk-containing polycarbonate resin composition according to claim 1 or 2, further comprising a styrene-based resin (D) or a (meth)acrylic resin (E).

5. 3. The cocoa husk containing polycarbonate resin composition according to claim 1 or 2, further comprising at least one selected from the group consisting of a heat stabilizer, an antioxidant, a colorant, a release agent, a softener, an antistatic agent and an impact modifier.

6. A molded article comprising the cocoa husk-containing polycarbonate resin composition according to claim 1 or 2.

7. The molded product according to claim 6, which is molded by injection molding or a 3D printer.

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