WO2013133228A1

WO2013133228A1 - Polycarbonate resin composition

Info

Publication number: WO2013133228A1
Application number: PCT/JP2013/055883
Authority: WO
Inventors: 野寺　明夫
Original assignee: 出光興産株式会社
Priority date: 2012-03-07
Filing date: 2013-03-04
Publication date: 2013-09-12

Abstract

The present invention provides a polycarbonate resin composition which comprises 100 parts by mass of a resin mixture comprising 99 to 60 mass% of a polycarbonate resin (A) and 1 to 40 mass% of cellulose fibers (B) having an average fiber diameter of 5 to 50 μm and an average fiber length of 0.03 to 1.5 mm and 0.2 to 30 parts by mass of a terpene compound (C), said resin composition having excellent environmental properties because a biomass material is used, having a low specific gravity, high stiffness, excellent molding appearance and good thermal stability, and being imparted with flame retardancy.

Description

Polycarbonate resin composition

The present invention is excellent in environmental characteristics by using a biomass material, has little reduction in impact strength, has a low specific gravity, high rigidity, excellent molding appearance, has good thermal stability, little coloration, and imparts flame retardancy. It is related with the made polycarbonate resin composition.

In recent years, biomass materials have attracted attention from the viewpoint of environmental protection, and natural organic fillers and composite materials with biopolymers have begun to be used as automobiles, OA / electrical and electronic materials. In addition, for the purpose of improving mechanical strength such as rigidity and heat resistance to the resin, a method of adding an inorganic filler such as glass fiber to the resin composition has been studied. There is a problem that the specific gravity of the wastewater increases, and the residue which becomes garbage at the time of incineration or disposal increases, which places a burden on the environment.

As a composite material in which a natural organic filler is blended, for example, Patent Document 1 discloses a technique of blending cellulose or a cellulose derivative in order to improve the fluidity and chemical resistance of a polycarbonate resin. However, Patent Document 1 is a polymer alloy technique such as cellulose acetate, and is not intended to improve mechanical strength such as rigidity by blending cellulose fibers.
Furthermore, in Patent Document 2, a natural organic filler is used to blend an aliphatic polyester and a natural organic filler into an aromatic polycarbonate resin to obtain a resin composition having excellent mechanical properties and flame retardancy. A technique in which a jute fiber or rayon fiber is used as a composite with a resin composition is disclosed. However, the resin composition obtained in Patent Document 2 has a large decrease in impact strength, an insufficient molding appearance, a large coloration, and an insufficient thermal stability during molding.

JP 60-158252 A JP 2010-215791 A

The present invention has been made under the above circumstances, and is excellent in environmental characteristics due to the use of biomass material, has little reduction in impact strength, has low specific gravity, high rigidity, excellent molding appearance, and good thermal stability. An object of the present invention is to provide a resin composition with little coloration and imparted with flame retardancy.

As a result of intensive studies, the present inventors solved the above problem by blending cellulose fibers having a specific average fiber diameter and average fiber length as a biomass material into a polycarbonate resin together with a terpene compound. Found to get.
That is, the present invention relates to the following polycarbonate resin composition.

1. (A) 99 to 60% by mass of polycarbonate resin and (B) 100% by mass of a resin mixture comprising 1 to 40% by mass of cellulose fibers having an average fiber diameter of 5 to 50 μm and an average fiber length of 0.03 to 1.5 mm. A polycarbonate resin composition containing 0.2 to 30 parts by mass of (C) a terpene compound relative to parts.
2. (B) The polycarbonate resin composition as described in 1 above, wherein the α-cellulose content in the cellulose fiber is 80% by mass or more.
3. (A) The polycarbonate resin composition according to the above 1 or 2, wherein the polycarbonate resin is a polycarbonate-polyorganosiloxane copolymer or contains a polycarbonate-polyorganosiloxane copolymer.
4). 4. The polycarbonate resin composition according to any one of 1 to 3, further comprising (D) 0.2 to 30 parts by mass of a phosphorus compound with respect to 100 parts by mass of a resin mixture comprising (A) a polycarbonate resin and (B) cellulose fibers. object.
5. 5. The polycarbonate according to any one of 1 to 4 above, further comprising 0.05 to 1 part by mass of (E) polytetrafluoroethylene with respect to 100 parts by mass of the resin mixture comprising (A) a polycarbonate resin and (B) cellulose fibers. Resin composition.

[(A) Polycarbonate resin]
In the polycarbonate resin composition of the present invention (hereinafter sometimes abbreviated as PC resin composition), (A) the polycarbonate resin may be an aromatic PC resin or an aliphatic PC resin, An aromatic PC resin is preferable from the viewpoint of impact resistance and heat resistance.
In the present invention, for example, an aromatic PC resin having a terminal group represented by the following general formula (1) can be used.

In the general formula (1), R ¹ is an alkyl group having 1 to 35 carbon atoms, and may be linear or branched. Further, the bond position may be any of p-position, m-position and o-position, but p-position is preferred. a represents an integer of 0 to 5.
The viscosity average molecular weight of this aromatic PC resin is usually 10,000 to 40,000, and is preferably 13,000 to 30,000, more preferably 15 from the viewpoint of imparting heat resistance, flame retardancy and impact resistance. , 4,000 to 24,000.
The viscosity average molecular weight (Mv) is a value obtained by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, obtaining the intrinsic viscosity [η] from this, and calculating by the following formula. [Η] = 1.23 × 10 ⁻⁵ Mv ^0.83

The aromatic PC resin having a terminal group represented by the general formula (1) can be easily produced by reacting a dihydric phenol with phosgene or a carbonate compound. That is, for example, in a solvent such as methylene chloride, by the reaction of a dihydric phenol and a carbonate precursor such as phosgene in the presence of a catalyst such as triethylamine and a specific end terminator, or between the dihydric phenol and diphenyl carbonate. It is produced by transesterification with such a carbonate precursor.
Examples of the dihydric phenol include compounds represented by the following general formula (2).

In the general formula (2), R ² and R ³ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different. Z is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylidene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group having 5 to 20 carbon atoms, or —SO ₂ —, — SO—, —S—, —O—, —CO— bond is shown. An isopropylidene group is preferred. b and c are integers of 0 to 4, preferably 0.

Examples of the dihydric phenol represented by the general formula (2) include 4,4′-dihydroxydiphenyl; 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, Bis (4-hydroxyphenyl) alkanes such as 2,2-bis (4-hydroxyphenyl) propane; bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) oxide; bis (4-hydroxyphenyl) sulfide Bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ketone, and the like. Of these, 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A] is preferable. These dihydric phenols may be used alone or in combination of two or more.
The dihydric phenol may be a homopolymer using one of the above dihydric phenols or a copolymer using two or more. Furthermore, the thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound together with the said bihydric phenol may be sufficient.

Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.
As the terminal terminator, a phenol compound in which the terminal group represented by the general formula (1) is formed, that is, a phenol compound represented by the following general formula (3) may be used. In the following general formula (3), R ¹ and a are as defined above.

Examples of the phenol compound represented by the general formula (3) include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, docosylphenol, tetracosyl. Examples include phenol, hexacosylphenol, octacosylphenol, triacontylphenol, dotriacontylphenol, tetratriacontylphenol, p-tert-pentylphenol, and the like. You may use these individually by 1 type or in mixture of 2 or more types. Further, these phenol compounds may be used in combination with other phenol compounds as necessary.
The aromatic PC resin produced by the above method has a terminal group represented by the general formula (1) substantially at one or both ends of the molecule.

In the present invention, the PC resin as the component (A) is abbreviated as a polycarbonate-polyorganosiloxane copolymer (hereinafter referred to as a PC-POS copolymer) from the viewpoint of improving heat resistance, flame retardancy and impact resistance. Or a PC resin containing the same. From the same viewpoint, the PC-POS copolymer is more preferably a polycarbonate-polydimethylsiloxane copolymer in which POS is polydimethylsiloxane.
The polyorganosiloxane part (segment) is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and further preferably 2 to 5% by mass in the component (A). Further, it is preferably 0.05 to 3% by mass in the PC resin composition of the present invention.
As the PC-POS copolymer, for example, one having a terminal group represented by the following general formula (4) can be used.

In the general formula (4), R ⁴ represents an alkyl group having 1 to 35 carbon atoms, and d represents an integer of 0 to 5.
Examples of the PC-POS copolymer include JP-A-50-29695, JP-A-3-292359, JP-A-4-202465, JP-A-8-81620, and JP-A-8-302178. And a copolymer disclosed in JP-A-10-7897. The alkyl group having 1 to 35 carbon atoms represented by R ⁴ may be linear or branched, The bonding position may be any of p-position, m-position and o-position, but p-position is preferred.

As the PC-POS copolymer, a polycarbonate part composed of a structural unit represented by the following general formula (5) and a polyorganosiloxane part composed of a structural unit represented by the following general formula (6) are preferably included in the molecule. The copolymer which has can be mentioned.

Here, R ⁵ and R ⁶ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different. R ⁷ to R ^{10 each} represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and is preferably a methyl group. R ⁷ to R ¹⁰ may be the same or different. R ¹¹ represents a divalent organic residue containing an aliphatic or aromatic group, and preferably an o-allylphenol residue, a p-hydroxystyrene residue or an eugenol residue.
Z ′ is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylidene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group having 5 to 20 carbon atoms, or —SO ₂ —, —SO—, —S—, —O—, —CO— bond is shown. An isopropylidene group is preferred. e and f are integers of 0 to 4, preferably 0. n is an integer of 1 to 500, preferably 5 to 200, more preferably 15 to 300, and still more preferably 30 to 150.

The PC-POS copolymer includes, for example, a polycarbonate oligomer (hereinafter abbreviated as a PC oligomer) constituting a polycarbonate part produced in advance, an o-allylphenol group and p-hydroxy at the terminal constituting the polyorganosiloxane part. A polyorganosiloxane (reactive POS) having a reactive group such as a styrene group or an eugenol residue is dissolved in a solvent such as methylene chloride, chlorobenzene, chloroform, and a caustic aqueous solution of a dihydric phenol is added. Interfacial polycondensation using tertiary amines (such as triethylamine) and quaternary ammonium salts (such as trimethylbenzylammonium chloride) in the presence of a general end-stopper consisting of a phenol compound represented by the following general formula (7) It can manufacture by reacting. In the following general formula (7), R ⁴ and d are as defined above.

Examples of the phenol compound represented by the general formula (7) include the same compounds as the exemplary compound of the general formula (3).
The PC oligomer used for the production of the PC-POS copolymer is obtained by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride, or of a dihydric phenol and diphenyl carbonate. It can manufacture by transesterification etc. with such a carbonate precursor. Here, as a dihydric phenol, the thing similar to the exemplary compound of the said General formula (2) can be used, and bisphenol A is especially preferable.

Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.
The PC oligomer used for the production of the PC-POS copolymer may be a homopolymer using one of the above dihydric phenols, or may be a copolymer using two or more. Furthermore, the thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound together with the said bihydric phenol may be sufficient.
In that case, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3 is used as a branching agent (polyfunctional aromatic compound). , 5-triisopropylbenzene, 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxylphenyl) ethyl] benzene, phloroglucin, Trimellitic acid, isatin bis (o-cresol) and the like can be used.

The PC-POS copolymer can be produced as described above. Generally, an aromatic PC resin is produced as a by-product, and the PC-POS copolymer is produced as an aromatic PC resin containing the PC-POS copolymer.
The aromatic PC-POS copolymer produced by the above method substantially has an aromatic end group represented by the general formula (4) on one or both of the molecules.

[(B) Cellulose fiber]
In the present invention, by using cellulose fibers having a specific average fiber diameter and average fiber length as the biomass material, coloring can be suppressed and a decrease in impact strength can be suppressed. Furthermore, since (B) cellulose fiber can improve rigidity, although it is low specific gravity compared with inorganic fibers, such as glass fiber, it can be set as the low specific gravity resin composition with high rigidity. Examples of cellulose fibers include cellulose fibers derived from natural plants such as wood fibers, bamboo fibers, sugarcane fibers, seed hair fibers, and leaf fibers. These cellulose fibers may be used alone or in combination of two or more. It may be used.

The cellulose fibers in the present invention have an average fiber diameter of 5 to 50 μm and an average fiber length of 0.03 to 1.5 mm as measured using an electron micrograph. When the average fiber diameter is less than 5 μm, the impact resistance strength and rigidity improvement effects are not exhibited, and when the average fiber diameter exceeds 50 μm, the molded appearance and impact strength are greatly reduced. Further, if the average fiber length is less than 0.03 mm, the impact strength and rigidity improving effects are not exhibited, and if the average fiber length exceeds 1.5 mm, the molded appearance is remarkably deteriorated. A more preferable average fiber diameter is 10 to 40 μm, and a more preferable average fiber length is 0.05 to 1.0 mm.
The cellulose fibers having the above size may be blended as they are, or may be blended after defibration with a mixer or the like.

Further, as the cellulose fiber, the content of α-cellulose is preferably 80% by mass or more, and more preferably 85% by mass or more. If the purity is higher than 80% by mass of α-cellulose, the fiber diameter and fiber length can be easily adjusted, and entanglement between fibers can be suppressed. For example, 80% by mass of α-cellulose such as well-known kenaf fiber or jute fiber Compared to the case of using less than 1%, the thermal stability at the time of melting is high, the impact strength is not lowered, the coloration suppressing effect is good, and the effect of the present invention is further improved. be able to.

In the resin mixture comprising (A) polycarbonate resin and (B) cellulose fiber, the content of each component is (A) component 99 to 60% by mass and (B) component 1 to 40% by mass. When the component (B) is less than 1% by mass, the effect of improving the mechanical properties such as the elastic modulus is not exhibited, and when it exceeds 40% by mass, the mechanical properties such as the impact strength are greatly deteriorated. The content of the component (B) in the resin mixture is preferably 5 to 30% by mass, and more preferably 5 to 25% by mass.

[(C) Terpene compound]
In the PC resin composition of the present invention, the cellulose fiber is uniformly dispersed in the resin composition, thereby improving the mechanical strength and fluidity of the resin composition and suppressing the coloring (C) a terpene compound. Contain.
In the present invention, the (C) terpene compound means a hydrocarbon having a composition of (C ₅ H ₈ ) _n and an oxygen-containing compound derived therefrom and those having different degrees of unsaturation.
More specifically, a terpene monomer (C ₁₀ H ₁₆ ) alone, a terpene monomer and an aromatic vinyl monomer, or a copolymer obtained by copolymerizing a terpene monomer and a phenol are listed. It is done. Moreover, the hydrogenated terpene type compound obtained by hydrogenating the obtained terpene type compound may be sufficient. These terpene compounds may be used alone or in combination of two or more.
Examples of the terpene monomer include α-pinene, β-pinene, dipentene, d-limonene, and the aromatic vinyl monomer includes styrene, α-methylstyrene, vinyltoluene, and the like. Examples of the phenols include phenol, cresol, bisphenol A, and the like.

These terpene compounds can be obtained by reacting in the presence of a Friedel-Craft type catalyst in an organic solvent together with a terpene monomer alone or an aromatic vinyl monomer and phenols.
That is, examples of terpene compounds include terpene resins, hydrogenated terpene resins, terpene-phenol resins, terpene-bisphenol A resins, and the like.
In the present invention, those containing phenols, such as terpene-phenol resin and terpene-bisphenol A resin, are preferable because of excellent fluidity and (B) dispersibility of cellulose fibers.

The content of the (C) terpene compound is 0.2 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the resin mixture composed of the components (A) and (B). The amount is preferably 5 to 15 parts by mass. When the content is less than 0.2 parts by mass, the effect of improving the dispersibility of the (B) cellulose fiber cannot be exhibited, and the fluidity improvement and coloring suppression effect of the resin composition cannot be obtained. Moreover, when this content exceeds 30 mass parts, the impact resistance and heat resistance fall remarkably.

[(D) phosphorus compound]
In the PC resin composition of the present invention, it is preferable to contain (D) a phosphorus compound from the viewpoint of further improving flame retardancy, fluidity, and coloring suppression.
(D) As a phosphorus compound, phosphoric acid ester, phosphorous acid ester, phosphonic acid ester, a phosphine, etc. are mentioned, These phosphorus compounds can be used individually by 1 type or in mixture of 2 or more types. Among the above phosphorus compounds, particularly from the viewpoint of suppressing coloring of the resin composition molded article, a phosphoric acid ester or a combined use of phosphoric acid ester and phosphite is preferable.

Examples of the phosphate ester include compounds represented by the following general formula (8).

In the general formula (8), R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or an organic group, X represents a divalent or higher valent organic group, and p is 0 or 1. Yes, q is an integer of 1 or more, and r represents an integer of 0 or more.
In the said General formula (8), an organic group means a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, etc. Examples of the substituent when substituted include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an arylthio group. Further, an arylalkoxyalkyl group that is a combination of these substituents, or an arylsulfonylaryl group that is a combination of these substituents bonded by an oxygen atom, nitrogen atom, sulfur atom, or the like is used as a substituent. Etc.

In the general formula (8), the divalent or higher organic group X means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the organic group. . For example, it is derived from an alkylene group, a (substituted) phenylene group, or a bisphenol that is a polynuclear phenol. Preferable examples include bisphenol A, hydroquinone, resorcinol, dihydroxydiphenyl, dihydroxynaphthalene and the like.

The phosphate ester may be a monomer, oligomer, polymer, or a mixture thereof. Specifically, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (2-ethylhexyl) phosphate, di- Isopropylphenyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tributyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, resorcinol-diphenyl phosphate, trioxybenzene triphosphate, cresyl diphenyl phosphate, etc. Can be mentioned. As the phosphate ester, a monoalkyl / dialkyl phosphate is preferable.

Examples of commercially available halogen-free phosphoric acid ester compounds that can be suitably used include, for example, AX-71 [mono-dialkoxy type phosphoric acid ester] manufactured by ADEKA Corporation, and Daihachi Chemical Industry Co., Ltd. TPP [triphenyl phosphate], TXP [trixylenyl phosphate], PFR [resorcinol (diphenyl phosphate)], PX200 [1,3-phenylene-teslakis (2,6-dimethylphenyl) phosphate], PX201 [1,4- Phenylene-tetrakis (2,6-dimethylphenyl) phosphate], PX202 [4,4′-biphenylene-teslakis (2,6-dimethylphenyl) phosphate] and the like.

The phosphite is represented by the following general formula (9).

In general formula (9), R ¹⁶ and R ¹⁷ each represent hydrogen, an alkyl group, a cycloalkyl group, or an aryl group. In addition, the cycloalkyl group and the aryl group may be substituted with an alkyl group.
Specific examples include compounds represented by the following formula (10) [ADEKA STAB (registered trademark) PEP-36: manufactured by ADEKA Corporation] and compounds of (11) to (14).

Further, as phosphites other than the above, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, triphenyl phosphite, tridecyl phosphite, trioctadecyl phosphite Etc. can be illustrated. As the phosphite, one containing a pentaerythritol structure or one containing an alkyl ester structure is preferable.

The content of the (D) phosphorus compound is preferably 0.2 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the resin mixture comprising the components (A) and (B). More preferably, it is 5 to 15 parts by mass. If this content is 0.2 parts by mass or more, the flame retardancy and fluidity are further improved, and a more excellent coloring suppression effect is obtained. Moreover, if this content is 30 parts by mass or less, impact resistance and heat resistance will not be lowered.

[(E) Polytetrafluoroethylene]
The polycarbonate resin composition of the present invention can contain (E) polytetrafluoroethylene from the viewpoint of suppressing melt dripping and imparting high flame retardancy.
(E) The polytetrafluoroethylene is preferably polytetrafluoroethylene (hereinafter abbreviated as PTFE) having a fibril-forming ability, and usually has an average molecular weight of about 500,000 or more. The average molecular weight is preferably 500,000 to 10,000,000, more preferably 1,000,000 to 10,000,000.

PTFE having fibril-forming ability is not particularly limited, and specifically, Teflon (registered trademark) 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Polyflon (registered trademark) manufactured by Daikin Industries, Ltd. D-1, F-103, F201, MPA FA-100, CD076 manufactured by Asahi Glass Fluoropolymers Co., Ltd., and Algoflon (registered trademark) F5 manufactured by Montefluos.

The PTFE having the fibril-forming ability as described above, for example, tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium or ammonium peroxydisulfide, usually at a pressure of about 7 to 700 kPa, at a temperature of 0 to 200 ° C. It can be obtained by polymerization at a degree, preferably 20 to 100 ° C.
In addition, (E) polytetrafluoroethylene can exhibit extremely high melt dripping suppression and flame retardancy when used in combination with a polycarbonate-polyorganosiloxane copolymer that can be included in (A) polycarbonate resin. it can.

The content of (E) polytetrafluoroethylene is preferably 0.05 to 1 part by mass, more preferably 0.1 to 100 parts by mass of the resin mixture composed of the component (A) and the component (B). Is 0.5 parts by mass. If this content is 0.05 parts by mass or more, the melt dripping suppression in the desired flame retardance will be sufficient. If this content is 1 part by mass or less, the appearance of the molded product does not become poor without lowering the impact resistance. Therefore, the amount of flame retardancy required for each molded product and the thickness can be appropriately determined in consideration of the amount used.

[Additive]
The polycarbonate resin composition of the present invention has other resins and additives at the time of mixing and molding, for example, pigments, dyes, reinforcing agents, fillers, heat-resistant agents, oxidation inhibitors, weathering agents, as long as the physical properties are not impaired. Further, a lubricant, a release agent, a crystal nucleating agent, a plasticizer, a fluidity improver, an antistatic agent and the like can be added.

[Polycarbonate resin composition]
As a manufacturing method of the polycarbonate resin composition of this invention, the method of melt-kneading each component by a conventionally well-known method is mentioned.
For example, a method in which each component is dispersed and mixed with a high speed mixer represented by a tumble mixer, a Henschel mixer, a ribbon blender, or a super mixer, and then melt-kneaded with an extruder, a Banbury mixer, a roll, or the like is appropriately selected.

There are no particular limitations on the molding method using the polycarbonate resin composition of the present invention, and molding methods such as injection molding, injection compression molding, extrusion molding, and hollow molding can be applied.
Since the molded article using the polycarbonate resin composition of the present invention has the above-mentioned properties, it can be suitably used, for example, in the field of office automation equipment, information / communication equipment, automobile parts or building materials.

In the present invention, by blending cellulose fiber as a biomass material in a polycarbonate resin, the impact strength is small and the rigidity is low and the specific gravity (MPa) is obtained by dividing the bending modulus (MPa) by the specific gravity. In addition, the surface roughness and the like are reduced, the molded appearance is excellent, the thermal stability is good, the coloring is small, and the dispersibility of the cellulose fiber is improved by adding a terpene compound. It is a resin composition.
Moreover, in addition to further suppressing coloring by blending a phosphorus compound, it is a resin composition that can be further flame retardant by blending a phosphorus compound and polytetrafluoroethylene.

The polycarbonate resin composition of the present invention generally has the Izod (IZOD) impact strength, specific rigidity, oxygen index (LOI), flame retardancy, and thermal stability of the molded product obtained in the performance evaluation described in the following examples. It has the characteristics that it satisfies the following performance and has an excellent molded appearance.
Izod (IZOD) impact strength, preferably 30 ~ 3kJ / m ^2, more preferably 30 ~ 5kJ / m ^2, particularly preferably 30 ~ 10kJ / m ^2. If the IZOD impact strength is 10 kJ / m ² or more, the housing strength of ordinary electronic / electrical equipment is satisfied, and if it is 3 kJ / m ² or less, the product may be damaged due to dropping or impact.
The specific rigidity is preferably 2000 MPa or more, more preferably 2300 MPa or more, and particularly preferably 2400 MPa or more, from the viewpoint of a balance between lightness and rigidity.
The oxygen index (LOI) is preferably 24% or more, more preferably 25% or more, particularly preferably 30% or more, and the flame retardancy is preferably V-1 or more.
The heat stability is preferably 45 or less in terms of yellow index (YI) from the viewpoint that coloring is suppressed.

The following examples further illustrate the present invention, but the present invention is not limited to these examples.

The components and performance evaluation methods used in Examples and Comparative Examples are shown below.
(A) Component: Polycarbonate resin / aromatic polycarbonate resin: Trade name FN1900A [manufactured by Idemitsu Kosan Co., Ltd., manufactured using bisphenol A as a raw material, viscosity average molecular weight = 19,500]
PC-PDMS: Viscosity average molecular weight = 17,000, PDMS content = 4.0% by mass, PDMS chain length (n) = 30 [see Production Examples 3 and 4 of JP-A-2002-12755]
Component (B): Cellulose fiber / Cellulose fiber 1: Trade name SW-10 [manufactured by Celite, average fiber diameter = 25 μm, average fiber length = 0.12 mm, α-cellulose content 90% by mass]
Cellulose fiber 2: trade name BH20 [manufactured by Celite, average fiber diameter = 25 μm, average fiber length = 0.065 mm, α-cellulose content 90% by mass]
Component (C): Terpene compound Terpene compound: Trade name YS Polystar T160 [terpene-phenol resin, manufactured by Yasuhara Chemical Co., Ltd.]
Component (D): Phosphorus compound Phosphorus compound: Trade name PX202 [4,4′-biphenylene-teslakis (2,6-dimethylphenyl) phosphate, manufactured by Daihachi Chemical Industry Co., Ltd.]
(E) component: polytetrafluoroethylene (PTFE)
PTFE: Product name CD076 [Asahi Glass Fluoropolymers Co., Ltd.]
(Other):
Cellulose fiber 3: Dissolved pulp NDT-T (trade name, manufactured by Nippon Paper Industries Co., Ltd.) was used to make a 5 mm square chip using a shredder and pulverized with a mill using this. [Average fiber diameter = 80 μm, average fiber length = 2 mm, α-cellulose content 90 mass%]
Jute fiber: [average fiber diameter = 50 μm, average fiber length = 0.1 mm, α-cellulose content 70% by mass]

[Performance evaluation method]
(1) MI: Melt index Measured according to ASTM D-1238 at 260 ° C. under a load of 2.16 kg. Unit: g / 10 min (2) Specific gravity Based on ASTM D792, test pieces of Examples and Comparative Examples obtained by injection molding were measured.
(3) IZOD (Izod impact strength):
In accordance with ASTM D256, a specimen having a thickness of 1/8 inch (1 / 20.3 cm) was used and measured at 23 ° C. Unit: kJ / m ²
(4) Flexural modulus Based on ASTM D-790, a test piece having a thickness of 3 mm was used and measured at 23 ° C. Unit: MPa
(5) Specific rigidity The specific rigidity was obtained by dividing the bending elastic modulus by the specific gravity. Unit: MPa
(6) LOI (oxygen index)
Measured according to ASTM D2863. unit:%
(7) Flame retardancy According to UL94 standard (Under Writer's Laboratories Inc., USA), a vertical combustion test was performed with a specimen thickness of 1.5 mm. Flame retardancy was classified according to UL94 standards, and those that did not fall under any classification and continued to burn were designated as “NG”.
(8) Molding appearance: 80 × 40 × 3 mm test pieces were molded and the surface roughness was evaluated visually.
A sample with no surface roughness was marked with ◯, and a sample with rough surface was marked with ×.
(9) YI (Yellow Index)
About thermal stability, the coloring degree at the time of shaping | molding evaluated the YI value of the test piece with the testing machine by Nippon Denshoku Industries Co., Ltd. based on JISK7103.

Examples 1 to 10 and Comparative Examples 1 to 12
Each component was mix | blended in the ratio shown in Table 1 or 2, and it supplied to the extruder (model name: VS40, Tanabe Plastic Machinery Co., Ltd.), melt-kneaded at 280 degreeC, and pelletized. In all Examples and Comparative Examples, Irganox (registered trademark) 1076 (manufactured by BASF) 0.2 mass as an oxidation inhibitor with respect to 100 mass parts of the resin mixture comprising the components (A) and (B). And 0.1 parts by mass of ADK STAB (registered trademark) C (manufactured by ADEKA) were blended.
The obtained pellets were dried at 120 ° C. for 12 hours, and then injection molded under the conditions of an injection molding machine (manufactured by Toshiba Machine Co., Ltd., model: IS100N) cylinder temperature 260 ° C. and mold temperature 80 ° C. Obtained. The performance was evaluated by various tests using the obtained test pieces, and the results are shown in Table 1 or 2.

According to Tables 1 and 2, the balance of impact strength, rigidity (flexural modulus), specific rigidity, flame retardancy, molded appearance and thermal stability is good in all examples. In Examples 2, 9, and 10, It can be seen that the flame retardance is further improved while maintaining a good balance by blending a phosphorus compound or polytetrafluoroethylene.
Further, by blending the terpene-based compound (C) from Example 1 and Comparative Example 4 or Example 8 and Comparative Example 12, the molding appearance and thermal stability were particularly improved. Example 1 and Comparative Examples 6 to 9, Alternatively, from Example 8 and Comparative Examples 10 and 11, it can be seen that impact strength, flame retardancy, molded appearance and thermal stability are reduced unless (B) cellulose fiber. Further, it can be seen from Comparative Examples 3 and 5 that the above-described good balance cannot be expressed unless the content ratio is defined in the present invention.

The present invention is excellent in environmental characteristics by using biomass material, has little decrease in impact strength, has low specific gravity and high rigidity, that is, high specific rigidity and excellent appearance, heat stability, flame retardancy Can be suitably used, for example, in the field of OA equipment, information / communication equipment, automobile parts or building materials.

Claims

(A) 99 to 60% by mass of polycarbonate resin and (B) 100% by mass of a resin mixture comprising 1 to 40% by mass of cellulose fibers having an average fiber diameter of 5 to 50 μm and an average fiber length of 0.03 to 1.5 mm. A polycarbonate resin composition containing 0.2 to 30 parts by mass of (C) a terpene compound relative to parts.
(B) The polycarbonate resin composition according to claim 1, wherein the content of α-cellulose in the cellulose fiber is 80% by mass or more.
(A) The polycarbonate resin composition according to claim 1 or 2, wherein the polycarbonate resin is a polycarbonate-polyorganosiloxane copolymer or contains a polycarbonate-polyorganosiloxane copolymer.
The polycarbonate resin according to any one of claims 1 to 3, further comprising 0.2 to 30 parts by mass of (D) a phosphorus compound with respect to 100 parts by mass of a resin mixture comprising (A) a polycarbonate resin and (B) cellulose fibers. Composition.
The composition according to any one of claims 1 to 4, further comprising 0.05 to 1 part by mass of (E) polytetrafluoroethylene with respect to 100 parts by mass of the resin mixture comprising (A) a polycarbonate resin and (B) cellulose fibers. Polycarbonate resin composition.