JP2007161943A - Cellulose ester resin composition - Google Patents

Abstract

The present invention provides a cellulose ester resin composition useful for obtaining a molded article excellent in stability against deformation (particularly, deformation stability under high temperature and high humidity) and the molded article thereof.
[MEANS FOR SOLVING PROBLEMS] Cellulose esters (such as cellulose acetate having a total average substitution degree of 2.7 or less), non-cellulose ester thermoplastic resins (such as aromatic polyester resins and aromatic polycarbonate resins), and plasticity to the cellulose esters. A cellulose ester-based resin composition is composed of an agent (such as phosphate ester or phthalate ester) and a bleed-out inhibitor (such as condensed phosphate ester) for suppressing or preventing bleed-out of the plasticizer.
[Selection figure] None

Description

  The present invention relates to a resin composition containing a cellulose ester, which is a renewable material, using a biological material as a starting material, and a molded article formed from the composition.

  Plastics such as polyester, polyamide, and polycarbonate include office automation (OA) equipment such as personal computers, home appliances such as TVs and refrigerators, packaging materials such as containers and packages, building materials such as walls and flooring, and automobiles. It is widely used as a material that constitutes transportation vehicles and is consumed in large quantities. Although the plastic is excellent in moldability, productivity, and mechanical properties, it is a synthetic resin, so it has a large environmental load, such as toxic substances flowing into the soil and generation of toxic gas due to disposal or incineration. .

  Therefore, the use of natural materials such as cellulose, starch-based plastics, and biodegradable plastics such as polylactic acid and caprolactone-based copolymers has been studied. However, these biodegradable plastics have low moldability, productivity, heat resistance and the like. For example, polylactic acid has a remarkably slow crystallization rate, a long molding cycle, and is not suitable for injection molding. A cellulose ester (for example, a low-substituted cellulose ester) has been proposed as a natural material-based plastic that overcomes such drawbacks. Such a cellulose ester is poor in moldability (thermoformability) as it is, and is usually thermoformed (such as injection molding) in a plasticized state by using a plasticizer in combination.

  For example, in Japanese Patent No. 2533764 (Patent Document 1), 0.001 to 0.05 parts by weight of a weak organic acid, 0.05 to 1 part by weight of a specific thioether compound with respect to 100 parts by weight of a fatty acid cellulose ester, A fatty acid ester resin composition comprising 0 to 1 part by weight of a phosphite compound and 0 to 5 parts by weight of an epoxy compound is disclosed. This document describes that fatty acid cellulose ester-based resins usually contain a plasticizer and are further added with a filler and the like. Japanese Patent Laid-Open No. 10-306175 (Patent Document 2) discloses that 0.05 to 1 part by weight of a phosphite compound having a melting point exceeding room temperature with respect to 100 parts by weight of a fatty acid cellulose ester, 0. A fatty acid cellulose ester-based resin composition comprising 001 to 0.05 parts by weight, a thioether compound 0.05 to 1 part by weight, and an epoxy compound 5 parts by weight or less is disclosed. This document describes that an appropriate amount of a normal phosphate ester such as triphenyl phosphate may be added as a plasticizer if necessary.

  Furthermore, Japanese Patent Application Laid-Open No. 2005-194302 (Patent Document 3) includes a cellulose ester (such as cellulose acetate) having an average substitution degree of 2.7 or less, a plasticizer (such as phosphate ester), and a filler (such as talc). An improved resin composition is disclosed. The composition of this document has high moldability and can suppress the generation of burrs even if it is thin and injection molded.

  However, the resin composition described in these documents (or a molded article formed with such a resin composition) is easily deformed under high temperature and high humidity due to moisture absorption of the cellulose ester, and is stable against deformation ( Poor dimensional stability and warpage stability.

  On the other hand, attempts have been made to combine biodegradable resins such as cellulose esters with other resins. For example, JP-A-59-206815 (Patent Document 4) essentially does not contain a low molecular weight plasticizer and is a cellulose ester of an aliphatic carboxylic acid (for example, cellulose acetopropionate, cellulose acetobutyrate, etc.). ) Polymer alloy, wherein the polymer alloy has (A) 97-70% by weight of a cellulose ester and (B) an ester and / or carbonate group in the polymer chain, and has a molecular weight of 2000 Contact lenses consisting of 3 to 30% by weight of aliphatic compounds of ˜300000 are disclosed. This document describes that polyester, polycarbonate, polyether ester and the like can be used as the aliphatic compound (B).

  Japanese Examined Patent Publication No. 2-503324 (Patent Document 5) is a molded article characterized in that it has a continuous polyester phase in which fine beads of cellulose acetate at least partially in contact with pore voids are dispersed. A molded product is disclosed in which the microbeads are present in an amount of 10-30% by weight based on the weight of the polyester, and the pore voids account for 2-50% by volume of the molded product. This document describes that the molded product can be produced by molding a mixture formed by mixing cellulose acetate with a polyester melt.

  Furthermore, Japanese Patent Application Laid-Open No. 2003-306577 (Patent Document 6) discloses a cellulose phase that constitutes a continuous phase and a plasticized cellulose derivative and a heat that has a refractive index different from that of the cellulose derivative and constitutes a dispersed phase. Plastic resin (olefin resin, halogen-containing resin, vinyl alcohol resin, vinyl ester resin, styrene resin, (meth) acrylic resin, polyester resin, polycarbonate resin, polyamide resin, polysulfone resin, polyphenylene resin Resin, polyacetal resin, thermoplastic elastomer, and the like). In this document, examples of the plasticized cellulose derivative include cellulose derivatives (such as cellulose acetate propionate) externally plasticized with a plasticizer such as phthalate ester, fatty acid ester, phosphate ester, and epoxy derivative. ing. In the composition of this document, by using a plasticized cellulose derivative and a thermoplastic resin having a different refractive index, the dispersed phase can be easily and efficiently transformed into an anisotropic shape, and has excellent optical properties. A molded body is obtained.

  In these documents, by combining a specific cellulose ester and a specific resin and molding by a specific method or conditions, a specific molded body corresponding to each application (contact lens application, foam application, optical application) is obtained. Obtainable. These documents do not describe the problem of moisture absorption of cellulose ester. For example, Patent Document 6 aims to improve transparency by adjusting the refractive index, and does not assume any moisture absorption of the cellulose ester and accompanying deformation under high temperature and high humidity.

JP-A-2004-2613 (Patent Document 7) discloses a thermoplastic resin, a starchy material and a compatibilizer (for example, an acid-modified polyolefin modified with an unsaturated dicarboxylic acid and / or an acid anhydride thereof). A starch-based composite resin composition containing a resin or the like is disclosed. This document exemplifies polyolefin resin and / or biodegradable resin (for example, polyvinyl alcohol resin, aliphatic polyester resin, aliphatic / aromatic polyester resin, etc.) as the thermoplastic resin. Examples of starchy materials include raw starch, modified starch, cellulose powder, cellulose derivatives (such as sodium carboxymethylcellulose, methylcellulose, and cellulose acetate), chitosan, noodle dough, and bread crumbs. Corn starch and / or crushed bread crumbs. Further, in this document, glycerin, 1, 3 is incorporated into the molecular structure of the starch-based composite resin composition, so as to be compatible and impart flexibility, fluidity, and the like, and plasticize the composite resin composition. -Plasticizers (modifiers) such as propanediol, polyethylene glycol, polypropylene glycol, fats and oils (coconut oil, palm oil, soybean oil, castor oil, etc.), oils and fats hardened oils (coconut oil hardened oil, palm extremely hardened oil, etc.) It is described that may be blended in the resin composition.
Japanese Patent No. 2533764 (Claim 1, page 2, column 3, lines 15-17, page 3, column 6, lines 9-20) JP-A-10-306175 (Claim 3, paragraph numbers [0023] [0028]) Japanese Patent Laying-Open No. 2005-194302 (Claims) JP 59-206815 (Claims) Japanese Patent Publication No. 2-503324 (Claims, lower right column on page 6) JP 2003-306577 A (claims, paragraph numbers [0006] [0021] [0022] [0031]) JP 2004-2613 A (claims, paragraph numbers [0022] [0023] [0025] [0031] [0032], Examples)

  Accordingly, an object of the present invention is to provide a cellulose ester resin composition useful for obtaining a molded article excellent in stability against deformation (or dimensional stability, particularly deformation stability under high temperature and high humidity) and molding thereof. Is to provide goods.

  Another object of the present invention is to provide a cellulose ester-based resin composition capable of suppressing the hygroscopic property of a molded product at a high level even if it is composed of a cellulose ester, and a molded product thereof.

  Still another object of the present invention is to provide a cellulose ester resin that can suppress or prevent bleeding out of a plasticizer at a high level even when a plasticizer for cellulose ester (eg, phosphate ester, phthalate ester, etc.) is used. The object is to provide a composition and a molded article thereof.

  Another object of the present invention is to suppress or prevent plasticizer bleed-out and various physical properties (mechanical properties such as mechanical strength and impact resistance, and chemical properties such as flame retardancy and heat resistance). It is in providing the cellulose-ester-type resin composition excellent in the balance of this, and its molded article.

  Still another object of the present invention is to provide a cellulose ester resin composition that can remarkably suppress the generation of off-flavors (especially organic acid odors such as acetic acid) from the cellulose ester during the molding process and after molding, and has excellent moldability. And providing a molded product thereof.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor has found that a cellulose ester containing a plasticizer for cellulose ester, a non-cellulose ester thermoplastic resin, and a bleed capable of suppressing or preventing bleed-out of the plasticizer. It has been found that when a resin composition combined with an out inhibitor is molded, a molded product excellent in stability against deformation (particularly, deformation stability or dimensional stability under high temperature and high humidity) can be obtained. completed.

  That is, the resin composition of the present invention (cellulose ester-based resin composition, cellulose-based resin composition) includes a cellulose ester and a non-cellulose ester-based thermoplastic resin (a thermoplastic resin other than a cellulose ester, a thermoplastic resin other than a cellulose ester). Resin), a plasticizer for the cellulose ester, and a bleed-out inhibitor for suppressing or preventing bleed-out of the plasticizer.

  The total average substitution degree of the cellulose ester may be, for example, 2.7 or less. The cellulose ester may be a cellulose ester having an average substitution degree at the 6-position of the glucose unit in a specific range (for example, the average substitution degree is about 0.35 to 0.8).

  The non-cellulose ester thermoplastic resin may be composed of at least one selected from an aromatic polyester resin and an aromatic polycarbonate resin. In the resin composition, the ratio of the non-cellulose ester thermoplastic resin may be about 5 to 100 parts by weight with respect to 100 parts by weight of the cellulose ester.

  The plasticizer may be composed of, for example, at least one selected from non-condensed phosphate esters and phthalate esters. The bleedout inhibitor may be composed of a condensed phosphate ester. In the resin composition, the ratio of the bleed out inhibitor may be about 3 to 50 parts by weight with respect to 100 parts by weight of the plasticizer.

  Typical examples of the resin composition include cellulose acetate having a total average substitution degree of about 2.1 to 2.7 and an average substitution degree of about 6 to 6 of the glucose unit, and a polybutylene terephthalate resin. And at least one non-cellulose ester thermoplastic resin selected from aromatic polycarbonate resins, a triaryl phosphate, and an aromatic condensed phosphate having a melting point of 70 to 150 ° C. The ratio of the non-cellulose ester-based thermoplastic resin is about 10 to 80 parts by weight with respect to 100 parts by weight of the cellulose acetate, and the ratio of the triaryl phosphate is 5 to 100 parts by weight with respect to the cellulose acetate. About 40 parts by weight, and the ratio of the aromatic condensed phosphate is 8 to 40 with respect to 100 parts by weight of the triaryl phosphate. Etc. The resin composition is about quantity unit.

  The resin composition of the present invention may further contain at least one compatibilizing agent selected from an epoxy resin and an epoxy-modified diene copolymer. Further, the resin composition of the present invention may further contain at least one filler selected from a fibrous filler, a plate-like filler, and a granular filler. Furthermore, the resin composition of the present invention may contain at least one epoxy compound selected from an alicyclic epoxy compound and a long-chain aliphatic epoxy compound. The resin composition may further contain at least one stabilizer selected from organic acids, thioether compounds, and phosphites.

  In addition, the resin composition of the present invention may contain a deodorant in order to suppress or prevent the generation of off-flavors (particularly organic acid odors such as acetic acid) from the cellulose ester. May comprise at least one selected from, for example, hydrated zirconium oxide, zirconium oxide and carbodiimide compounds. Furthermore, the resin composition of the present invention may contain an acid-modified resin. Such an acid-modified resin can efficiently prevent obstacles in melt-kneading and can suppress generation of acid derived from cellulose ester (especially organic acid such as acetic acid) at a high level by combination with the deodorant.

  The resin composition of the present invention can be suitably used in a molding method including a melting step at a high temperature, and may be used, for example, for injection molding. The molded product formed with the said resin composition is also contained in this invention.

  The resin composition of the present invention can obtain a molded article having excellent stability against deformation (or dimensional stability, particularly deformation stability under high temperature and high humidity) despite being composed of cellulose ester. Useful for. Moreover, even if the resin composition of this invention is comprised with the cellulose ester, it can suppress the hygroscopic property of a molded article at a high level. Furthermore, in the resin composition of the present invention, even if a plasticizer for cellulose ester (for example, phosphate ester, phthalate ester, etc.) is used, bleeding out of this plasticizer can be suppressed or prevented at a high level. A molded product can be obtained with dimensional stability. Molded articles formed with such a resin composition of the present invention can suppress or prevent plasticizer bleed-out, and have various physical properties (mechanical properties such as mechanical strength and impact resistance, and flame retardancy. Excellent balance of chemical properties such as heat resistance. Further, in the present invention, by using a specific deodorant, it is possible to remarkably suppress the generation of off-flavors (especially organic acid odors such as acetic acid) from the cellulose ester during the molding process and after molding, and to improve moldability. An excellent cellulose ester resin composition and a molded product thereof can be obtained.

  The cellulose ester resin composition of the present invention is composed of a cellulose ester, a plasticizer, a bleedout inhibitor for suppressing or preventing the bleedout of the plasticizer, and a non-cellulose ester thermoplastic resin. Yes.

  In this invention, by comprising by such a combination, the deformation | transformation of the molded article (or resin composition) containing a cellulose ester can be suppressed at a high level. The reason why the deformation can be suppressed is not clear, but the following reasons are conceivable. That is, cellulose ester (for example, cellulose acetate) inherently easily absorbs moisture, and the absorbed water has a function of plasticizing the cellulose ester. Therefore, when a molded product containing cellulose ester is left as it is, moisture absorption causes the glass transition point of the cellulose ester to shift to a low temperature side, releasing internal stress in the molded product and causing deformation. Such moisture absorption is particularly likely to occur at high temperatures and high humidity. On the other hand, since the cellulose ester is poor in moldability, it is usually used with a plasticizer added, but this plasticizer tends to bleed out from the molded product (or resin composition).

  Therefore, in the present invention, the above combination suppresses bleed-out and moisture absorption of the plasticizer, and even if it is composed of a cellulose ester as a biological material, the resin composition has excellent stability (or dimensional stability) against deformation. To the product (or its molded product).

[Cellulose ester]
Examples of cellulose esters include cellulose organic acid esters [cellulose C _2-6 carboxylic acid esters such as cellulose acetate (cellulose acetate), cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate], Derivatives of the organic acid esters (grafts such as polycaprolactone-grafted cellulose acetate), cellulose organic acid esters / ethers (C _2-6 acyl cellulose C _1-6 alkyl such as acetyl methyl cellulose, acetyl ethyl cellulose, acetyl propyl cellulose) ethers, acetyl hydroxyethylcellulose, _{C 2-6} acyl cellulose hydroxyalkyl _{C 2-6} alkyl such as acetyl hydroxypropylcellulose Such ether), cellulose inorganic acid esters (cellulose nitrate, cellulose sulfate, cellulose phosphate), and the like cellulose organic acid and inorganic acid mixed ester (such as nitric acid cellulose acetate). These cellulose esters can be used alone or in combination of two or more.

  Of these cellulose esters, cellulose organic acid esters, particularly cellulose acetate (or cellulose acetate) are preferred.

  In cellulose ester (for example, cellulose acetate), the total average substitution degree of substituents (or ester groups or acyl groups) (total average substitution degree of ester groups substituted at 2, 3 and 6 positions of glucose units constituting cellulose) Is usually 2.7 or less (for example, about 1.7 to 2.7) in terms of moldability and mechanical properties, preferably 1.8 to 2.7, more preferably 1 .9 to 2.65 (for example, 2 to 2.55), usually about 2.1 to 2.7 (for example, 2.2 to 2.6). In terms of biodegradability, the total average substitution degree of the cellulose ester is, for example, 1.7 to 2.5, preferably 1.8 to 2.4, more preferably 1.9 to 2.3 (particularly 2 To about 2.2).

  In the cellulose ester (for example, cellulose acetate), the average substitution degree at the 6-position of the glucose unit is, for example, 0.95 or less (for example, about 0.3 to 0.9), preferably 0.85 or less (for example, 0.35 to 0.8), more preferably 0.75 or less (for example, about 0.4 to 0.7), particularly 0.65 or less (for example, about 0.45 to 0.6). May be. Such a cellulose ester having a relatively low average degree of substitution at the 6-position can further improve moldability for injection molding and the like.

  The degree of polymerization of the cellulose ester is not particularly limited, and may be about 100 to 1000, preferably 100 to 500, and more preferably about 200 to 500 (particularly 200 to 400) in terms of viscosity average degree of polymerization.

[Non-cellulose ester thermoplastic resin]
The non-cellulose ester-based thermoplastic resin (sometimes simply referred to as a thermoplastic resin) is not particularly limited as long as the deformation stability of the cellulose ester composition (or a molded product thereof) can be improved by combination with the cellulose ester, Various thermoplastic resins, for example, addition polymerization resins {for example, olefin resins (poly α-C _2-10 olefins such as polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene, cyclopentadiene resins, norbornene) Cyclic olefin resins such as resin, halogen-containing resins [for example, chlorine-containing resins (polyvinyl chloride, etc.), carboxylic acid vinyl ester resins (vinyl acetate resins such as polyvinyl acetate, polyvinyl butyrate, etc.) ), Vinyl alcohol resin (polyvinyl chloride) Alcohol, ethylene-vinyl alcohol copolymer, etc.), styrene resin (eg, polystyrene, syndiotactic polystyrene, acrylonitrile-styrene resin, styrene-methyl methacrylate resin, acrylonitrile-butadiene-styrene copolymer, etc.), acrylic Resin [for example, a homopolymer or copolymer of (meth) acrylic monomer such as polymethyl methacrylate, (meth) acrylic acid- (meth) acrylic ester, methyl methacrylate-styrene copolymer, etc.), heat Plastic elastomer (styrene thermoplastic elastomer, olefin thermoplastic elastomer etc.)}, condensation polymerization resin {eg polycarbonate resin (eg bisphenol A polycarbonate etc.), polyester resin [eg aromatic Reester-based resin, aliphatic polyester-based resin (for example, polylactic acid, polyhydroxybutyrate, polycaprolactone, polyethylene succinate, polybutylene succinate adipate, lactone or aliphatic oxycarboxylic acid alone or Copolymer, etc.), polyamide resins (for example, polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide MXD, etc.), polyacetal resins (polyoxymethylene homo or copolymers, etc.), polysulfone resins, Poly (thio) ether resins [for example, polyphenylene ether resins (polyphenylene ether, modified polyphenylene ether, etc.), polysulfide resins (polyphenylene sulfide, polybiphenyle, etc.) Polysulfone resin (polysulfone, polyethersulfone, etc.), polyketone resin (polyetherketone, polyetheretherketone, polyphenylene sulfide ketone, etc.), polyimide resin (eg, polyimide, polyetherimide, Etc.) can be exemplified.

  Among these resins, a thermoplastic resin having a relatively low hygroscopic property is particularly preferable from the viewpoint of hygroscopic property. Also, a resin having a high glass transition temperature and good heat resistance (eg, polyamide resin, aromatic polyester resin, polyacetal resin, polycarbonate resin, poly (thio) ether resin, polysulfide resin, polysulfone resin, polyketone) Based resins, polyimide resins, etc.) are also preferred. Furthermore, a thermoplastic resin that can be processed (or molded) at a temperature lower than the decomposition temperature of cellulose ester (for example, about 240 ° C. for cellulose acetate) can also be suitably used. Furthermore, from the viewpoint of affinity for the cellulose ester, a thermoplastic resin having a polar group is also preferable.

  From this viewpoint, aromatic polyester resins, aromatic polycarbonate resins and the like are particularly preferable overall.

(Aromatic polyester resin)
Examples of the aromatic polyester-based resin include a polycondensate of an aromatic dicarboxylic acid component and a diol component. The aromatic polyester resin may be a liquid crystal polyester. Examples of the aromatic dicarboxylic acid component include C _8-16 arene dicarboxylic acid (for example, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, etc.), diaryl dicarboxylic acid (for example, 4,4′- Biphenyl dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid and the like), diarylalkane dicarboxylic acid (diphenyl C _1-10 alkane dicarboxylic acid such as 4,4′-diphenylmethane dicarboxylic acid), diaryl ketone dicarboxylic acid (4,4 '-Diphenylketone dicarboxylic acid and the like) and derivatives thereof (lower alkyl esters, derivatives capable of forming an ester such as acid anhydrides) and the like. The aromatic dicarboxylic acid component may be used alone or in combination of two or more. Furthermore, you may use together polyvalent carboxylic acid, such as trimellitic acid and a pyromellitic acid, as needed.

The diol component, for example, aliphatic diols [such as alkylene glycols (e.g., ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, _{C 2-10} alkylene glycol such as hexane diol, preferably _{C 2 -6} alkylene glycol), polyalkylene glycol (for example, diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, polytetramethylene glycol, etc.)], alicyclic diol [for example, 1,4-cyclohexanediol, Cycloalkane dialkanol (such as C _5-6 cycloalkane di C _1-2 alkanol such as 1,4-cyclohexanedimethanol), hydrogenated bisphenol A, etc.], aromatic diol { Hydroquinone, resorcinol, biphenol, bisphenol or its C _2-3 alkylene oxide adduct [2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (4- (2-hydroxyethoxy) phenyl) propane Etc.], xylylene glycol, etc.}. Usually, the diol component often comprises at least an aliphatic diol and / or an alicyclic diol. The diol components may be used alone or in combination of two or more. Furthermore, if necessary, trifunctional or higher functional polyols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol may be used in combination.

Typical aromatic polyester-based resins include polyester resins having at least terephthalate units, such as polyethylene terephthalate resins [for example, polyethylene terephthalate, ethylene terephthalate units as main components (for example, 50 to 100% by weight of the whole polymer, Copolyester (polyethylene terephthalate copolyester, etc., preferably about 75 to 100% by weight)], polypropylene terephthalate resin [for example, polypropylene terephthalate, propylene terephthalate unit as a main component (for example, 50 to 100% by weight of the whole polymer) Copolyester (polypropylene terephthalate copolyester), etc., preferably about 75 to 100% by weight)], polybutylene terephthalate resin [for example Polybutylene terephthalate, composed mainly of butylene terephthalate units (e.g., 50 to 100% by weight of the total polymer, preferably about 75 to 100 wt%) copolyester (polybutylene terephthalate copolyester) Poly _{C 2-4,} such as Examples include alkylene terephthalate resins; polycycloalkanedialkylene terephthalate resins (for example, poly 1,4-cyclohexanedimethylene terephthalate) and the like.

  Of these aromatic polyester resins, polybutylene terephthalate resins are particularly preferable. Aromatic polyester resins may be used alone or in combination of two or more.

(Aromatic polycarbonate resin)
As an aromatic polycarbonate-type resin, the polymer (for example, bisphenol A type polycarbonate resin etc.) etc. which are obtained by reaction with an aromatic diol component and a carbonate formation compound etc. are mentioned, for example.

Examples of the aromatic diol component include bisphenols such as di (hydroxy C _6-10 arene) s (4,4′-dihydroxybiphenyl and the like), bis (hydroxyphenyl) alkanes [eg bis (4-hydroxyphenyl) Methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2 , 2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-) Bis (hydroxyphenyl) C _1-10 alkanes such as hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl) hexafluoropropane, preferably bis (hydroxyphenyl) C _1-8 alkanes etc.], bis (hydroxy Phenyl) cycloalkanes [for example, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3 Bis (hydroxyphenyl) C _5-8 cycloalkane such as 1,5-trimethylcyclohexane And bis (hydroxyphenylaryl) alkanes [eg, bis (hydroxybiphenylyl) C _1-10 alkanes such as 2,2-bis (4-hydroxy-3,3′-biphenylyl) propane], bis (hydroxy Phenyl) ethers (eg, 4,4′-dihydroxydiphenyl ether), bis (hydroxyphenyl) sulfones (eg, 4,4′-dihydroxydiphenyl sulfone), bis (hydroxyphenyl) sulfoxides (eg, 4,4′-dihydroxydiphenyl sulfoxide, etc.), bis (hydroxyphenyl) sulfides (eg, 4,4′-dihydroxydiphenyl sulfide, etc.), bis (hydroxyphenyl-alkyl) arenes {eg, 4,4′- (M-phenylenediisopropylidene) diph Phenol, and the like Bis (such as hydroxyphenyl _{-C 1-4 alkyl) C 6-10} arene}.

Among these aromatic diol components, in particular, bis (hydroxyphenyl) alkanes [particularly bis (hydroxyphenyl) C _1-4 alkanes such as 2,2-bis (4-hydroxyphenyl) propane, in particular 2, 2-bis (hydroxyphenyl) propanes (for example, bisphenol A and the like)] are preferable. The aromatic diol components may be used alone or in combination of two or more.

  Examples of the carbonate-forming compound (carbonate precursor) include compounds capable of forming a carbonate bond, such as phosgene (phosgene, diphosgene, triphosgene, etc.), carbonates [eg, dialkyl carbonate (dimethyl carbonate, diethyl carbonate, etc.), etc. And carbonic acid diesters such as diaryl carbonate (diphenyl carbonate, dinaphthyl carbonate, etc.). Of these, phosgene, diphenyl carbonate and the like are preferable. The carbonate-forming compounds may be used alone or in combination of two or more.

  Aromatic polycarbonate resins may be used alone or in combination of two or more.

  The number average molecular weight of the thermoplastic resin is not particularly limited and can be appropriately selected according to the type and use of the resin. For example, it can be selected from a range of about 5,000 to 2,000,000, preferably 10,000 to 1,000,000, and more preferably about 20,000 to 1,000,000. . In particular, when the thermoplastic resin is composed of a polyester resin or a polycarbonate resin, the number average molecular weight may be, for example, 5,000 to 1,000,000, preferably 10,000 to 500,000, and more preferably about 15,000 to 300,000.

  The ratio of the non-cellulose ester thermoplastic resin is, for example, 1 to 150 parts by weight (for example, 3 to 120 parts by weight), preferably 5 to 100 parts by weight (for example, 10 to 80 parts) with respect to 100 parts by weight of the cellulose ester. Parts by weight), more preferably about 15 to 75 parts by weight (for example, 20 to 70 parts by weight).

[Plasticizer]
As the plasticizer, a compound capable of plasticizing cellulose ester, for example, phosphate ester, carboxylic acid ester [aromatic carboxylic acid ester, fatty acid ester, polyhydric alcohol (glycerin, trimethylolpropane, pentaerythritol, sorbitol, etc.) Lower fatty acid esters (such as triacetin (TA) and diglycerin tetraacetate), glycol esters (such as dipropylene glycol dibenzoate), citric acid esters (such as acetyltributyl citrate (OACTB))], amides [eg, N -Sulfonamides such as butylbenzenesulfonamide (BM-4)], ester oligomers (such as caprolactone oligomers) and the like.

Examples of phosphoric acid esters (non-condensed phosphoric acid esters) include aliphatic phosphoric acid esters [for example, trialkyl phosphoric acid esters (tri-C _1-12 alkyl esters such as triethyl phosphate and tributyl phosphate), triphosphoric acid phosphates. Alkoxyalkyl esters (for example, tri-C _1-6 alkoxy C _1-12 alkyl esters such as tributoxyethyl phosphate)], aromatic phosphates [alkyl diaryl esters of phosphate (eg, octyl diphenyl phosphate, Phosphoric acid C _1-20 alkyl-diC _6-15 aryl ester such as 2-ethylhexyldiphenyl phosphate, preferably phosphoric acid C _1-12 alkyl-di C _6-10 aryl ester), phosphoric acid triaryl ester (eg , Triphenyl phosphate (TPP), tricres phosphate Le (TCP), phosphoric acid tri (isopropylphenyl), trixylenyl phosphate, tri _{C 6-15} aryl esters such as phosphate, cresyl diphenyl cresyl phosphate-2,6-di (xylenyl), preferably phosphorus Acid tri-C _6-10 aryl ester and the like] and the like.

Aromatic carboxylic acid esters include aromatic polycarboxylic acid esters such as aromatic dicarboxylic acid esters [for example, dialkyl phthalates (for example, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate ( DBP), dihexyl phthalate, dioctyl phthalate (DOP), di-C _1-12 alkyl esters such as di-2-ethylhexyl phthalate (DEHP)), di (alkoxyalkyl) esters of phthalic acid (eg, phthalates) Phthalic acid C _1-6 alkoxy C _1-12 alkyl ester such as dimethoxyethyl acid), phthalic acid alkyl-aralkyl ester (eg phthalic acid C _1-12 alkyl- (C _6-10 aryl) such as butylbenzyl phthalate) -C _1-4 alkyl) esters ), Alkyl phthalyl alkyl glycolate (e.g., ethyl phthalyl ethylene glycolate, a C _1-6 alkyl phthalyl C _2-4 alkylene glycolate and butyl phthalyl butylene glycolate) such as phthalic acid esters, such as, Aromatic tricarboxylic acid ester (for example, trimellitic acid tri-C _1-12 alkyl ester such as trimethyl trimellitic acid, triethyl trimellitic acid, trioctyl trimellitic acid, tri-2-ethylhexyl trimellitic acid (TOTM)), aromatic tetra Carboxylic acid ester (for example, pyromellitic acid tetra C _1-12 alkyl ester such as pyromellitic acid tetraoctyl) may be mentioned.

Examples of fatty acid esters (aliphatic carboxylic acid esters) include aliphatic dicarboxylic acid esters (for example, dibutyl adipate, dioctyl adipate, butoxyethoxyethyl benzyl adipate, dibutoxyethoxyethyl adipate (BXA), etc.) _C6-12 dicarboxylic acid C _1-12 alkyl ester such as azelaic acid ester such as diethyl azelaate, dibutyl azelate, dioctyl azelate, sebacic acid ester such as dibutyl sebacate, dioctyl sebacate), unsaturated fatty acid ester (C _8-30 alkene carboxylic acid-C _1-12 alkyl ester such as butyl oleate and methyl acetyl ricinoleate) and the like.

  These plasticizers can be used alone or in combination of two or more.

  Of these plasticizers, phosphoric acid esters, phthalic acid esters (such as phthalic acid dialkyl esters), and ester oligomers are preferred. In particular, phosphoric acid esters (non-condensed phosphoric acid esters) [especially phosphoric acid triaryl esters (phosphorus) Aromatic phosphoric acid esters such as triphenyl acid) are preferred. In addition, when phosphoric acid ester is used as a plasticizer, flame retardance and heat resistance can also be improved.

  The plasticizer may be at least a plasticizer for the cellulose ester (that is, a plasticizer capable of plasticizing at least the cellulose ester), and in particular, a plastic capable of plasticizing both the cellulose ester and the non-cellulose ester thermoplastic resin. An agent may be used. As such a plasticizer capable of plasticizing both, for example, the thermoplastic resin is a polyester-based resin (such as an aromatic polyester-based resin) or a polycarbonate-based resin, which will be described later, for example. In some cases, plasticizers such as phosphate esters and phthalate esters are used. Also from such a point, a plasticizer such as a phosphate ester can be suitably used.

In addition, the plasticizer may have SP value comparable as the solubility parameter (SP value) of the said cellulose ester from a compatible viewpoint with the said cellulose ester. The SP value of the organic acid cellulose ester varies depending on the degree of substitution and the type, but is, for example, about 10 to 11 (MPa) ^{1/2 for} cellulose acetate. Therefore, SP value of the plasticizer, for example, 8 to 12 (MPa) ^1/2, a preferably 8.5-12 (MPa) ^1/2, more preferably 9 to 12 (MPa) about ^1/2 May be. In addition, the solubility parameter (SP, δ in the following formula) in the present invention conforms to the Small formula represented by the following formula.

δ = dΣ (Δδ) / M
(Where d is the density, Δδ is the solubility parameter corresponding to the constituent atomic group, and M is the molecular weight)
The small equation is an equation for obtaining a solubility parameter for a substance with an unknown SP value using the solubility parameter (or solubility parameter) corresponding to the constituent atomic group as described above. For details, refer to, for example, “Plasticizers-Theory and Application (First Edition, First Printing), Koichi Murai, pages 14 to 16;

  The plasticizer may be solid at room temperature or liquid. Even a plasticizer that is solid at room temperature is kneaded by a mixer such as a Henschel mixer, and the temperature in the system rises above the melting point of the plasticizer by external heating or frictional heat due to rotation in the mixer. In this case, the plasticizer and the cellulose ester are sufficiently mixed. A liquid plasticizer and a solid plasticizer may be used in combination.

  The ratio of the plasticizer (phosphate ester or the like) is, for example, 1 to 60 parts by weight, preferably 3 to 50 parts by weight (for example, 5 to 40 parts by weight), more preferably 8 to 100 parts by weight of the cellulose ester. About 30 parts by weight (particularly, 10 to 20 parts by weight) may be used.

  Moreover, the ratio of a plasticizer is 0.3-40 weight part (for example, 0.5-30 weight part) with respect to 100 weight part of total amounts of a cellulose ester and a non-cellulose ester type thermoplastic resin, Preferably, it is preferable. It may be about 1 to 25 parts by weight (for example, 2 to 20 parts by weight), more preferably about 3 to 18 parts by weight (particularly 5 to 15 parts by weight).

[Bleed-out inhibitor]
The bleed-out inhibitor can suppress bleed-out of the plasticizer from a composition (and a molded product thereof) containing a cellulose ester, a non-cellulose ester thermoplastic resin, and a plasticizer (plasticizer for the cellulose ester). Any compound may be used.

  Examples of such a compound that acts as a bleedout inhibitor include condensed phosphate esters (usually aromatic condensed phosphate esters), ketene dimers having a hydrocarbon group (hereinafter simply referred to as ketene dimers, ketene dimers, And succinic anhydrides having a hydrocarbon group (hereinafter sometimes simply referred to as succinic anhydrides).

(Condensed phosphate ester)
The condensed phosphate ester only needs to be a compound that can suppress bleed-out of the plasticizer. Usually, a phosphorus component such as phosphorus oxychloride and a polyhydroxy compound [or polyols (usually aromatic polyols)] A reaction product (especially an aromatic condensed phosphate ester) with monools (or monohydroxy compounds, especially monohydroxyarenes such as phenols), and at least two (especially two) phosphoric acids A compound having a unit in the molecule.

  Examples of the polyols include non-aromatic polyols (for example, aliphatic polyols) and aromatic polyols (usually polyhydric phenols, bisphenols, etc.). The polyols are usually composed of at least an aromatic polyol.

As typical polyhydric phenols (polyhydroxybenzene), for example, dihydroxybenzene (catechol, resorcinol, hydroquinone), dihydroxybenzene having a substituent {alkyl-dihydroxybenzene [dihydroxytoluene (3,5-dihydroxytoluene, etc.)] Mono- or di-C _1-10 alkyl-dihydroxybenzene such as 5-t-butylresorcinol, dihydroxyxylene (such as 2,6-dihydroxy-p-xylene)], aryl-dihydroxybenzene (such as 2,4-dihydroxybiphenyl) the _{C 6-10} aryl - such as dihydroxybenzene), halo - mono or dihalo, such as dihydroxybenzenes (2,4-difluoro hydroquinone - dihydroxybenzene etc.), acyl - dihydroxy Ben Emissions [alkylcarbonyl - dihydroxybenzene _{(C 2-6} alkylcarbonyl, such as 2,4-dihydroxy acetophenone - such as dihydroxybenzene), arylcarbonyl - dihydroxybenzene (e.g., _{C 6-10} arylcarbonyl such as 2,4-dihydroxybenzophenone -Dihydroxybenzenes, etc.}; trihydroxybenzenes corresponding to these dihydroxybenzenes [for example, trihydroxybenzene (pyrogallol, hydroxyhydroquinone, phloroglucinol), trihydroxyacetophenone, etc.] It is done.

Typical bisphenols include 4,4′-dihydroxybiphenyl, bis (hydroxyphenyl) alkanes [for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis ( 4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3 -Dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2- Bis (hydroxyphenyl) C _1-10 alkane _optionally having substituents such as bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) diphenylmethane], bis (hydroxyphenyl) cycloalkanes [For example, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxy Bis (hydro) optionally having a substituent such as phenyl) cyclohexane _{Shifeniru) C 5-10} cycloalkane, bis (hydroxyphenyl) ethers (4,4'-dihydroxy diphenyl ether - ether, etc.), bis (hydroxyphenyl) sulfones (4,4'-dihydroxydiphenyl sulfone), Bis (hydroxyphenyl) sulfoxides (such as 4,4′-dihydroxydiphenyl sulfoxide), bis (hydroxyphenyl) sulfides (such as 4,4′-dihydroxydiphenyl sulfide), bis (hydroxyphenyl-alkyl) arenes [4, 4 ′-(m-phenylenediisopropylidene) diphenol etc.] and the like.

  Of these, preferred polyols are dihydroxybenzenes [dihydroxybenzene (resorcinol, hydroquinone, etc.), alkyl-dihydroxybenzene, halo-dihydroxybenzene and the like which may have a substituent (particularly, a substituent). And resorcinol that may be present)].

Examples of monools (including phenols) include non-aromatic monoalcohols (such as aliphatic alcohols) and monohydroxyarenes. Monools may usually be monohydroxyarenes. Typical monohydroxyarenes include, for example, phenols {for example, phenol, phenol having a substituent [alkylphenol (o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5 Mono- or di-C _1-10 alkylphenols such as dimethylphenol, 2,6-dimethylphenol, 2,6-di-t-butylphenol, preferably mono- or di-C _1-6 alkylphenols, more preferably di-C _1-4 Hydrocarbon groups such as alkylphenol), arylphenol (mono- or di-C _{6-10 arylphenol} such as o-phenylphenol), cycloalkylphenol (mono- or di-C _5-10 cycloalkylphenol such as 2-cyclohexylphenol), etc. Have Phenol, (such as o- methoxy mono- or di-C _1-10 alkoxy phenols such as phenol) alkoxy phenol, (including mono- or di-halo phenols such as chlorophenol) halophenol, C, such as acyl phenol [alkylcarbonyl phenol (hydroxyacetophenone Monohydroxy C _6-10 arene and the like which may have a substituent such as _2-6 alkylcarbonylphenol), arylcarbonyl-dihydroxybenzene (for example, C _6-10 arylcarbonylphenol such as hydroxybenzophenone)] included.

  Among these monools, phenols and phenols having a hydrocarbon group are preferable, and alkylphenols are particularly preferable. The monools to be reacted with the phosphorus component and the polyols may be used alone or in combination of two or more.

  Preferred condensed phosphate esters are aromatic condensed phosphate esters (ie, condensed phosphate esters in which the polyols are aromatic polyols and the monols are monohydroxyarenes).

  Typical condensed phosphate esters include, for example, compounds represented by the following formula (1) (condensed phosphate esters using phenols and dihydroxybenzenes as raw materials).

(In the formula, R ^{1 to} R ³ are the same or different and represent a substituent, k and m represent an integer of 0 to 5, and n represents an integer of 0 to 4.)
In the above formula (1), examples of the substituent represented by R ^{1 to} R ³ include a hydrocarbon group [alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, C _1-10 alkyl group such as t-butyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group, etc., cycloalkyl group (C _5-10 cycloalkyl such as cyclohexyl group) Group), aryl group (C _6-10 aryl group such as phenyl group, tolyl group, xylyl group, etc.), etc.], alkoxy group (C _1-4 alkoxy group such as methoxy group, etc.), acyl group (acetyl group etc.) _C, such as _1-6 acyl group), and like _{C 1-4} alkoxycarbonyl group such as an alkoxycarbonyl group (methoxycarbonyl group), a halogen atom (fluorine atom, chlorine Child, such as a bromine atom), and the like.

Preferred substituents (for example, R ¹ and R ² ) include hydrocarbon groups, particularly alkyl groups (such as C _1-4 alkyl groups such as a methyl group) and the like.

  In many cases, the total number of substitutions k, m, and n is an integer of 1 or more (for example, 2 to 8, preferably about 3 to 6). In particular, k and m are each 1 or more (for example, 2 to 2). 4, preferably 2-3, in particular 2).

The substitution position of the substituents R ^{1 to} R ³ is not particularly limited. For example, the substituents R ¹ and R ² of the terminal benzene ring can be appropriately selected from the 2 to 6 positions of the benzene ring, and are usually at least the 2 position. The substituent R ¹ or R ² may be substituted at (or 6-position). For example, the substituents R ¹ and R ² may be substituted at the 2-position, 6-position, 2-position, 3-position, 2-position, 4-position, etc., when k and m are 2, particularly the 2-position And may be substituted at the 6-position.

  Among the compounds represented by the formula (1), preferable condensed phosphate esters include compounds represented by the following formula (2).

(In formula, R ^<1a> , R ^<1b> , R ^<2a> and R ^<2b> are the same or different, and show an alkyl group.)
In the above formula (2), examples of the alkyl group represented by R ^1a , R ^1b , R ^2a and R ^2b include the alkyl groups exemplified above (C _1-4 alkyl groups such as a methyl group).

  Examples of the compound represented by the formula (1) or (2) include resorcinol bisaryl phosphates such as resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), and resorcinol bis (dixyl phosphate) (described later). A compound represented by the formula (3)); hydroquinone bisaryl phosphates such as hydroquinone bis (diphenyl phosphate), hydroquinone bis (dicresyl phosphate) and hydroquinone bis (dixyl phosphate).

  Among the compounds represented by the above formula (2), particularly preferred condensed phosphate esters include resorcinol bis (2,6-dialkylphenyl phosphate), that is, a compound represented by the following formula (3). It is.

(Wherein, R ^1a , R ^1b , R ^2a and R ^2b are the same as above.)
The condensed phosphate ester may be liquid or solid at room temperature (for example, about 15 to 30 ° C.). Preferred condensed phosphate esters include condensed phosphate esters that are solid at room temperature from the viewpoint of efficiently suppressing bleed out.

  The melting point of the condensed phosphate ester (condensed phosphate ester that is solid at room temperature) can be selected from the range of, for example, 10 ° C. or more (for example, about 20 to 250 ° C.), for example, 30 ° C. or more (for example, 35 to 220). Degree C.), preferably 40 ° C. or higher (eg, about 50 to 200 ° C.), more preferably 60 ° C. or higher (eg, about 70 to 150 ° C.), particularly 80 ° C. or higher (eg, about 85 to 130 ° C.). May be. In addition, when combining 2 or more types of condensed phosphate ester, the melting | fusing point of each condensed phosphate ester may be the said range, and the melting | fusing point of the whole condensed phosphate ester may be the said range. Further, when the condensed phosphate ester contains impurities, the melting point of the condensed phosphate ester itself [or the condensed phosphate ester of high purity (for example, purity of about 99 to 100%)] may be in the above range.

(Ketene dimers)
The ketene dimers (or diketenes) may have at least one ketene dimer skeleton (ketene dimer unit), and a plurality (for example, 2 to 20, preferably 2 to 15, more preferably 2 to 8). Degree) ketene dimer skeleton. For example, the ketene dimers may be ketene dimers (or ketene multimers) in which a plurality of ketene dimer skeletons are linked via a linking group such as an alkylene group. The ketene dimers (diketenes) may be ketoketens or aldketene dimers, or may be ketketene and aldketene dimers. The ketene dimers may usually be ketoketen dimers.

  Furthermore, diketenes include diketene derivatives. Examples of such a diketene derivative include a compound (hydrogenated product) having a lactone (β-lactone) skeleton in which hydrogen or the like is added to the carbon-carbon double bond of a diketene. Such a hydrogenated product can be obtained by catalytic reduction of diketene.

  Typical ketene dimers include compounds having one ketene dimer skeleton in the molecule, for example, a compound represented by the following formula (4) or a derivative thereof (hydrogenated product or the like).

(In the formula, R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. However, R ⁴ and R ⁵ do not simultaneously become a hydrogen atom. )
In the formula (4), examples of the hydrocarbon group represented by R ⁴ and R ⁵ include an aliphatic hydrocarbon group [for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, C _1-40 alkyl group such as heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group (or stearyl group), eicosyl group), alkenyl group (allyl group, butenyl group, hexenyl group) , octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, etc. _{C 2-40} alkenyl group such as eicosenyl group), alkadienyl groups (octadienyl group, _{C 4-40} alkadienyl, such octadecadienyl group Group)], alicyclic hydrocarbon group [for example, cycloalkyl group ( In example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, _{C 4-15} alkyl groups such as cyclooctyl group, preferably a _{C 5-10} cycloalkyl group), etc.], an aromatic hydrocarbon group [for example, an aryl group (e.g., A C _6-10 aryl group such as a phenyl group or a naphthyl group), an aralkyl group (for example, a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group or a phenethyl group) and the like.

The hydrocarbon group represented by R ⁴ and R ⁵ may have a substituent. Examples of the substituent include a hydrocarbon group [for example, an alkyl group (such as the above exemplified alkyl group), an alkenyl group (such as the above exemplified alkenyl group), a cycloalkyl group (such as the above exemplified cycloalkyl group), an aryl group (such as phenyl). Such as the above exemplified aryl groups such as a group)], an alkoxy group (such as an alkoxy group corresponding to the alkyl group such as a methoxy group, an ethoxy group, and a propoxy group), a hydroxyl group, a carboxyl group, an amino group, a substituted amino group ( A mono- or dialkylamino group such as a methylamino group), a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an acyl group (for example, a C _1-4 alkyl-carbonyl group such as an acetyl group), Ester group [eg alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl A C _1-4 alkoxy-carbonyl group such as a bonyl group) and the like. The hydrocarbon group may have these substituents alone or in combination of two or more.

Of these hydrocarbon groups represented by R ⁴ and R ⁵ , a long-chain aliphatic hydrocarbon group which may have a substituent (for example, a C _6-40 aliphatic hydrocarbon group, preferably C _{8 -35} aliphatic hydrocarbon group, more preferably C _10-30 aliphatic hydrocarbon group, etc., and an alicyclic hydrocarbon group which may have a substituent (for example, C _4-10 alicyclic hydrocarbon) A group, preferably a C _5-8 alicyclic hydrocarbon group, etc., an optionally substituted aromatic hydrocarbon group (eg, a C _6-20 aromatic hydrocarbon group, preferably a C _6-15 An aromatic hydrocarbon group, more preferably a C _6-8 aromatic hydrocarbon group and the like, and a long-chain aliphatic hydrocarbon group which may have a substituent [particularly, a long-chain alkyl group (for example, , _{C 6-40} alkyl group, preferably a _{C 8-35} alkyl group, further Preferably _{C 10-30} alkyl group, especially _{C 12-22} alkyl group), etc.] is preferable.

In general, both R ⁴ and R ⁵ are often hydrocarbon groups. R ⁴ and R ⁵ may be different, but usually may be the same.

Specific ketene dimers having a hydrocarbon group include, for example, alkyl ketene dimers (in the formula (1), R ⁴ and R ⁵ are alkyl groups which may have a substituent). ), Alkenyl ketene dimers (in the formula (4), R ⁴ and R ⁵ are alkene groups which may have a substituent), cycloalkyl ketene dimers (in the formula (4), R ⁴ and R ⁵ are ketene dimers that are optionally substituted cycloalkyl groups), aryl ketene dimers (in the above formula (4), R ⁴ and R ⁵ are substituted) A ketene dimer which is a good aryl group) an aralkyl ketene dimer (in the above formula (1), R ⁴ and R ⁵ may have a substituent). Ketene dimer which is an alkyl group).

Examples of the alkyl ketene dimer include a ketene dimer having a long-chain alkyl group (for example, decyl ketene dimer (that is, ketene dimer in which R ⁴ and R ⁵ are decyl groups in the formula (4), the same applies hereinafter), , Tetradecyl ketene dimer, hexadecyl ketene dimer, octadecyl ketene dimer (stearyl ketene dimer), eicosyl ketene dimer, C _8-35 alkyl-ketene dimer, preferably C _10-30 alkyl-ketene dimer, more preferably C _12-26 alkyl-ketene dimer, especially _C14-22 alkyl-ketene dimer] and the like.

Alkenyl ketene dimers include ketene dimers having a long-chain alkenyl group [for example, octenyl ketene dimer, decenyl ketene dimer, dodecenyl ketene dimer, tetradecenyl ketene dimer, hexadecenyl ketene dimer, octadecenyl ketene dimer, _C8-35 alkenyl-ketene dimer, such as _decenyl ketene dimer, _eicocenyl ketene dimer, preferably _C10-30 alkenyl-ketene dimer, more preferably _C12-26 alkenyl-ketene dimer, especially _C14-22 Alkenyl-ketene dimer, etc.].

The cycloalkyl ketene dimer includes a cycloalkyl ketene dimer having an alkyl group (for example, a C _4-30 alkyl-C _4-10 cycloalkyl-ketene dimer such as nonyl cyclohexyl ketene dimer, preferably C _6-25 alkyl-C _{5. -8} cycloalkyl-ketene dimer, etc.). As the aryl ketene dimer, an aryl ketene dimer having an alkyl group (for example, C _4-30 alkyl-C _6-20 aryl-ketene dimer such as octylphenyl ketene dimer, nonylphenyl ketene dimer, dodecylphenyl ketene dimer, preferably And C _6-25 alkyl-C _6-15 aryl-ketene dimer). Examples of the aralkyl ketene dimer include C _6-10 aryl-C _1-4 alkyl-ketene dimer such as phenethyl ketene dimer, preferably C _6-8 aryl-C _1-2 alkyl-ketene dimer.

Preferred ketene dimers include compounds represented by the following formula (4A) or derivatives thereof (hydrogenated products, etc.) among the compounds represented by the formula (4) or derivatives thereof (hydrogenated products, etc.). In particular, ketene dimers having a long-chain aliphatic hydrocarbon group [for example, ketene dimers having a long-chain alkyl group (for example, C _10-30 alkyl-ketene dimer) and the like] are preferable.

(In the formula, R ^4a and R ^5a are the same or different and are a hydrogen atom, a C _6-40 aliphatic hydrocarbon group which may have a substituent, or an alicyclic group which may have a substituent. A hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, provided that R ^4a and R ^5a are not simultaneously hydrogen atoms)
The ketene dimers can be obtained, for example, by producing a corresponding ketene from a carboxylic acid or a derivative thereof (for example, a carboxylic acid halide such as carboxylic acid chloride) as a raw material, and polymerizing the ketene (dimerization). it can. The ketene dimers (ketene multimers) having a plurality of ketene dimer skeletons are, for example, at least part or all of carboxylic acid or a derivative thereof (for example, carboxylic acid halide such as carboxylic acid chloride) as a polycarboxylic acid. It may be obtained by replacing with (for example, dicarboxylic acid).

(Succinic anhydrides)
The succinic anhydrides may have a succinic anhydride which may have a substituent [succinic anhydride substituted with an alkyl group such as succinic anhydride or methyl succinic anhydride; an succinic anhydride substituted with an aryl group such as phenyl succinic anhydride. It is a compound in which a hydrocarbon group which may have a substituent is substituted on an acid or the like, particularly succinic anhydride].

  That is, the succinic anhydride has maleic anhydride (maleic anhydride corresponding to the succinic anhydride such as maleic anhydride and methylmaleic anhydride) which may have the substituent, and at least allyl hydrogen. An ene adduct obtained by subjecting a compound (for example, an internal olefin optionally having a substituent) to an ene addition reaction, and usually a compound having a carbon-carbon double bond at least in the β-position (or its) Derivatives) in many cases. The succinic anhydride includes derivatives of the ene adduct. Examples of such derivatives include hydrogenated products in which hydrogen is added to an unsaturated hydrocarbon group (or a β position thereof) that is substituted with succinic anhydrides. Such a hydrogenated product can be obtained, for example, by hydrogenating an unsaturated bond at the β-position by catalytic reduction or the like.

  Examples of succinic anhydrides having a typical hydrocarbon group include a compound represented by the following formula (5) or a derivative thereof (such as a hydrogenated product).

(Wherein R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent, and R ⁸ represents a hydrogen atom or a substituent.)
Examples of the hydrocarbon group represented by the groups R ⁶ and R ⁷ include an aliphatic hydrocarbon group [for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, an octyl group). Group, a C _1-30 alkyl group such as a decyl group, preferably a C _2-20 alkyl group, more preferably a C _3-10 alkyl group), an alkenyl group (for example, a C _2-10 alkenyl group such as an allyl group). Etc.], alicyclic hydrocarbon groups [for example, cycloalkyl groups (such as the above-mentioned cycloalkyl groups such as cyclohexyl groups), etc.], aromatic hydrocarbon groups [eg, aryl groups (such as the above-mentioned aryl groups such as phenyl groups, etc.) Group etc.) etc.] etc. are mentioned, An aliphatic hydrocarbon group is preferable.

The hydrocarbon groups represented by the groups R ⁶ and R ⁷ may have a substituent. Examples of the substituent include the substituents exemplified in the section of the ketene dimers (for example, hydrocarbon groups such as alkyl groups, alkoxycarbonyl groups, etc.). The base ^{[R 6 -CH = CH-CHR} 7 -] substituting the succinic anhydride in, ^{R 6} and ^{R 7} carbon atoms (total carbon number), for example, 0 to 45 (e.g., 1-35 ), Preferably 4 to 30, more preferably 6 to 25, particularly 10 to 22 (for example, 12 to 20).

In addition, examples of the substituent represented by the group R ⁸ include the substituents exemplified in the section of the ketene dimers. Preferable group R ⁸ includes a hydrogen atom or a hydrocarbon group (for example, an alkyl group such as a methyl group, an aryl group such as a phenyl group) and the like, and a hydrogen atom is particularly preferable.

Specific succinic anhydrides include succinic anhydrides having an aliphatic hydrocarbon group, such as alkenyl succinic anhydrides (eg, β-alkenyl succinic anhydrides), such as β-butenyl succinic anhydride, β-octenyl anhydride. Β-C _6-35 alkenyl-succinic anhydrides such as succinic acid, β-decenyl succinic anhydride, β-dodecenyl succinic anhydride, β-tetradecenyl succinic anhydride, β-hexadecenyl succinic anhydride, β-octadecenyl succinic anhydride , Preferably β-C _8-30 alkenyl-succinic anhydrides, more preferably β-C _10-25 alkenyl succinic anhydrides, in particular β-C _12-22 alkenyl succinic anhydrides), and the corresponding alkyl succinic anhydrides. Examples include acids (hydrogenated products of alkenyl succinic anhydrides).

  Succinic anhydrides may be used alone or in combination of two or more.

Preferred succinic anhydrides include compounds represented by the following formula (5A) or derivatives thereof (hydrogenated products, etc.) among the compounds represented by the formula (5) or derivatives thereof (hydrogenated products, etc.). In particular, succinic anhydrides having a long-chain aliphatic hydrocarbon group [for example, succinic anhydrides having a long-chain alkenyl group (for example, β-C _8-30 alkenyl succinic anhydrides) and the like] and the like can be mentioned.

(In the formula, R ^6a and R ^7a are the same or different, and a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent, the total number of carbon atoms of R ^6a and R ^7a is 1 to 35. And R ^8a represents a hydrogen atom or a substituent.)
The ketene dimers and succinic anhydrides may be liquid at room temperature, and usually may be solid. The ketene dimers and / or succinic anhydrides may be used as an emulsion. When using such an emulsion-like bleedout inhibitor, for example, cellulose ester, thermoplastic resin, plasticizer, and the like, and an emulsion-like bleedout inhibitor are mixed by an extruder or the like, and moisture constituting the emulsion. The resin composition may be prepared while removing the above through a vent or the like.

  Of these compounds, the bleed-out inhibitor is preferably composed of at least a condensed phosphate ester, and may be composed of only a condensed phosphate ester. Bleed-out inhibitors may be used alone or in combination of two or more.

  The ratio of the bleed out inhibitor (the ratio of the solid content in the emulsion or the like, hereinafter the same) is, for example, 1 to 60 parts by weight, preferably 3 to 50 parts by weight (for example, 5 to 45 parts by weight) relative to 100 parts by weight of the plasticizer. Parts by weight), more preferably about 8 to 40 parts by weight (for example, 10 to 30 parts by weight).

  Moreover, the ratio of a bleed-out inhibitor is 0.3-50 weight part with respect to 100 weight part of cellulose ester, Preferably it is 0.5-30 weight part, More preferably, it is 1-15 weight part (for example, 1.5-7 parts by weight).

  Furthermore, the ratio of the bleed-out inhibitor is, for example, 0.1 to 40 parts by weight, preferably 0.3 to 20 parts by weight with respect to 100 parts by weight of the total amount of the cellulose ester and the non-cellulose ester thermoplastic resin. More preferably, it may be about 0.5 to 10 parts by weight (for example, 1 to 5 parts by weight).

[Compatibilizer]
The resin composition of the present invention may contain a compatibilizer as necessary. When the compatibilizing agent is included, layer peeling in the resin composition (or molded product) can be efficiently prevented or suppressed.

The compatibilizing agent can be appropriately selected according to the type of non-cellulose ester thermoplastic resin (and cellulose ester). For example, an oxazoline compound, a modifying group (carboxyl group, acid anhydride group, epoxy group, oxazolinyl group, etc.) Modified resins (having modified groups), dienes or rubber-containing polymers [for example, diene monomers (C _4-20 conjugated dienes _optionally having substituents such as butadiene, isoprene, etc.) ) Homopolymer or copolymer, diene monomer and copolymerizable monomer (aromatic vinyl monomer such as styrene, (meth) acrylic monomer, maleimide monomer, etc.) Diene polymers such as copolymers (random copolymers) obtained by polymerization; diene polymers such as acrylonitrile-butadiene-styrene copolymers (ABS resin) Raft copolymer; styrene-butadiene (SB) block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer (SEBS), hydrogenated (styrene-ethylene / butylene- Diene-based block copolymers such as styrene) block copolymers or hydrogenated products thereof], diene or rubber-containing polymers modified with the above-mentioned modifying groups (such as epoxy groups), and the like. These compatibilizers can be used alone or in combination of two or more.

  In addition, modification is a monomer corresponding to the modification group (for example, carboxyl group-containing monomer such as (meth) acrylic acid for carboxyl group modification, maleic anhydride for acid anhydride group modification, and (meta) for ester group modification. ) Acrylic monomers, maleimide monomers for maleimide group modification, and epoxy group-containing monomers such as glycidyl (meth) acrylate for epoxy modification) or epoxidize unsaturated double bonds And so on.

  Preferred compatibilizers include epoxy resins and epoxy-modified diene copolymers.

(Epoxy resin)
Examples of the epoxy resin include aromatic epoxy resins such as ether type epoxy resins {for example, biphenyl type epoxy resins (for example, 3,3 ′, 5,5′-tetramethylbiphenol type epoxy resins), bisphenol type epoxy resins, Novolak type epoxy resin [for example, novolak resin (for example, C _1-20 alkyl group, preferably C _1-4 alkyl group such as methyl group, ethyl group, etc.) _optionally substituted on the aromatic ring] , Phenol novolac resins, cresol novolac resins, etc.)], unsaturated cyclic hydrocarbon compound-modified epoxy resins (eg, (di) cyclopentadiene type epoxy resins), stilbene type epoxy resins, etc.], aromatic amine components [eg, Monocyclic aromatic amines (aniline, toluidine, etc.), monocyclic Aromatic diamines (diaminobenzene, xylylenediamine, etc.), monocyclic aromatic amino alcohols (aminohydroxybenzene, etc.), polycyclic aromatic diamines (diaminodiphenylmethane, etc.), polycyclic aromatic amines, etc.] The amine-based epoxy resin used is included. Epoxy resins may be used alone or in combination of two or more.

Examples of the bisphenol constituting the bisphenol type epoxy resin include the same compounds as the bis (hydroxyphenyl) alkanes. Preferred bisphenol type epoxy resins include epoxy resins formed by reaction of bisphenols with epichlorohydrin, such as bis (hydroxyaryl) C _1-6 alkanes, particularly glycidyl ethers such as bisphenol A, bisphenol AD, and bisphenol F. It is done. The bisphenol-type epoxy resin also includes the bisphenol glycidyl ether (that is, phenoxy resin) having a large molecular weight.

  The number average molecular weight of the epoxy resin may be, for example, 200 to 200,000, preferably 300 to 150,000, and more preferably about 400 to 100,000 (for example, about 400 to 80,000). In particular, the number average molecular weight of the phenoxy resin may be, for example, 10,000 to 180,000, preferably 20,000 to 120,000, and more preferably about 30,000 to 100,000 (for example, about 40,000 to 80,000).

  The epoxy equivalent of the epoxy resin may be, for example, 100 to 40000 g / eq, preferably 120 to 30000 g / eq, and more preferably about 150 to 20000 g / eq. In particular, the epoxy equivalent of the phenoxy resin is, for example, 1000 to 35000 g / eq, preferably 2000 to 25000 g / eq (for example, 3000 to 15000 g / eq), and more preferably 4000 to 13000 g / eq (for example, 5000 to 12000 g / eq). eq) degree.

  The epoxy resin can also be obtained from Japan Epoxy Resins Co., Ltd. as a registered trademark “Epicoat” series.

(Epoxy-modified diene copolymer)
The epoxy-modified diene copolymer (or epoxidized diene copolymer) may be any of random, block, and graft copolymers, but a block copolymer can be preferably used. Epoxy-modified diene copolymers may be used alone or in combination of two or more.

  Examples of the epoxy-modified diene block copolymer include the conjugated diene block (or a part thereof) such as the diene block copolymer exemplified above or a hydrogenated product thereof, for example, a styrene-butadiene-styrene (SBS) block copolymer. And a conjugated diene block copolymer composed of a hydrogenated block) and a non-conjugated diene block (for example, an aromatic vinyl block).

  In epoxy-modified diene block copolymer (or epoxidized diene block copolymer), ratio (weight ratio) of non-conjugated diene block (especially aromatic vinyl block) and conjugated diene block (or its hydrogenated block) ), For example, the former / the latter = about 5/95 to 80/20 (for example, about 25/75 to 80/20), and usually about 50/50 to 80/20.

  In the epoxidized diene block copolymer, part or all of the double bonds may be epoxidized. In the epoxidized diene block copolymer, the ratio of the epoxy group may be, for example, about 0.1 to 8% by weight (for example, 1 to 5% by weight) as the oxygen concentration of oxirane. The equivalent may be, for example, about 300 to 1000, preferably about 500 to 900.

  For the epoxidized block copolymer, a diene block copolymer (or a partially hydrogenated block copolymer) is epoxidized by a conventional method (for example, epoxidation of peracids, hydroperoxides, etc.) For example, epoxidation with an agent).

  The molecular structure of the block copolymer may be linear, branched, radial, or a combination thereof. Examples of the block structure of the block copolymer include a multi-block structure such as a monoblock structure and a teleblock structure, a trichain radial teleblock structure, and a tetrachain radial teleblock structure.

  The proportion of the compatibilizing agent is, for example, 0.3 to 30 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight (for example, 2 to 10 parts by weight) with respect to 100 parts by weight of the cellulose ester. Part by weight).

  The proportion of the compatibilizer is, for example, 0.1 to 20 parts by weight, preferably 0.3 to 15 parts by weight, more preferably 100 parts by weight of the total amount of the cellulose ester and the non-cellulose ester thermoplastic resin. May be about 0.5 to 10 parts by weight (for example, 1 to 7 parts by weight).

[filler]
The resin composition of the present invention may further contain a filler. Combining cellulose ester, non-cellulosic thermoplastic resin, plasticizer and bleed-out inhibitor, and filler efficiently produces a resin composition with low environmental impact and excellent fluidity, rigidity, and dimensional accuracy. Obtainable.

  Fillers include fibrous fillers and non-fibrous fillers (such as granular or plate-like fillers). These fillers can be used alone or in combination of two or more.

  Examples of the fibrous filler include organic fibers (natural fibers, papers, etc.), inorganic fibers (glass fibers, asbestos fibers, carbon fibers, silica fibers, silica / alumina fibers, wollastonite, zirconia fibers, potassium titanate. Fibers), metal fibers, and the like. These fibrous fillers can be used alone or in combination of two or more.

  Of these fibrous fillers, natural fibers such as natural fibers, papers, glass fibers, and potassium titanate fibers are particularly preferable. Natural fibers include, for example, pulp [cotton, seed hair (kapok, pompacs, etc.), bast fibers (flax, cannabis, ramie, jute, kozo, mitsumata etc.), monocotyledonous fibers (bamboo, straw, bagasse, Esparto, etc.), wood fibers (eg, wood fibers such as conifers, hardwoods, etc.), leaf fibers (manila hemp, sisal etc.) etc.] or regenerated pulp, bast fiber, monocot plant fiber, leaf fiber without pulping Directly obtained fibers can be exemplified. The paper may be waste paper.

  The average fiber length of the fibrous filler (for example, natural fiber) is, for example, 10 mm or less (for example, 0.1 to 10 mm), preferably from the viewpoint of smoothly feeding in melt-kneading and improving impact resistance. It is about 0.5 to 10 mm, more preferably about 1 to 5 mm. The average fiber diameter of the fibrous filler is, for example, about 0.1 to 50 μm, preferably about 0.5 to 30 μm, and more preferably about 1 to 10 μm.

  Among the non-fibrous fillers, as granular or plate-like fillers, mineral particles [talc, mica, calcined siliceous earth, kaolin, sericite, bentonite, smectite, clay, silica, quartz powder, glass beads, Glass powder, glass flake, milled fiber, wollastonite (or wollastonite), etc.], boron-containing compounds (boron nitride, boron carbide, titanium boride, etc.), metal carbonates (magnesium carbonate, heavy calcium carbonate, light Calcium carbonate, etc.), metal silicates (calcium silicate, aluminum silicate, magnesium silicate, alumino magnesium silicate, etc.), metal oxides (magnesium oxide, etc.), metal hydroxides (aluminum hydroxide, calcium hydroxide, magnesium hydroxide, etc.) ), Metal sulfates (calcium sulfate, barium sulfate, etc.) Metal carbides (silicon carbide, aluminum carbide, and titanium carbide), metal nitride (aluminum nitride, silicon nitride, titanium nitride, etc.), white carbon, and various metal foils. These non-fibrous fillers can be used alone or in combination of two or more.

  Of these non-fibrous fillers, mineral particles (talc, mica, silica, wollastonite, etc.), boron-containing compounds (boron nitride, etc.) are preferred, and mineral particles are particularly preferred. As the talc, for example, talc obtained by classifying talc ore collected from a mine by a conventional method can be used. As boron nitride, for example, boron nitride obtained by adding urea, dicyandiamide, ammonium chloride or the like to boric acid, reducing and nitriding at high temperature in ammonium, and classifying by a conventional method can be used.

  The average particle size of the non-fibrous filler (powder filler) can be selected from a range of about 30 μm or less, for example, 10 μm or less (0.1 to 10 μm), preferably 5 μm or less (for example, 0.3 to 5 μm). ), More preferably about 0.5 to 5 μm (particularly 1 to 5 μm).

  Of these inorganic fillers, normally, particulate fillers, particularly mineral fine particles (for example, talc) are preferably used. From the viewpoint of moldability, fibrous fillers can also be preferably used.

  The proportion of the filler is, for example, 1 to 40 parts by weight, preferably 2 to 30 parts by weight (for example, 3 to 25 parts by weight), more preferably 4 to 20 parts by weight (for example, with respect to 100 parts by weight of the cellulose ester. 5 to 15 parts by weight). The proportion of the filler is, for example, 0.5 to 30 parts by weight, preferably 1 to 25 parts by weight (for example, 2 to 20 parts by weight) with respect to 100 parts by weight of the total amount of the cellulose ester and the non-cellulosic thermoplastic resin. Part), more preferably about 3 to 15 parts by weight (for example, 4 to 10 parts by weight).

  The ratio of the filler in the resin composition is, for example, about 0.1 to 20% by weight, preferably 0.5 to 15% by weight, and more preferably about 1 to 10% by weight of the entire resin composition. May be.

  The ratio (weight ratio) between the plasticizer and the filler can be selected from the range of the former / the latter = 99/1 to 10/90, but is usually 95/5 to 30/70, preferably 90/10 to 40. / 60, more preferably about 85/15 to 50/50 (for example, 80/10 to 55/45). When the plasticizer and the filler are combined in such a range, the fluidity and rigidity of the resin composition can be improved efficiently.

[Epoxy compound]
The resin composition of the present invention further includes an epoxy as a stabilizer from the viewpoint of reducing generation of volatile components such as organic acids (such as acetic acid) by molding having a melting step (for example, injection molding). It is preferred to add the compound. Moreover, coloring of a resin composition (or molded article) can be efficiently suppressed or prevented by using an epoxy compound.

  Examples of the epoxy compound (an epoxy compound that is not the epoxy resin and the epoxy-modified diene copolymer) include an alicyclic epoxy compound, a glycidyl ester compound, a glycidyl amine compound, and a long-chain aliphatic epoxy compound. These epoxy compounds can be used individually or in combination of 2 or more types.

Examples of the alicyclic epoxy compound include vinylcyclohexene dioxide, dicyclopentadiene oxide, 3,4-epoxy-1- [8,9-epoxy-2,4-dioxaspiro [5.5] undecan-3-yl. ] -Epoxy such as cyclohexane- [epoxy-oxaspiro _C8-15 alkyl] -cycloC _5-12 alkane, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and 4,5-epoxycyclo Epoxy C _5-12 cycloalkyl C _1-3 alkyl-epoxy C _5-12 cycloalkane carboxylate, such as octylmethyl-4 ', 5'-epoxycyclooctanecarboxylate, bis (2-methyl-3,4-epoxy Bis (such as cyclohexylmethyl) adipate _1-3 alkyl epoxy _{C 5-12} cycloalkyl _{C 1-3} alkyl) and di carboxylate. These alicyclic epoxy compounds can be used alone or in combination of two or more.

Examples of glycidyl ester compounds include aliphatic carboxylic acid glycidyl esters (saturated C _2-24 aliphatic carboxylic acid glycidyl esters such as glycidyl acetate, glycidyl butyrate, glycidyl laurate, glycidyl palmitate, and glycidyl stearate). And aliphatic dicarboxylic acid diglycidyl ester such as adipic acid diglycidyl ester and dodecanedioic acid diglycidyl ester), unsaturated carboxylic acid glycidyl ester [(meth) acrylic acid glycidyl ester, oleic acid glycidyl ester, linoleic acid glycidyl ester unsaturated C _2-24 aliphatic carboxylic acid glycidyl ester, etc.], an aromatic carboxylic acid glycidyl ester (glycidyl benzoate, such as, phthalic acid jig Etc. glycidyl ester), and the like. These glycidyl ester compounds can be used alone or in combination of two or more.

  Examples of the glycidylamine compound include tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, diglycidylaniline, diglycidyltoluidine, and the like. These glycidylamine compounds can be used alone or in combination of two or more.

Examples of long-chain aliphatic epoxy compounds include epoxidized oils (epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, etc.), epoxidized fatty acid alkyls (epoxidized methyl stearate, epoxidized butyl stearate, epoxy) _Epoxidized C _8-24 fatty acid C _1-12 alkyl, etc.), epoxidized polybutadiene, long chain α-olefin oxide, and the like. These long-chain alicyclic epoxy compounds can be used alone or in combination of two or more. Epoxidized soybean oil can be obtained, for example, from Daicel Chemical Industries, Ltd. under the trade name Daimac “S-300K” (melting point—5 ° C. to 5 ° C., specific gravity 0.991).

Among these epoxy compounds, alicyclic epoxy compounds and long-chain aliphatic epoxy compounds, particularly 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 4,5-epoxycyclooctylmethyl- Epoxy C _5-12 cycloalkyl C _1-3 alkyl-epoxy C _5-12 cycloalkane carboxylate such as 4 ′, 5′-epoxycyclooctanecarboxylate, and epoxidized oil such as epoxidized soybean oil are preferred.

  The ratio of the epoxy compound can be selected from a range of about 0.05 to 10 parts by weight with respect to 100 parts by weight of the cellulose ester, and the generation of volatile components to such an extent that no odor of organic components (organic acid odor etc.) is felt. From the point of suppression, for example, it is about 0.1 to 5 parts by weight, preferably about 0.3 to 4 parts by weight, more preferably about 0.4 to 3 parts by weight (for example, 0.5 to 1 part by weight). Also good.

  The proportion of the epoxy compound is, for example, 0.05 to 4 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 100 parts by weight of the total amount of cellulose ester and non-cellulose ester thermoplastic resin. It may be about 0.2 to 2 parts by weight (for example, 0.3 to 0.8 parts by weight).

[Stabilizer]
The resin composition of the present invention may further contain a stabilizer such as an organic acid, a thioether compound, or a phosphite compound. By using these stabilizers, coloring of the resin composition (or molded product) can be efficiently suppressed or prevented. These stabilizers can be used alone or in combination of two or more.

(Organic acid)
As the organic acid, a weak organic acid having a pKa value of usually 1 or more (for example, 1 to 10), preferably about 2 or more (for example, 2 to 8) can be used. Examples of such organic acids include monocarboxylic acids [aliphatic carboxylic acids (such as C _1-10 aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid and caprylic acid), and alicyclic carboxylic acids (cyclohexane). Carboxylic acids, etc.), aromatic carboxylic acids (benzoic acid, C _7-12 aromatic carboxylic acids such as naphthoic acid), etc.], polycarboxylic acids [aliphatic saturated polycarboxylic acids (oxalic acid, malonic acid, succinic acid, C _2-10 aliphatic saturated polycarboxylic acid such as glutaric acid, adipic acid and sebacic acid), aliphatic unsaturated polycarboxylic acid (C _4-10 aliphatic such as maleic acid, fumaric acid, itaconic acid and sorbic acid) unsaturated polycarboxylic acids, etc.), alicyclic polycarboxylic acid (1,4-cyclohexanedicarboxylic acid, C _8-10 alicyclic such as tetrahydrophthalic acid Poly such as carboxylic acid), aromatic polycarboxylic acids (e.g., phthalic acid, such as C _8-12 aromatic polycarboxylic acid such as trimellitic acid), etc.], oxycarboxylic acids [aliphatic hydroxycarboxylic acid (glycolic acid, lactic acid, oxy C _2-10 aliphatic oxycarboxylic acids such as butyric acid and glyceric acid), aromatic oxycarboxylic acids (such as C _7-12 aromatic oxycarboxylic acids such as salicylic acid, oxybenzoic acid and gallic acid)], oxypoly Carboxylic acids [aliphatic oxypolycarboxylic acids (such as C _2-10 aliphatic _{oxypolycarboxylic} acids such as tartaric acid, citric acid and malic acid)], heterocyclic carboxylic acids (such as pyridinecarboxylic acid), and aromatic sulfonic acids (C _6-10 aromatic sulfonic acid such as benzenesulfonic acid and toluenesulfonic acid). These organic acids may be anhydrides, hydrates and the like. These organic acids can be used alone or in combination of two or more.

Among these organic acids, monocarboxylic acids such as aliphatic carboxylic acids (acetic acid, propionic acid, etc.), aliphatic saturated polycarboxylic acids (oxalic acid, malonic acid, etc.) and aliphatic unsaturated polycarboxylic acids (maleic acid, Fumaric acid etc.) polycarboxylic acids, aliphatic oxycarboxylic acids (glycolic acid, lactic acid etc.) oxycarboxylic acids, aliphatic oxypolycarboxylic acids (citric acid, malic acid etc.) oxypolycarboxylic acids, especially C _3-8 aliphatic oxypolycarboxylic acids such as citric acid or hydrates thereof are preferred.

  The proportion of the organic acid is, for example, 0.005 to 0.5 parts by weight, preferably 0.01 to 0.1 parts by weight, and more preferably 0.02 to 0.05 parts by weight with respect to 100 parts by weight of the cellulose ester. About a part. Moreover, the ratio of the organic acid is, for example, 0.001 to 0.4 parts by weight, preferably 0.005 to 0.08 parts by weight, with respect to 100 parts by weight of the total amount of the cellulose ester and the non-cellulosic thermoplastic resin. More preferably, it is about 0.01-0.04 weight part. When an organic acid is used, coloring of the molded product can be suppressed, and deterioration of physical properties due to decomposition of the cellulose ester can also be suppressed.

(Thioether compound)
Thioether compounds are used to prevent oxidation (and coloration), such as dilauryl-3,3'-thiodibropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3 '. -Thiodipropionate, dipalmityl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, palmitylstearyl-3, Examples thereof include dialkylthiodicarboxylates such as 3'-thiodipropionate. These thioether compounds can be used alone or in combination of two or more.

Among these thioether compounds, di-C _10- such as dilauryl-3,3′-thiodibropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate. Preferred are ₂₂ alkyl-3,3′-thiodiC _2-6 aliphatic carboxylate.

  The ratio of the thioether compound is, for example, 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 1 part by weight (particularly 0.2 parts by weight) with respect to 100 parts by weight of the cellulose ester. About 0.5 part by weight).

  The ratio of the thioether compound is, for example, 0.005 to 4 parts by weight, preferably 0.01 to 2 parts by weight, and more preferably 0 to 100 parts by weight of the total amount of the cellulose ester and the non-cellulosic thermoplastic resin. It may be about 0.05 to 0.8 part by weight (particularly 0.1 to 0.4 part by weight).

(Phosphite compound)
Phosphite compounds are used to improve thermal stability, for example, triaryl phosphites (triphenyl phosphite, tricresyl phosphite, trixylenyl phosphite, trinaphthyl phosphite, etc.), diarylalkyls Phosphites (such as diaryl C _1-18 alkyl phosphites such as diphenylisooctyl phosphite, diphenyl decyl phosphite), aryl dialkyl phosphites (such as aryl C _1-18 dialkyl phosphites such as phenyl diisooctyl phosphite), Trialkyl phosphites (trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, etc. Birds, etc. _{C 1-18} alkyl phosphites), and _{di-C 1-18} alkyl phosphites such as dialkyl phosphite (dilauryl phosphite) phosphite containing an alkyl aryl units [tris (2, 4-t-butylphenyl ) Phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, dinonylphenyl-o-biphenyl phosphite, etc., tris (C _1-18 alkyl-aryl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite etc.], aliphatic carboxylic acid phosphite (C _1-18 aliphatic carboxylic acid phosphite such as tristearyl phosphite), alkylene oxide Phosphite containing units (polydipropylene glycol) Urnonylphenyl phosphate, tetraphenyldipropylene glycol phosphite, etc.), phosphites containing cyclic neopentane units [cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbis (2,4 -Di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite etc.], diphosphites (diisodecylpentaerythritol diphosphite, di Dodecyl pentaerythritol diphosphite, 4,4'-isopropylidenediphenyl didodecyl diphosphite, etc.), triphosphites [heptasis dipropylene glycol triphosphite, hexa-tridecyl-1 , 1,3-tri (3-t-butyl-6-methyl-4-oxyphenyl) -3-methylpropane triphosphite]. These phosphite compounds can be used alone or in combination of two or more.

Among these phosphite compounds, phosphites containing branched alkyl groups, such as tri-C _6-18 alkyl phosphites (such as triisodecyl phosphite), branched C _3-6 alkyl groups (such as t-butyl group) ) -Containing phosphites [tris (2,4-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, etc.] and the like.

  The ratio of the phosphite compound is, for example, 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 1 part by weight (particularly, based on 100 parts by weight of the cellulose ester. 0.3 to 0.8 parts by weight).

  The ratio of the phosphite compound is, for example, 0.005 to 4 parts by weight, preferably 0.01 to 2 parts by weight, more preferably 100 parts by weight of the cellulose ester and non-cellulose ester thermoplastic resin. May be about 0.05 to 1 part by weight (particularly 0.1 to 0.7 part by weight).

[Deodorants]
The resin composition of the present invention may further contain a deodorant (or deodorant component). The deodorizer is not particularly limited as long as it can deodorize (or deodorize) the odor generated from the resin composition. In particular, the odor of at least acetic acid is often deodorized.

  Typical deodorants include inorganic deodorants and carbodiimide compounds. Deodorants may be used alone or in combination of two or more. The inorganic deodorant only needs to deodorize at least, and may be an inorganic substance that acts as a deodorant and a filler.

(Inorganic deodorant)
The inorganic deodorant can be appropriately selected according to the use of the resin composition (for example, presence or absence of coloring), and minerals or derivatives thereof [hydrotalcite compound (hydrotalcite compound) or fired product thereof] , Zeolite, montmorillonite, diatomaceous earth, white clay, barley stone, etc.], metal compound [metal oxide or metal hydroxide, metal phosphate (tetravalent metal phosphate, etc.), metal sulfate (ferrous sulfate, etc.) ), Metal inorganic acid salts such as metal carbonates (such as zinc carbonate)], charcoal (such as activated carbon, charcoal, bamboo charcoal) and the like.

  Examples of the metal oxide or metal hydroxide include transition metal oxide or transition metal hydroxide [titanium oxide or hydroxide (such as titanium oxide), zirconium oxide or hydroxide (hydrated zirconium oxide, Periodic Table Group 4 metal oxides or hydroxides such as zirconium oxide; Periodic Table Group 8 metal oxides or hydroxides such as iron oxides or hydroxides (iron oxide, iron hydroxide, etc.); Periodic Table Group 11 metal oxides or hydroxides such as zinc oxide or hydroxide (such as zinc oxide)], aluminum oxides or hydroxides [alumina (such as activated alumina)], silicon oxide or Hydroxides (such as silica gel), calcium oxides or hydroxides (such as hydroxyapatite) are included. These inorganic deodorants may be used alone or in combination of two or more.

  Among these inorganic deodorants, a deodorant having high affinity for the acid-modified resin described later, such as a hydrotalcite compound (hydrotalcite compound) or a fired product thereof, zirconium oxide or hydroxide ( Hydrated zirconium oxide, zirconium oxide) and metal phosphates (tetravalent metal phosphate, etc.) are preferred.

  The hydrotalcite compound is a compound (hydrotalcite, hydrotalcite-like compound) having a hydrotalcite structure represented by the following formula (6).

^{_{M 1 (1-x) M}} 2 x (OH) 2 A n- (x / n) · mH 2 O (6)
(Wherein, ^{M 1} is a divalent metal, ^{M 2} is a trivalent metal, x is a number greater than 0 and 0.5 or ^{less, A n-is} the n-valent anion, m is a positive number.)
In the above formula (6), examples of the divalent metal (or metal ion) represented by M ¹ include magnesium (Mg ²⁺ ) and zinc (Zn ²⁺ ), and the trivalent metal represented by M ² ( Examples of the metal ion include aluminum (Al ³⁺ ) and rhodium (Rh ³⁺ ). As the anion represented by A ^n-, carbonate ion, sulfate ion, nitrate ion, (such as chloride ion) halogen ion, and the like.

  The calcined hydrotalcite is a compound obtained by calcining a hydrotalcite compound at about 500 ° C. or more and releasing hydroxyl groups, water and A (or components corresponding to A, carbonate radicals, etc.). .

A preferred hydrotalcite compound includes a magnesium-aluminum hydrotalcite compound (or a fired product thereof) in which M ¹ is magnesium and M ² is aluminum.

  The hydrated zirconium oxide may be crystalline or amorphous, and is a compound having the same meaning as zirconium oxyhydroxide, zirconium hydroxide, hydrous zirconium oxide and zirconium oxide hydrate. Hydrated zirconium oxide is a known compound, and its production method is not particularly limited, but a preferred method is a wet method. In such a wet method, hydrated zirconium oxide can be easily obtained by hydrolyzing a zirconium-containing aqueous solution such as a zirconium oxychloride aqueous solution with water or an alkaline aqueous solution.

  Zirconium oxide may be either crystalline or amorphous, but amorphous is preferable in order to exhibit high deodorizing properties. In the present invention, as the zirconium oxide, a commercially available product may be used as it is, or a fired product (anhydride) obtained by firing the hydrated zirconium oxide may be used. A preferred firing temperature for firing the hydrated zirconium oxide to obtain amorphous zirconium oxide may be about 150 to 350 ° C.

  Such hydrotalcite compounds, hydrated zirconium oxide and zirconium oxide exhibit excellent deodorizing properties against lower fatty acids such as acetic acid, valeric acid and butyric acid, and aldehydes such as formaldehyde and acetaldehyde. In particular, the production method is not limited.

  Examples of the metal phosphate include a tetravalent metal phosphate that is insoluble or hardly soluble in water represented by the following formula (7).

H _a M ³ _b M ⁴ _c M ⁵ _d O _e (PO ₄ ) _f · nH ₂ O (7)
(Wherein M ³ is a monovalent metal, M ⁴ is a divalent metal, M ⁵ is a tetravalent metal, a, b, c, e and n are 0 or a positive number, b And c are not 0, and d and f are positive numbers and satisfy a + b + 2c + 4d = 2e + 3f.)
In the above formula (7), examples of the tetravalent metal (tetravalent metal ion) represented by M ⁵ include zirconium, titanium, tin, cerium, hafnium and the like, and zirconium and titanium are particularly preferable. Examples of the monovalent metal represented by M ³ and / or the divalent metal represented by M ⁴ include lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, copper, iron, zinc, nickel, Examples include manganese and cobalt. Of these, sodium, potassium, copper, zinc and manganese are preferred. In a preferred embodiment, the coefficients a, b, c, d, e, and f satisfy either of the following formulas (provided that a, b, and c may be 0, but b and c are Neither is 0).

a + b + c = 1, d = 1, e = 1, f = 1
a + b + c = 1, d = 2, e = 0, f = 3
a + b + c = 2, d = 1, e = 0, f = 2.

  A particularly preferred embodiment of the tetravalent metal phosphate is a coefficient satisfying the formula (a + b + c = 2, d = 1, e = 0, f = 2) (where a, b and c may be 0, b A crystalline compound having a γ-type layered structure.

  Such metal phosphates exhibit excellent deodorizing properties for sulfur-containing gases such as hydrogen sulfide and methyl mercaptan in addition to lower fatty acids such as acetic acid, valeric acid, and butyric acid.

  Of these inorganic deodorants (deodorants with high affinity for acid-modified resins), hydrotalcite compounds or calcined products thereof, hydrated zirconium oxide, and zirconium oxide are preferred. Zirconium is preferred. Such an inorganic deodorant has high compatibility with the cellulose ester, and can efficiently enhance the deodorizing ability.

  The inorganic deodorant may be used alone or in combination of two or more.

  The deodorant may be a deodorant described in JP-A-10-279817. Zirconium compounds (hydrated zirconium oxide, zirconium oxide) can be obtained from Toagosei Co., Ltd. under the trade names “NS-70” and “NS-80E” of Kesmon (registered trademark).

  The shape (or form) of the inorganic deodorant is not particularly limited, but usually it is often granular (or powder). The average particle diameter of the inorganic deodorant (powdered deodorant) may be, for example, 0.01 to 20 μm, preferably 0.02 to 10 μm, and more preferably about 0.05 to 5 μm. If the average particle size is too small (for example, less than 0.01 μm), reaggregation tends to occur and handling is difficult. Moreover, when an average particle diameter is too large (for example, larger than 20 micrometers), there exists a possibility that the dispersibility with respect to resin (cellulose ester) may fall.

(Carbodiimide compound)
The carbodiimide compound may be a compound having at least one carbodiimide group [—N═C═N—] in the molecule, and may be monocarbodiimides or polycarbodiimides.

  The monocarbodiimides include compounds having one carbodiimide group in the molecule, such as compounds represented by the following formula (A).

R ¹ —N═C═N—R ² (A)
(In formula, R < ¹ > and R < ² > shows the hydrocarbon group which may have a substituent.)
Examples of the hydrocarbon group represented by R ¹ and R ² include aliphatic hydrocarbon groups [for example, alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group). C _1-30 alkyl group such as octyl group and octadecyl group, preferably C _1-25 alkyl group, more preferably C _1-20 alkyl group, especially C _1-10 alkyl group)], etc. A hydrogen group [eg, a cycloalkyl group (eg, a C _4-10 cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 Cycloalkyl group and the like), cycloalkenyl group (for example, C _4-10 cycloalkenyl such as cyclohexenyl group) Group, preferably a C _5-8 cycloalkenyl group, more preferably a C _5-6 cycloalkenyl group, etc.], an aromatic hydrocarbon group [eg, C _6-15 aryl such as an aryl group (phenyl group, naphthyl group, etc.) Group, preferably C _6-10 aryl group, more preferably C _6-8 aryl group), aralkyl group (C _6-10 aryl-C _1-4 alkyl group such as benzyl group, phenethyl group, etc.)] and the like. Can be mentioned.

The hydrocarbon group may have a substituent. Examples of the substituent include the hydrocarbon group (alkyl group, cycloalkyl group, aryl group and the like), acyl group (C _1-6 acyl group such as acetyl group), alkoxycarbonyl group (C methoxycarbonyl group and the like). _1-4 alkoxycarbonyl group, etc.), amino group, substituted amino group [for example, N, N-dialkylamino group (for example, N, N-diC _1-6 alkylamino group such as N, N-dimethylamino group, Preferably N, N-diC _1-4 alkylamino group)], hydroxyl group, nitro group, halogen atom (fluorine atom, chlorine atom, etc.), cyano group, ketone group [or oxo group (the hydrocarbon group is And a carbon atom constituting a carbon-oxygen double-bonded oxygen atom)]. The substituents may be substituted singly or in combination of two or more.

In the formula (A), R ¹ and R ² may be the same group or different groups.

  Representative monocarbodiimide compounds include aliphatic monocarbodiimides, alicyclic monocarbodiimides, aromatic monocarbodiimides, and the like.

Aliphatic monocarbodiimides include, for example, dialkylcarbodiimides [for example, 1,3-dimethylcarbodiimide, 1,3-diisopropylcarbodiimide, 1-isopropyl-3-t-butylcarbodiimide, 1,3-dihexylcarbodiimide, 1, Di-C ₁ which may have a substituent such as 3-dioctylcarbodiimide, 1-isopropyl-3-dodecylcarbodiimide, 1,3-dioctyldecylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide _-30 alkyl carbodiimide (preferably di-C _1-25 alkyl carbodiimide, more preferably di-C _1-20 alkyl carbodiimide) and the like.

Examples of alicyclic monocarbodiimides include dicycloalkyl carbodiimides [for example, di-C _4-10 cycloalkyl carbodiimide (preferably di-C ₅ which may have a substituent such as 1,3-dicyclohexylcarbodiimide). _-8 cycloalkyl carbodiimide, more preferably diC _5-6 cycloalkyl carbodiimide) and the like.

Aromatic monocarbodiimides include, for example, diaryl carbodiimides [for example, N, N′-diphenylcarbodiimide, N, N′-ditolylcarbodiimide (N, N′-dio-tolylcarbodiimide, N, N′-di). p-tolylcarbodiimide), N, N′-bis (2,6-dimethylphenyl) carbodiimide, N, N′-bis (2,4,6-trimethylphenyl) carbodiimide, N, N′-bis (2, 6-diethylphenyl) carbodiimide, N, N′-bis (2-ethyl-6-isopropylphenyl) carbodiimide, N, N′-bis (dipropylphenyl) carbodiimide, N, N′-bis (diisopropylphenyl) carbodiimide ( N, N′-bis (2,6-diisopropylphenyl) carbodiimide, etc.), N, N′-bis (2,4 6-triisopropylphenyl) carbodiimide, N, N′-bis (2-isobutyl-6-isopropylphenyl) carbodiimide, N, N′-bis (2,6-dit-butylphenyl) carbodiimide, N, N′- Bis (2,4,6-triisobutylphenyl) carbodiimide, N-phenyl-N′-tolylcarbodiimide, N, N′-di-β-naphthylcarbodiimide, N, N′-di (nitrophenyl) carbodiimide (N, N'-di (p-nitrophenyl) carbodiimide), N, N'-di (aminophenyl) carbodiimide (N, N'-di (p-aminophenyl) carbodiimide, etc.), N, N'-di (hydroxy) Phenyl) carbodiimide (N, N′-di (p-hydroxyphenyl) carbodiimide, etc.) _6-15 arylcarbodiimide (preferably diC _6-10 arylcarbodiimide, more preferably diC _6-8 arylcarbodiimide), benzylisopropylcarbodiimide, etc.], aromatic monocarbodiimides having an alicyclic hydrocarbon group [for example, Arylcycloalkyl carbodiimides (e.g. C _6-15 aryl-C _4-10 cycloalkyl carbodiimide _optionally having substituents such as N-tolyl-N′-cyclohexylcarbodiimide, preferably C _6-10 aryl- C _5-8 cycloalkylcarbodiimide, more preferably C _6-8 aryl-C _5-6 cycloalkylcarbodiimide) and the like.

  The polycarbodiimides include compounds having at least two carbodiimide groups in the molecule, for example, compounds having a structural unit (repeating unit) represented by the following formula (B).

− (N = C = N−R ³ ) _n − (B)
(In the formula, R ³ is a divalent hydrocarbon group which may have a substituent, and n represents an integer of 2 or more.)
In the above formula (B), as the group R ³ , a divalent group corresponding to the hydrocarbon group (monovalent hydrocarbon group) represented by R ¹ and R ² in the above examples, for example, an aliphatic hydrocarbon Group [for example, an alkylene group or an alkylidene group (a C _1-30 alkylene group such as a methylene group, an ethylene group, a tetramethylene group, a hexamethylene group, preferably a C _1-25 alkylene group, more preferably a C _1-20 alkylene group etc.), etc.], alicyclic hydrocarbon group {e.g., a cycloalkylene group (e.g., C _4-10 cycloalkylene group such as cyclohexylene group, preferably a C _5-8 cycloalkylene group), a cycloalkenylene group (e.g., C _5-10 cycloalkenylene group such as cyclohexenylene group), alkyl cycloalkane (e.g., methylcyclohexane) Response to the divalent group (e.g., methylene - _{C 1-10} alkylene _{-C 4-10} cycloalkylene group such as cyclohexylene group, such as preferably a _{C 1-6} alkylene _{C 5-8} cycloalkylene group), dicycloalkyl alkanes A divalent group corresponding to (for example, a diC _4-10 cycloalkyl-C _1-10 alkane-diyl group such as a dicyclohexylmethane-4,4′-diyl group, preferably a diC _5-8 cycloalkyl-C _{1 -6} alkane-diyl group, more preferably diC _5-6 cycloalkyl-C _1-4 alkane-diyl group etc.}}, aromatic hydrocarbon group {arylene group [phenylene group (1,4-phenylene group etc.) ), A C _6-15 arylene group such as a naphthylene group, preferably a C _6-10 arylene group, more preferably a C _6-8 arylene group Etc.], an araliphatic hydrocarbon group [for example, a divalent group corresponding to a diarylalkane (a diC _6-15 aryl-C _1-10 alkane such as a diphenylmethane-4,4′-diyl group, preferably diC _{6 -10} aryl-C _1-6 alkane, more preferably diC _6-8 aryl-C _1-4 alkane and the like, and divalent groups corresponding to dialkylarenes (eg, diC such as α, α'-xylylene group) _1-10 alkyl-C _6-15 arene-diyl group, preferably diC _1-6 alkyl-C _6-10 arene-diyl group, more preferably di-C _1-4 alkyl-C _6-8 arene-diyl group Etc.) etc.}.

Furthermore, the radicals R ³ may have a substituent, and examples of such substituents, wherein examples of substituents the same substituent (e.g., alkyl group, an aryl group) can be exemplified.

In the formula (B), the groups R ³ may be the same or different for each repeating unit. That is, the polycarbodiimide compound may be a homopolymer or a copolymer using a different monomer (such as a diisocyanate compound) as a raw material.

  In the formula (B), the number of repeating units n may be 2 or more (for example, about 2 to 100), for example, 3 to 50, preferably 4 to 40, more preferably 5 to 30 (for example, 8). ~ 20) degree may be sufficient. The structure of the polycarbodiimides may be a chain (straight chain or branched chain), a network, or the like, and may usually be a chain.

  Representative polycarbodiimides include, for example, aliphatic polycarbodiimides, alicyclic polycarbodiimides, aromatic polycarbodiimides, and the like.

Aliphatic polycarbodiimides include, for example, polyalkylene carbodiimides [eg poly (C _2-30 alkylene carbodiimides) such as polyhexamethylene carbodiimide, poly (3-methylhexamethylene carbodiimide), preferably poly (C _2-25 Alkylene carbodiimide), more preferably poly (C _2-20 alkylene carbodiimide), especially poly (C _2-10 alkylene carbodiimide)] and the like.

Examples of the alicyclic polycarbodiimides include polydicycloalkylalkanecarbodiimides [eg, poly (diC _4-10 cycloalkyl-C _1-10 alkanecarbodiimide) such as poly (4,4′-dicyclohexylmethanecarbodiimide), Preferably, poly (diC _5-8 cycloalkyl-C _1-6 alkanecarbodiimide), more preferably poly (diC _5-6 cycloalkyl-C _1-4 alkanecarbodiimide), etc.] are included.

Aromatic polycarbodiimides include, for example, polyarylene carbodiimide [for example, poly m-phenylene carbodiimide, poly p-phenylene carbodiimide, polytolylene carbodiimide, poly (diisopropylphenylene carbodiimide), poly (methyldiisopropylphenylene carbodiimide), poly ( Poly (C _6-15 arylene carbodiimide) such as triisopropylphenylene carbodiimide), preferably poly (C _6-10 arylene carbodiimide), more preferably poly (C _6-8 arylene carbodiimide)], polydiarylalkanecarbodiimides [eg , poly (4,4'-diphenylmethane carbodiimide) poly (di _{C 6-15} aryl _{-C 1-10} alkane carbodiimide), such as, preferred Ku poly _{(di-C 6-10} aryl _{-C 1-6} alkane carbodiimide), more preferably contains a poly _{(di-C 6-8} aryl _{-C 1-4} alkane carbodiimide), etc.].

The end of the polycarbodiimide (the end of the compound represented by the formula (B)) is not particularly limited, and may be a group derived from a raw material (particularly, an isocyanate group) or the like. Compounds having reactive groups such as amines (primary or secondary amines), carboxylic acids or acid anhydrides, alcohols [eg alkanols (eg alkanols such as methanol), glycols (ethylene Glycols, diethylene glycols, (poly) alkylene glycols such as polyethylene glycols, etc.)], monoisocyanates [eg, alkyl isocyanates (C _1-20 alkyl isocyanates such as ethyl isocyanate), cycloalkyl isocyanates (C ₅ such as cyclohexyl isocyanate, etc.) _-1 Cycloalkyl isocyanates, etc.), etc. C _6-10 aryl isocyanates and aryl isocyanates (phenyl isocyanate)] may be blocked by using a. These compounds having a group reactive with an isocyanate group may be used alone or in combination of two or more.

  Carbodiimide compounds (monocarbodiimides, polycarbodiimides) may form a salt (for example, hydrochloride).

  Such a carbodiimide compound may be a commercially available product, or can be synthesized by a conventional method using isocyanates (monoisocyanates, diisocyanates, etc.). For example, monocarbodiimides can be obtained by reacting (decarboxylating) monoisocyanates, and polycarbodiimides can be polyisocyanates (particularly diisocyanates) or multimers thereof (dimers, trimers). Etc.) can be obtained by reaction (decarboxylation). The reaction of isocyanates may be carried out in the absence of a catalyst, and may be a carbodiimide production catalyst [for example, phospholine compound, phospholine oxide compound (for example, 1-methyl-1-oxophospholine, 1-ethyl-3 -Phosphorus compounds such as -methyl-3-phospholine-1-oxide) and phosphorous sulfide compounds].

The monoisocyanates, mono-isocyanates corresponding to the groups R ¹ and R ^2, for example, aliphatic monoisocyanate (e.g., alkyl isocyanates (e.g., C _1-30 alkyl isocyanates such as methyl isocyanate), alicyclic Examples thereof include monoisocyanates (for example, C _4-10 cycloalkyl isocyanate such as cyclohexyl isocyanate), aromatic monoisocyanates (for example, C _6-15 aryl isocyanate such as phenyl isocyanate), and the like.

Examples of the diisocyanates include diisocyanates corresponding to the group R ³ such as aliphatic diisocyanate [alkane diisocyanate (for example, C _2-30 alkane diisocyanate such as trimethylene diisocyanate)], alicyclic diisocyanate {for example, cyclohexane. Alkane diisocyanates (eg C _4-10 cycloalkane diisocyanates such as 1,4-cyclohexane diisocyanate), cycloaliphatic diisocyanates [eg isocyanatoalkyl-isocyanatocycloalkanes (eg 3-isocyanatomethyl-3,5 , 5-isocyanato _{C 1-10} alkyl such as trimethylcyclohexyl isocyanate - isocyanato _{C 4-10} cycloalkane), diisocyanato alkyl cycloalkane (e.g. If, 1,4-bis (isocyanatomethyl) di (isocyanato _{C 1-10 alkyl)} such as cyclohexane _{C 4-10} cycloalkane), diisocyanato cycloalkyl alkanes (e.g., 4,4'-methylenebis (cyclohexyl isocyanate ), Di (isocyanato C _4-10 cycloalkyl) C _1-10 alkane), etc.] such as 4,4′-methylenebis (2-ethyl-6-methylcyclohexyl isocyanate), etc.], aromatic diisocyanate {eg Natoarenes [for example, diisocyanato C ₆ such as p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,6-diisopropylbenzene diisocyanate, 1,3,5-triisopropyl-2,4-diisocyanatobenzene, etc. _-15 arene], Kaoru Aliphatic diisocyanates [e.g., diisocyanato alkyl arene (e.g., xylylene diisocyanate, di tetramethyl xylylene diisocyanate (isocyanato _{C 1-10 alkyl) C 6-15} arene), diisocyanato aryl alkanes (e.g., 4 , 4′-diphenylmethane diisocyanate and the like (di (isocyanato C _6-15 aryl) C _1-10 alkane) and the like]. Diisocyanates may be used alone or in combination of two or more.

  Preferred carbodiimide compounds include aliphatic monocarbodiimides, alicyclic monocarbodiimides, aromatic monocarbodiimides, aliphatic polycarbodiimides, alicyclic polycarbodiimides, aromatic polycarbodiimides and the like.

  In particular, from the viewpoint of safety (or toxicity), polycarbodiimides (for example, at least one selected from aliphatic polycarbodiimides, alicyclic polycarbodiimides, and aromatic polycarbodiimides) are preferably used. May be.

  The carbodiimide compounds may be used alone or in combination of two or more.

  The ratio of the deodorant can be selected from the range of about 0.01 to 20 parts by weight with respect to 100 parts by weight of the cellulose ester, for example, 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight, More preferably, it may be about 0.3 to 5 parts by weight (for example, 0.4 to 3 parts by weight).

  In particular, the proportion of the inorganic deodorant can be selected from a range of about 0.01 to 10 parts by weight with respect to 100 parts by weight of the cellulose ester, and is usually 0.05 to 5 parts by weight, preferably 0.1 to 0.1 parts by weight. It may be about 5 parts by weight, more preferably about 0.2 to 3 parts by weight. In particular, when an inorganic deodorant (especially an intangible deodorant) and an acid-modified resin described later are combined, 0.1 to 1.5 parts by weight, preferably 0.8. Even a small amount of a deodorant of about 2 to 1.2 parts by weight, more preferably about 0.3 to 1 part by weight, can deodorize the cellulose ester with high deodorizing ability.

  In particular, when a carbodiimide compound is used as a deodorant, the proportion of the carbodiimide compound can be selected from a range of about 0.01 to 10 parts by weight with respect to 100 parts by weight of the cellulose ester. It may be about 5 parts by weight, preferably about 0.1 to 4 parts by weight, and more preferably about 0.2 to 3 parts by weight.

  In addition, the ratio of a deodorizer can be selected from the range of about 0.01-20 weight part with respect to 100 weight part of total amounts of a cellulose ester and a non-cellulose ester type thermoplastic resin, for example, 0.03-10 weight Part, preferably 0.05 to 5 parts by weight, more preferably about 0.1 to 3 parts by weight (for example, 0.3 to 2 parts by weight).

[Acid-modified resin]
The resin composition of the present invention may further contain an acid-modified resin. If an acid-modified resin is added to the resin composition, the acid-modified resin may act as a lubricant (external lubricant), or an obstacle in melt-kneading [for example, damage to the cylinder, friction noise in the kneader (such as screw friction noise)] Can be efficiently prevented. In addition, by using the deodorant and combining the deodorant and the acid-modified resin, generation of acid derived from cellulose ester (especially organic acid such as acetic acid) can be suppressed at a high level, and the resin composition Unpleasant odor (organic acid odor such as acetic acid) from the product (and its molded product) can be remarkably suppressed or reduced. In particular, when a deodorant (zirconium oxide, hydrated zirconium oxide, etc.) having high affinity for the acid-modified resin is combined with the acid-modified resin, the acid-modified resin becomes dispersible (or compatible) with the deodorant. It is possible to efficiently suppress the off-flavor.

  The acid-modified resin is modified with an acid group (such as a carboxyl group or an acid anhydride group) or a derivative group thereof (such as an amide group, an imide group, or an ester group). Examples of the resin constituting the acid-modified resin include conventional thermoplastic resins such as olefin resins, vinyl resins (polyvinyl acetate, polyvinyl alcohol, etc.), styrene resins [polystyrene, acrylonitrile-styrene copolymers, acrylonitrile- Butadiene-styrene block copolymers], halogen-containing vinyl resins (polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, etc.), acrylic resins (polymethyl methacrylate, methyl methacrylate-styrene copolymers, etc.) Vinyl polymer resins such as polyester resins (polyalkylene arylates such as polyethylene terephthalate and polybutylene terephthalate, or copolyesters thereof), polyamide resins (polyamide 6, polyamide 66, polyamide 610, polyamido) 612, polyamide 11 and polyamide 12), and the like condensation resins such.

Examples of olefin resins include α-olefins (α-C _2-10 olefins) such as ethylene, propylene, butene, and methylpentene-1, or copolymers, and copolymers of α-olefins and copolymerizable monomers. Polymers can be used. Examples of such olefin resins include polyethylene resins (polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic ester copolymer). And ionomer resins), polypropylene resins (polypropylene, propylene-ethylene random copolymers, propylene-ethylene block copolymers, propylene-butene copolymers, etc.). As the olefin resin, a polypropylene resin containing at least a propylene unit is preferable.

  The modification can be performed by a conventional method. For example, in a vinyl polymerization resin, a method of copolymerizing (random, block or graft copolymerization) a corresponding vinyl monomer and a compound (monomer) having an acid group (or an inductive group thereof), vinyl An acid group may be introduced (or modified with an acid group) by a method such as graft polymerization of a compound having an acid group to a polymerization resin. In the condensation resin, an acid group may be introduced (or modified with an acid group) by graft polymerization of a compound (monomer) having an acid group onto the resin (condensation resin).

Such compounds (or monomers) having an acid group include unsaturated carboxylic acids such as unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angelic acid, etc. C _3-8. Alkene carboxylic acids, preferably C _3-6 alkene carboxylic acids; sorbic acid, etc.), alkene dicarboxylic acids (C _4-10 alkene dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, preferably C _4-8 alkene dicarboxylic acid, etc.), acid anhydrides (maleic anhydride, itaconic anhydride, citraconic anhydride, etc.) corresponding to these unsaturated carboxylic acids, and derivatives of these compounds (alkali or alkaline earth) Metal salts such as metals, amides, imides, esters, etc.) are also included. Of these, unsaturated dicarboxylic acids or anhydrides thereof, particularly unsaturated dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride are preferred. The compounds having an acid group may be used alone or in combination of two or more.

  Preferred acid-modified resins include acid-modified olefin resins (olefin resins modified with acid groups), particularly acid-modified polypropylene resins (polypropylene, etc.) modified with maleic anhydride, itaconic anhydride, etc. It is. Such an acid-modified olefin resin is excellent in compatibility with the cellulose ester.

  The acid-modified resins may be used alone or in combination of two or more.

  The number average molecular weight of the acid-modified resin may be, for example, about 5,000 to 100,000, preferably about 8,000 to 75,000, and is usually 10,000 or more (for example, 10,000 to 70,000, preferably 15,000 to 70,000, more preferably 20,000 to 50,000). ) Degree.

  In the acid-modified resin, the ratio of the acid group (or the copolymerization ratio of the compound having an acid group) is, for example, 0.5 to 30% by weight, preferably 1 to 20% by weight, based on the acid-modified resin. Preferably, it may be about 3 to 15% by weight.

  The ratio of the acid-modified resin can be selected from the range of about 0.05 to 20 parts by weight with respect to 100 parts by weight of the cellulose ester, for example, 0.1 to 15 parts by weight, preferably 0.2 to 10 parts by weight ( For example, it may be about 0.3 to 8 parts by weight), more preferably about 0.4 to 5 parts by weight (for example, 0.5 to 3 parts by weight).

  The ratio of the acid-modified resin is, for example, 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 100 parts by weight of the total amount of cellulose ester and non-cellulose ester thermoplastic resin. May be about 0.2 to 4 parts by weight (for example, 0.3 to 2 parts by weight).

  Depending on the application, the resin composition of the present invention may contain conventional additives such as other stabilizers (for example, antioxidants, ultraviolet absorbers, heat stabilizers, light-resistant stabilizers), colorants (dyes). , Pigments, etc.), flame retardants, antistatic agents, lubricants, antiblocking agents, dispersants, fluidizing agents, anti-dripping agents, antibacterial agents and the like. These additives can be used alone or in combination of two or more.

  In the resin composition of the present invention, the cellulose ester and the non-cellulose ester-based thermoplastic resin may be compatible with each other, and usually may be phase-separated from each other. In the resin composition having such a phase separation structure, (i) one component (for example, cellulose ester) forms a matrix (or continuous phase), and the other component (for example, non-cellulose ester thermoplastic resin). May be a resin composition in which a dispersed phase is formed, or (ii) a resin composition having a bicontinuous structure in which both components form a continuous phase.

  The resin composition (i) may be a polymer blend having a sea-island structure in which a dispersed phase is dispersed independently of a continuous phase, and the dispersed phase has a particle shape, an ellipsoidal shape, a spherical shape, a rod shape, a fiber It may be a shape. The average particle size of the dispersed phase may be, for example, about 0.1 to 1000 μm, preferably about 1 to 750 μm, and more preferably about 10 to 500 μm.

  The resin composition of the present invention can be prepared by a conventional method. For example, each component [cellulose ester, non-cellulose ester-based thermoplastic resin, plasticizer, bleedout inhibitor, and others as necessary. And the like (for example, deodorant, filler, stabilizer, etc.) may be mixed by dry or wet mixing using a mixer such as a tumbler mixer, a Henschel mixer, a ribbon mixer, or a kneader.

  Furthermore, after premixing with the mixer, it may be prepared by mixing with an extruder such as a single-screw or twin-screw extruder to prepare pellets, or by melt-kneading with a kneader such as a heating roll or a Banbury mixer. . The temperature of melt kneading can be selected according to the melting point of each component such as a plasticizer, and may be, for example, about 100 to 250 ° C, preferably about 110 to 240 ° C, and more preferably about 120 to 240 ° C.

  The resin composition thus obtained can be molded into various molded products by injection molding, extrusion molding, vacuum molding, profile molding, foam molding, injection press, press molding, blow molding, gas injection molding, and the like. . Among these molding methods, it is preferable to use in a molding method including a melting step at a high temperature. Particularly, since the fluidity, rigidity and dimensional accuracy are high, it is preferable to use for injection molding. Furthermore, since the resin composition has the above characteristics, the occurrence of burrs is suppressed even if it is thin (for example, about 0.5 to 3 mm) and molded by injection molding. The cylinder temperature in the injection molding is not particularly limited, and is 100 to 250 ° C. (for example, 100 to 220 ° C.), preferably 120 to 240 ° C. (for example, 120 to 200 ° C.), more preferably 130 to 230 ° C. (for example, 130 to 180 ° C.). The mold temperature is not particularly limited, and can be selected from a range of about 30 to 150 ° C. For example, the mold temperature may be about 40 to 120 ° C, preferably about 45 to 110 ° C (for example, 50 to 100 ° C). .

  Since the resin composition of the present invention is composed of cellulose ester, the environmental load is small. In addition, the hygroscopicity can be suppressed in spite of being composed of cellulose ester, and the plasticizer bleed-out can be suppressed or prevented at a high level. It is useful for obtaining a molded article excellent in deformation stability under humidity. Moreover, since the resin composition of the present invention is composed of a cellulose ester and a non-cellulose ester thermoplastic resin, the moldability (particularly, injection moldability) is high. Furthermore, the obtained molded product (usually a non-foamed molded product) has few off-flavors and has high flame retardancy and heat resistance. Therefore, the resin composition of the present invention is used in various applications, for example, OA / home appliance field, electrical / electronic field, communication field, sanitary field, transportation vehicle field such as automobile, housing related field such as furniture / building material, miscellaneous goods. It can be suitably used for various parts such as fields, housings, casings, housings, and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Kneading method]
Among the components shown in Table 1, cellulose acetate, TPP, PX200, epoxy compound, so that the frictional heat in the mixer is 70 ° C. or higher using a Henschel mixer (Mitsui Mining Co., Ltd., FM type 20L) The thioether compound and the phosphite were mixed with stirring. The obtained mixture and the remaining components shown in Table 1 were further mixed and supplied to a twin-screw extruder (Ikemi Co., Ltd., PCM30, cylinder temperature: 230 ° C., die temperature: 240 ° C.) and extruded. Pelletized. The obtained pellets were supplied to an injection molding machine (Toshiba Machine Co., Ltd., IS100E), and the cylinder temperature was 230 ° C, the mold temperature was 50 ° C, and the molding cycle was 30 seconds (injection 15 seconds, cooling time 15 seconds). Each test piece was injection molded under the conditions. Table 1 shows the results of the following characteristic evaluation of the obtained test piece.

[Content of each component]
The contents of the components shown in Table 1 are shown below. In Table 1, “part” means “part by weight”.

Cellulose acetate: manufactured by Daicel Chemical Industries, Ltd., trade name “L40”, total average substitution degree 2.5, viscosity average polymerization degree 170, SP value 11
Aromatic polycarbonate (PC): Idemitsu Kosan Co., Ltd., trade name "Iupilon H4000"
Polybutylene terephthalate (PBT): Wintech Polymer Co., Ltd., trade name "Duranex 300FP"
Triphenyl phosphate (TPP): manufactured by Daihachi Chemical Industry Co., Ltd., molecular weight 326, phosphorus content 9.5% by weight, boiling point 399 ° C., specific gravity 1.21, melting point 48.5 ° C., flash point 225 ° C., SP value 10.5
Condensed phosphate ester (PX200): manufactured by Daihachi Chemical Industry Co., Ltd., trade name “PX200”, resorcinol bis (dixylyl phosphate), phosphorus content 8.7% or more [OC ₆ H ₃ (CH ₃ ) ₂ ] _{2 P (O) OC 6 H 4} OP (O) {OC 6 H 3 (CH 3) 2} 2
Phenoxy resin: manufactured by Japan Epoxy Resin Co., Ltd., trade name “Epicoat 1256”
Epoxidized diene block copolymer (ESBS copolymer): manufactured by Daicel Chemical Industries, Ltd., trade name “Epofriend AT501-EA-001”
Deodorant: manufactured by Toagosei Co., Ltd., trade name “Kesmon NS-80E”, zirconium oxide, average particle size 1.3 μm
Unsaturated carboxylic acid-modified resin (modified PP): Sanyo Chemical Co., Ltd., trade name “Yumex 1010”, maleic anhydride 10% modified polypropylene epoxy compound: Daicel Chemical Industries, Ltd., trade name “Celoxide 2021P”, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate thioether compound: manufactured by NOF Corporation, trade name “Antiox L”, dilauryl thiodipropionate Phosphite: Asahi Denka Kogyo Product name “Adeka Stub 3010”, triisodecyl phosphite wollastonite manufactured by Kawatetsu Mining Co., Ltd., product name “PH450S-A100”.

[Water absorption rate]
The water absorption was measured by measuring the weight before and after the obtained molded article (50 mm × 100 mm × 1 mm test piece) was left for 24 hours under the conditions of 90% humidity and 65 ° C.

[Presence of deformation]
A flat plate of 75 mm × 100 mm × 1.5 mm was prepared by injection molding using a mold having four gates located at a distance of 1.3 mm from each corner, and this flat plate was formed with a humidity of 90% and a temperature of 65 ° C. After leaving for 24 hours under the conditions, the presence or absence of deformation was evaluated according to the following criteria.

○… When a three-dimensional measuring device (Tokyo Seimitsu Co., Ltd., XYZAX SP600A) is used to quantify the warp in the long side direction of the test piece, and the deviation from the horizontal (warp) is less than 0.7 mm. Using a three-dimensional measuring device (Tokyo Seimitsu Co., Ltd., XYZAX SP600A) to quantify the warp in the long side direction of the test piece, and the deviation from the horizontal (slave) is 0.7 mm or more.

[Heat deformation temperature (HDT)]
Based on ISO75, the load was measured at 0.45 MPa.

[Bending strength]
It measured according to ISO178 (unit: MPa).

[Bending elastic modulus]
Based on ISO178, the flexural modulus was measured (unit: MPa).

[Impact resistance (Charpy impact strength)]
The impact strength (kJ / m ² ) was measured according to ISO 179.

[Bleed-out test]
The obtained pellets were molded into a 0.5 mm × 5 cm × 10 cm flat plate, letters (ABC) were written on the surface with oil-based ink, and the flat plate was allowed to stand at 65 ° C. and 90% RH for 4 hours. And the bleed-out state of the plasticizer on the flat plate surface was visually evaluated according to the following criteria.

○: There is almost no bleed-out and ink characters are hardly blurred. △: Bleed-out is slightly observed and ink characters are blurred. ×: The bleed-out is remarkable and the ink characters are blurred to a level that cannot be read. .

[Quantification method of free acetic acid concentration]
A small amount of the obtained molded product (50 mm × 90 mm × 1 mm flat plate (molded product)) is cut out, heated to collect the generated gas, analyzed by HSS-GC (Head Space Sampler-Gas Chromatography), and acetic acid concentration Asked. In addition, the measurement (analysis) conditions of free acetic acid concentration are as follows.

  HSS apparatus (manufactured by Agilent Technology, “HP7694”): oven temperature 60 ° C., loop temperature 80 ° C., line (Tr. Line) temperature 120 ° C., heating equilibration time (EQ Time) 30 minutes, loop volume 1 ml, sample Vial volume 20 ml, sample (cut-out molded product) weight 0.5-0.7 g.

GC device (manufactured by Agilent Technology, “HP6890”): Column [J & W, “DB-1” 30 m-0.25 mm I.D. D. −1.00 um (62)], carrier [helium He, gas flow rate (const. Flow mode) 1 ml / min], injection (INJ) temperature 200 ° C., detector (DET / FID) = 280 ° C., split (Split) = 10: 1, oven temperature [40 ° C. (3 min.) − 10 ° C./min. −200 ° C. (1 min.) → 15 ° C./min. −280 ° C. (10 min.)]
In Table 1, the acetic acid concentration “0” means that it was below the detection limit, indicating that no peak corresponding to acetic acid was detected.

[Sensory test 1]
The obtained molded product (79 mm × 10 mm × 4 mm bar type test piece) was put in a polyethylene bag, sealed, and left for 2 hours. The odor in the polyethylene bag immediately after opening the left polyethylene bag was subjected to sensory evaluation based on the following criteria based on human sense of smell.

○: Odorless or almost no acetic acid odor Δ: Slightly acetic acid odor x: Acetic acid odor In addition, the above evaluation was performed by five people extracted at random, but the evaluation was the same.

[Sensory test 2]
In addition, when the injection molding machine (manufactured by Toshiba Corporation, IS100E) is set to a cylinder temperature of 220 ° C. and a mixture having the composition shown in Table 1 is weighed at a back pressure of 0 Pa, the friction noise of the screw (squeaking and squeaking noise) ) Was evaluated by human hearing according to the following criteria.

○… Friction noise is not heard even if the ears are stolen. △… Friction noise is slightly heard. ×… Friction noise is clearly audible. It was.

Claims (17)

  A resin composition comprising a cellulose ester, a non-cellulose ester thermoplastic resin, a plasticizer for the cellulose ester, and a bleedout inhibitor for suppressing or preventing bleedout of the plasticizer.   The resin composition according to claim 1, wherein the total average substitution degree of the cellulose ester is 2.7 or less.   The resin composition according to claim 1, wherein the cellulose ester is a cellulose ester having an average substitution degree at the 6-position of a glucose unit of 0.35 to 0.8.   The resin composition according to claim 1, wherein the non-cellulose ester thermoplastic resin is composed of at least one selected from an aromatic polyester resin and an aromatic polycarbonate resin.   The resin composition according to claim 1, wherein the ratio of the non-cellulose ester thermoplastic resin is 5 to 100 parts by weight with respect to 100 parts by weight of the cellulose ester.   The resin composition according to claim 1, wherein the plasticizer comprises at least one selected from non-condensed phosphate esters and phthalate esters.   The resin composition according to claim 1, wherein the bleedout inhibitor is composed of a condensed phosphate ester.   The resin composition according to claim 1, wherein the ratio of the bleedout inhibitor is 3 to 50 parts by weight with respect to 100 parts by weight of the plasticizer.   Cellulose acetate having a total average substitution degree of 2.1 to 2.7 and an average substitution degree of 0.4 to 0.7 at the 6th position of the glucose unit, and at least one selected from a polybutylene terephthalate resin and an aromatic polycarbonate resin It is composed of a kind of non-cellulose ester thermoplastic resin, a triaryl phosphate, and an aromatic condensed phosphate ester having a melting point of 70 to 150 ° C., and the ratio of the non-cellulose ester thermoplastic resin is 10 to 80 parts by weight with respect to 100 parts by weight of the cellulose acetate, and the proportion of the triaryl phosphate is 5 to 40 parts by weight with respect to 100 parts by weight of the cellulose acetate, and the aromatic condensed phosphate The resin composition according to claim 1, wherein the ratio is from 8 to 40 parts by weight based on 100 parts by weight of the triaryl phosphate ester.   The resin composition according to claim 1, further comprising at least one compatibilizer selected from an epoxy resin and an epoxy-modified diene copolymer.   Furthermore, the resin composition of Claim 1 containing the at least 1 type of filler selected from the fibrous filler, the plate-shaped filler, and the granular filler.   The resin composition according to claim 1, further comprising at least one epoxy compound selected from an alicyclic epoxy compound and a long-chain aliphatic epoxy compound.   The resin composition according to claim 1, further comprising at least one stabilizer selected from organic acids, thioether compounds, and phosphites.   The resin composition according to claim 1, further comprising at least one deodorant selected from hydrated zirconium oxide, zirconium oxide, and carbodiimide compound.   Furthermore, the resin composition of Claim 1 containing acid-modified resin.   The resin composition according to claim 1, which is used for injection molding.   A molded article formed from the resin composition according to claim 1.