WO2014087801A1 - Composition de résine de cellulose et son utilisation - Google Patents

Composition de résine de cellulose et son utilisation Download PDF

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Publication number
WO2014087801A1
WO2014087801A1 PCT/JP2013/080285 JP2013080285W WO2014087801A1 WO 2014087801 A1 WO2014087801 A1 WO 2014087801A1 JP 2013080285 W JP2013080285 W JP 2013080285W WO 2014087801 A1 WO2014087801 A1 WO 2014087801A1
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group
cellulose
derivative
cardanol
acid
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PCT/JP2013/080285
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English (en)
Japanese (ja)
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幸浩 木内
曽山　誠
修吉 田中
位地　正年
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日本電気株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
    • C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6484—Polysaccharides and derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • the present invention relates to a cellulose resin composition containing a cellulose resin and an olefin resin and its use.
  • Bioplastics made from plant-derived materials can contribute to oil depletion countermeasures and global warming countermeasures.
  • general products such as packaging, containers, and textiles, they are also durable products such as electronic devices and automobiles.
  • ordinary bioplastics such as polylactic acid, polyhydroxyalkanoate, starch modified products, etc. all start from starch-based materials, ie, edible parts, which are polymers of ⁇ -glucose molecules.
  • starch-based materials ie, edible parts, which are polymers of ⁇ -glucose molecules.
  • cellulose As bioplastics mainly made from non-edible parts, various bioplastics using cellulose, which is the main component of wood and plants that are non-edible parts, have already been developed and commercialized.
  • cellulose itself is a polymer in which ⁇ -glucose molecules are linearly polymerized by ⁇ (1 ⁇ 4) glycosidic bonds, and since it has high crystallinity, it is hard, brittle and does not have thermoplasticity.
  • cellulose itself contains many hydroxy groups, its water absorption is high and its water resistance is low. For this reason, various examinations for improving the characteristics of cellulose have been conducted for use in durable products as described above.
  • Patent Document 1 discloses thermoplasticity obtained by subjecting cellulose acetate having a hydroxy group (—OH) to ring-opening graft polymerization of ⁇ -caprolactone using the remaining hydroxy group (—OH). Biodegradable graft polymers are disclosed.
  • biodegradable materials using non-edible components derived from plants have also been developed.
  • cardanol derived from cashew nut shell has been applied to various uses because it has a stable molecular output and is excellent in functionality from a characteristic molecular structure.
  • Patent Document 2 discloses a brake formed using a fiber base material made of aramid pulp and cellulose fiber, a filler made of calcium carbonate and cashew dust, and a binder made of phenol resin.
  • a friction material is disclosed.
  • Patent Document 3 discloses a friction material formed using a base substrate made of aramid fibers and cellulose fibers, a filler made of graphite and cashew dust, and an organic-inorganic composite binder. It is described that this friction material is applied to a clutch facing of a power transmission system such as an automobile.
  • Non-Patent Document 1 describes that the water resistance of paper can be improved by immersing the paper sheet in cardanol and performing a grafting reaction that binds cardanol to cellulose constituting the paper sheet.
  • Non-Patent Document 2 an epoxy group is introduced into hydroxyethyl cellulose by utilizing a ring-opening addition reaction to an epoxy ring by an alcoholic hydroxy group (—CH 2 —OH) (phenolic hydroxy group (—OH)). It is described that the water resistance of the cellulose is improved by bonding cardanol (which has been subjected to O- (2,3-epoxypropyl) ation using a condensation reaction between chloroquine and epichlorohydrin).
  • Patent Document 4 a cellulose resin produced using cellulose and cardanol as starting materials, and uses of the cellulose resin are proposed in Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7, respectively.
  • Patent Document 4 discloses a cellulose resin composition containing a cardanol-modified filler in which “cardanol or a derivative thereof” is immobilized on the surface using a cellulose resin and a silane coupling agent. At this time, as the cellulose-based resin contained in the cellulose-based resin composition, “cardanol or a derivative thereof” is bonded (grafted) using a hydroxy group (—OH) of cellulose or a derivative thereof.
  • the cellulosic resin is preferably used.
  • Patent Document 5 uses a cellulose-based resin to which “cardanol or a derivative thereof” is bonded (grafted) using a hydroxy group (—OH) of cellulose or a derivative thereof;
  • a cellulosic resin composition comprising a cardanol-modified silicone compound in which “cardanol or a derivative thereof” is bonded to a silicone compound is disclosed.
  • Patent Document 6 discloses a cellulose resin in which “cardanol or a derivative thereof” and “soft component” are bonded (grafted) to each other by utilizing a hydroxy group (—OH) of cellulose or a derivative thereof.
  • a cellulose-based resin composition comprising a cellulose-based resin in which a thermoplastic polyurethane elastomer or a modified silicone compound, and the above-mentioned “cardanol or derivative thereof” and “soft component” are bonded (grafted), respectively.
  • Patent Document 7 discloses that cellulose or a derivative thereof is converted to —O—CO—O by utilizing the hydroxy group (—OH) of cellulose or a derivative thereof and the hydroxy group (—OH) of “cardanol or a derivative thereof”.
  • cellulose in which “cardanol or a derivative thereof” is added (grafted) via a modified silicone compound and the —O—CO—O— (carbonate) bond or —O—CO—NH— (urethane) bond Discloses a cellulose resin composition containing a resin.
  • Patent Document 8 discloses a hydroxy group (—OH) of cellulose or a derivative thereof, a hydroxy group (—OH) of a hydrogenated cardanol containing 3-pentadecylcyclohexanol, and a diisocyanate compound (O ⁇ C ⁇ N—RN—). ⁇ C ⁇ O) is reacted with an isocyanate group (—N ⁇ C ⁇ O) to give the hydrogenated cardanol to —O—CO—NH—R—NH—CO—O— Cellulosic resins are disclosed that are linked via a linker structure.
  • thermoplastic polyurethane elastomer or a modified silicone compound a cellulose resin to which the hydrogenated cardanol is added (grafted)
  • the “thermoplastic polyurethane elastomer or modified silicone compound” has a function of improving the impact resistance of the disclosed cellulose resin composition.
  • thermoplasticity and elongation at break by adding a plasticizer to the disclosed cellulose resin composition.
  • Patent Document 9 by performing mercerization treatment, hydrogen (H) of a hydroxy group (—OH) of cellulose or a derivative thereof is substituted with M (M represents an alkali metal), and a hydroxy group (—OH ) Is converted to —OM (M represents an alkali metal), and the mercerized cellulose is bound to “cardanol or a derivative thereof” having a functional group capable of reacting with the functional group (—OM) of the mercerized cellulose.
  • a cellulosic resin is disclosed.
  • the “cardanol or derivative thereof” added with a thermoplastic resin excellent in flexibility such as a thermoplastic polyurethane elastomer or an impact modifier such as a modified silicone compound is added (grafted).
  • a cellulose resin composition containing a cellulose resin is disclosed.
  • an object of the present invention is to provide a cellulose-based resin composition having a novel configuration that can achieve both impact resistance and strength, and has a high utilization rate of non-edible biodegradable raw materials derived from plants. .
  • the cellulose-based resin composition in which a thermoplastic resin, in particular, an olefin-based resin is added instead of a plasticizer to a cellulose-based resin is, for example, a resin of a molding material for injection molding processing. It was found that it can be used as an ingredient. In a molded article produced using a molding material that uses a cellulose resin composition containing the cellulose resin and an olefin resin as a resin component, high impact resistance can be achieved. It has been found that the mechanical strength due to the resin can be maintained.
  • the inventors completed the present invention based on the above findings.
  • the cellulose resin composition according to the present invention is A cellulose resin composition comprising the following cellulose resin (X) and olefin resin (Y).
  • the (Y) olefin resin is selected from the group consisting of polyethylene, polyethylene having a polar group in part of its structure, polypropylene, polypropylene having a polar group in part of its structure, and an olefinic thermoplastic elastomer. Is preferred.
  • the cellulose resin composition according to the present invention contains a plasticizer (Z) in addition to the cellulose resin (X) and the olefin resin (Y). It is also possible to adopt the form of a thing.
  • the cellulosic resin composition according to the present invention which employs the above form, It is a cellulose resin composition characterized by containing the following cellulose resin (X), an olefin resin (Y), and also a plasticizer (Z).
  • the (Y) olefin resin is selected from the group consisting of polyethylene, polyethylene having a polar group in part of its structure, polypropylene, polypropylene having a polar group in part of its structure, and an olefinic thermoplastic elastomer. Is preferred. Moreover, it is preferable to select the plasticizer which shows compatibility with the said cellulose resin (X) as said (Z) plasticizer.
  • the molding material according to the present invention is a molding material containing a resin component exhibiting thermoplasticity, and includes the cellulose resin composition according to the present invention as the resin component exhibiting thermoplasticity.
  • the molded product according to the present invention is a molded product produced using a molding material containing a thermoplastic resin component, and the thermoplastic resin component contained in the molding material is the present invention. It is a cellulose resin composition concerning this.
  • the cellulosic resin composition according to the present invention combines the cellulosic resin and the olefinic resin, for example, to use non-edible material and achieve good impact resistance and strength. it can. For this reason, according to the present invention, for example, it is possible to provide a molding material and a molded product such as a durable product such as an electronic device by using the raw material of the non-edible part.
  • FIG. 1 is a flowchart illustrating a synthesis process of a cellulose resin 1 used for preparing a cellulose resin composition according to the present invention, which is exemplified in an example described later.
  • the cellulose resin composition according to the present invention includes the following cellulose resin (X) and the following olefin resin (Y).
  • R—CO— an acyl group represented by R—CO—, wherein R is an aromatic hydrocarbon group having 6 to 12 carbon atoms;
  • Olefin resin Olefin resin.
  • the (Y) olefin resin is selected from the group consisting of polyethylene, polyethylene having a polar group in part of its structure, polypropylene, polypropylene having a polar group in part of its structure, and an olefinic thermoplastic elastomer. Is preferred.
  • cellulose resin composition In the cellulose resin composition according to the present invention, Cellulosic resin (X) to which (X1) cardanol or a derivative thereof is added, A hydroxy group of the (X1) cardanol or a derivative thereof or a substituent thereof; By reaction between the hydroxy group of cellulose or cellulose derivative or its substituents,
  • the cellulose or cellulose derivative is preferably a cellulose resin in which the (X1) cardanol or a derivative thereof is added via a covalent bond.
  • R1 is a saturated aliphatic hydrocarbon group represented by — (CH 2 ) 14 CH 3
  • R3 is an unsaturated aliphatic hydrocarbon group represented by — (CH 2 ) 7 CH ⁇ CHCH 2 CH ⁇ CH (CH 2 ) 2 CH 3
  • the hydrogen of the phenolic hydroxy group (—OH) may be substituted with a substituent.
  • (X1) cardanol or a derivative thereof is It may be a fully hydrogenated cardanol represented by the following formula (3):
  • R is a saturated aliphatic hydrocarbon group represented by — (CH 2 ) 14 CH 3 ;
  • the hydrogen of the hydroxy group (—OH) may be substituted with a substituent.
  • the fully hydrogenated cardanol represented by the formula (3) is 3-pentadecylcyclohexanol.
  • the cellulose resin (X) is It is desirable to be a cellulose resin grafted with the cardanol of (X1) or a derivative thereof.
  • R is preferably a linear or branched aliphatic hydrocarbon group having 12 to 29 carbon atoms.
  • R is preferably a saturated or unsaturated aliphatic hydrocarbon group having 12 to 29 carbon atoms.
  • R is preferably a phenyl group.
  • the cellulose resin composition according to the present invention In the cellulose resin composition according to the present invention, In the cellulose resin composition containing the cellulose resin (X) and the olefin resin (Y), The ratio of the weight W X of the cellulose resin (X) contained and the weight W Y of the olefin resin (Y); W X : W Y is selected in the range of 100: 1 to 100: 17.5 It is preferable.
  • the cellulose resin composition according to the present invention in addition to the cellulose resin (X) and the olefin resin (Y), when adopting a form containing a plasticizer (Z),
  • the cellulose resin composition according to the present invention is It is a cellulose resin composition characterized by containing the following cellulose resin (X), an olefin resin (Y), and also a plasticizer (Z).
  • the (Y) olefin resin is selected from the group consisting of polyethylene, polyethylene having a polar group in part of its structure, polypropylene, polypropylene having a polar group in part of its structure, and an olefinic thermoplastic elastomer. Is preferred. Moreover, it is preferable to select the plasticizer which shows compatibility with the said cellulose resin (X) as said (Z) plasticizer.
  • the plasticizer (Z) As the cellulose resin (X), As the cellulose resin (X), As the cellulose resin (X), When adopting a cellulose resin in which the (X1) cardanol or a derivative thereof is added via a urethane bond (—O—CO—NH—), The ratio of the weight W X of the cellulosic resin (X) contained and the weight W Z of the plasticizer (Z); W X : W Z is selected in the range of at least 100: 0 to 100: 17.5 It is preferable that
  • the plasticizer (Z) preferably contains a compound having a structure in which two ester bonds (—O—CO—) are contained in the molecule. At that time, it is more preferable that a divalent linear hydrocarbon group having 6 or less carbon atoms exists between the two ester bonds (—O—CO—).
  • the cellulose resin (X) is represented by, for example, “(X1) cardanol or a derivative thereof”, “(X2) R—CO—, and R is 12 carbon atoms.
  • R is 12 carbon atoms.
  • Cellulosic resin made may be used.
  • the cellulosic resin (X) is represented by, for example, the above “(X1) cardanol or a derivative thereof” or “(X2) R—CO— in the same cellulose skeleton, where R is 12 to 29 carbon atoms.
  • acyl group that is an aliphatic hydrocarbon group ”or“ acyl group represented by (X3) R—CO—, wherein R is an aromatic hydrocarbon group having 6 to 12 carbon atoms ” is added. It may be a cellulosic resin to which any two types are added, or a cellulose resin to which all three types are added. In the cellulose-based resin, for example, in the same cellulose skeleton, the “(X1) cardanol or a derivative thereof” added may be either cardanol or a cardanol derivative, or both.
  • acyl group represented by (X2) R—CO— wherein R is an aliphatic hydrocarbon group having 12 to 29 carbon atoms” or “(X3) R—CO— , R is an aromatic hydrocarbon group having 6 to 12 carbon atoms ", each may be one kind of acyl group or two or more kinds of acyl groups.
  • the cellulose resin (X) may be one kind or a combination of two or more kinds.
  • the cellulosic resin (X) is, for example, a cellulosic resin to which the “(X1) cardanol or a derivative thereof” is added, or the “(X2) R— A cellulose resin to which an “acyl group represented by CO— and R is an aliphatic hydrocarbon group having 12 to 29 carbon atoms” is added, or “(X3) R—CO—, wherein R is carbon Any one of the cellulose resins to which the “acyl group as an aromatic hydrocarbon group of formula 6 to 12” has been added may be used, any two of them may be used together, or all three of them may be used together.
  • the cellulose resin contained in the cellulose resin composition according to the present invention may be only the cellulose resin (X) or may further contain other cellulose resins.
  • the cellulose resin to which the “(X1) cardanol or derivative thereof” used in the cellulose resin composition according to the present invention is added is, for example, a phenolic hydroxy group of the “(X1) cardanol or derivative thereof”. Or the cellulose resin to which the said "(X1) cardanol or its derivative (s)" was added by reaction with the substituent and the hydroxyl group or its substituent of cellulose or a cellulose derivative is mentioned.
  • the reaction is, for example, a “combination” of the phenolic hydroxy group and its substituent of “(X1) cardanol or a derivative thereof” and the hydroxy group or a substituent of “cellulose or a cellulose derivative” involved in the reaction. Depending on it, it can be selected as appropriate.
  • the reaction is “ ⁇ OH + HO ⁇ ⁇ ⁇ O ⁇ + H”.
  • the reaction is “ ⁇ OH + HO ⁇ ⁇ ⁇ O ⁇ + H”.
  • the hydrogen may be substituted with halogen (X) such as Cl, F, Br, and I.
  • the “(X1) cardanol and its derivative” can be represented by, for example, the formula (2), and there are four types having different unsaturated bonds in R.
  • the “(X1) cardanol and its derivative” added to “cellulose or a cellulose derivative” is any one of, for example, It may be a kind, a mixture of two kinds, a mixture of three kinds, or a mixture of four kinds.
  • R is the following R1, R2, R3 or R4:
  • R1 is a saturated aliphatic hydrocarbon group represented by — (CH 2 ) 14 CH 3 ;
  • R3 is an unsaturated aliphatic hydrocarbon group represented by — (CH 2 ) 7 CH ⁇ CHCH 2 CH ⁇ CH (CH 2 ) 2 CH 3 ;
  • the hydrogen of the hydroxy group (—OH) may be substituted.
  • the group in which the hydrogen of the hydroxy group (—OH) is substituted can be represented by —OX, and examples of X include halogens such as Cl, F, Br, and I.
  • R is preferably R1 of a saturated aliphatic hydrocarbon group.
  • (X1) cardanol and derivatives thereof” includes a hydrogenated cardanol in which R is R1 of a saturated aliphatic hydrocarbon group, and an unsaturated aliphatic hydrocarbon group other than R1 (R2, R3, R4).
  • hydrogenation treatment is performed on the mixture, that is, hydrogen is added to unsaturated bonds of unsaturated aliphatic hydrocarbon groups (R2, R3, R4) other than R1, It is preferable to perform a treatment for converting the unsaturated aliphatic hydrocarbon group (R2, R3, R4) into a saturated aliphatic hydrocarbon group (R1).
  • the unsaturated aliphatic hydrocarbon group (R2, R3 and R4) having an unsaturated bond in the formula (2) becomes R1 which is a saturated aliphatic hydrocarbon group.
  • cardanol having a saturated aliphatic hydrocarbon group represented by R1 is also referred to as hydrogenated cardanol (hydrogenated cardanol).
  • the “hydrogenated cardanol” is 3-n-pentadecylphenol.
  • the “(X1) cardanol and its derivative” to be added is, for example, any one of R, R2, R3, and R4 in the formula (2). Alternatively, any two types, any three types, all four types, or a derivative thereof may be used.
  • the cellulose resin (X) to which the “(X1) cardanol and its derivative” is added is obtained by, for example, grafting the “cardanol or its derivative” represented by the formula (2) onto the “cellulose or cellulose derivative”.
  • a cellulosic resin is preferred.
  • the cellulose resin (X) to which the “(X1) cardanol and its derivative” is added may be obtained by grafting, for example, the “totally hydrogenated cardanol” represented by the formula (3) onto the “cellulose or cellulose derivative”. It is preferable that it is a cellulose resin.
  • the “acyl group of (X2)” is represented by R—CO—, and R is an aliphatic hydrocarbon group having 12 to 29 carbon atoms.
  • the “acyl group (R—CO—) of (X2)” is also referred to as an alkanoyl group when R is an alkyl group.
  • the carbon number of R as the aliphatic hydrocarbon group is not particularly limited as long as it is in the range of 12 to 29 carbon atoms. For example, it is more preferable to select the carbon number in the range of 13 to 20.
  • the total number of carbon atoms represented by R—CO— in the “acyl group (R—CO—) of (X2)” is in the range of 13 to 30, and more preferably in the range of 14 to 21.
  • an aliphatic hydrocarbon is defined as an acyclic or cyclic, non-aromatic hydrocarbon (RH).
  • RH non-aromatic hydrocarbon
  • a monovalent aliphatic hydrocarbon group means a group (R—) obtained by removing one hydrogen (H) from an aliphatic hydrocarbon (R—H).
  • a monovalent aliphatic hydrocarbon group (R—) derived from a saturated aliphatic hydrocarbon is referred to as a monovalent saturated aliphatic hydrocarbon group, and is a monovalent aliphatic derived from an unsaturated aliphatic hydrocarbon.
  • the group hydrocarbon group (R—) is referred to as a monovalent unsaturated aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group (R) includes, for example, a linear or branched aliphatic hydrocarbon group.
  • the acyl group (R—CO—) in which R is a linear or branched aliphatic hydrocarbon group is adopted as the “(X2) acyl group (R—CO—)”
  • the “(X2) The cellulose resin to which the acyl group (R—CO—) ”is added is referred to as the“ (X2) acyl group (R—CO—) ”.
  • R is a linear aliphatic hydrocarbon group. Only an acyl group (R—CO—) may be added, or only an acyl group (R—CO—) which is a branched aliphatic hydrocarbon group may be added to R, or both It may be added.
  • examples of the aliphatic hydrocarbon group (R) include a saturated or unsaturated aliphatic hydrocarbon group.
  • R is an acyl group (R—CO—), which is a saturated or unsaturated aliphatic hydrocarbon group, as the “(X2) acyl group (R—CO—)”
  • the “(X2) Cellulosic resin (X) to which “acyl group (R—CO—)” is added is referred to as “(X2) acyl group”.
  • R is an acyl group (R) that is a saturated aliphatic hydrocarbon group. Only -CO-) may be added, or only an acyl group (R-CO-) which is an unsaturated aliphatic hydrocarbon group may be added to R, or both may be added.
  • acyl group (R—CO—) of“ (X2) ” is not particularly limited as long as the total number of carbon atoms in the acyl group (R—CO—) is in the range of 13 to 30, for example, a tridecanoyl group ( C13), tetradecanoyl group (C14), pentadecanoyl group (C15), hexadecanoyl group (C16), palmitoleyl group (unsaturated C16), heptadecanoyl group (C17), stearoyl group (octadecanoyl group, C18), cis, cis-9,12-octadecadienoyl (unsaturated C18), 9,12,15-octadecantrienoyl (unsaturated C18), 6,9,12-octadecatrienoyl (unsaturated C18) ), 9,11,13-octadecatrienoyl (uns
  • the “(X3) acyl group (R—CO—)” is represented by R—CO—, and R is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • R—CO— is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • the carbon number of R, which is an aromatic hydrocarbon group is not particularly limited as long as it is in the range of 6 to 12. For example, R It is more preferable to select 6 carbon atoms.
  • aromatic hydrocarbon is defined as a compound composed of only hydrocarbons among aromatic compounds having aromaticity (aromatic compound).
  • Aromatic hydrocarbons are roughly classified into benzene aromatic hydrocarbons and non-benzene aromatic hydrocarbons.
  • a monovalent aromatic hydrocarbon group means a group (R—) obtained by removing one hydrogen (H) from an aromatic hydrocarbon (R—H).
  • a monovalent aromatic hydrocarbon group obtained by removing one hydrogen (H) on a benzene ring from a monovalent aromatic hydrocarbon group (R-) derived from a benzene aromatic hydrocarbon is an aryl group. It is called a group.
  • the aromatic hydrocarbon group is preferably, for example, a phenyl group (Ph—) having a basic ring of 6 carbon atoms.
  • the carbon constituting the benzene ring of the phenyl group may be bonded to hydrogen except for carbon bonded to the ketone group (—CO—) in the acyl group (R—CO—), or the hydrogen Instead of, it may be substituted with a substituent.
  • the substituent present on the carbon constituting the benzene ring include a halogen and an aliphatic hydrocarbon group.
  • the olefin resin (Y) contained in the cellulose resin composition according to the present invention is polyethylene, polyethylene having a polar group in a part of the structure, polypropylene, polypropylene having a polar group in a part of the structure, and olefin. It is preferable to select from the group consisting of thermoplastic elastomers.
  • the polyethylene used as the olefin resin (Y) is, for example, a linear high-density polyethylene with a small amount of comonomer and a rich ethylene, and a linear low amount with a large amount of comonomer that inhibits crystallization.
  • Low-density polyethylene using a density polyethylene and a metallocene catalyst and having a narrow molecular weight distribution controlled is preferable.
  • polyethylene synthesized using the lowest density metallocene catalyst is preferable because of its high impact resistance improving effect.
  • the polyethylene used as the olefin resin (Y) and having a polar group introduced into a part of its structure is preferably polyethylene modified with maleic anhydride.
  • the polypropylene used as the olefin resin (Y) and having a polar group introduced into a part of its structure is preferably a polypropylene modified with maleic anhydride.
  • the olefinic thermoplastic elastomer used as the olefinic resin (Y) is composed of polypropylene as a hard segment and ethylene propylene rubber as a soft segment, and the hard segment and the soft segment are simply mechanically kneaded and blended. Examples thereof include a type in which only the soft segment is crosslinked with an organic peroxide, but are not limited thereto.
  • the olefin resin (Y) contained in the cellulose resin composition according to the present invention may be, for example, only one type or a combination of two or more types.
  • the content ratio of the cellulose resin (X) and the olefin resin (Y) is such that the content of the cellulose resin (X) is the content of the olefin resin (Y).
  • the ratio of the content (wt) W Y of the olefin resin (Y) is, for example, the weight ratio W X : W Y is selected in the range of at least 100: 1 to 100: 100.
  • Weight ratio; W X : W Y is usually in the range of 100: 2 to 100: 50, preferably in the range of 100: 3 to 100: 30, more preferably in the range of 100: 4 to 100: 25. More preferably, it is desirable to select in the range of 100: 5 to 100: 17.5, particularly in the range of 100: 5 to 100: 15.
  • the cellulose resin composition according to the present invention contains a plasticizer (Z) in addition to the cellulose resin (X) and the olefin resin (Y).
  • a plasticizer (Z) in addition to the cellulose resin (X) and the olefin resin (Y).
  • the ratio of (weight) W Z is, for example, the weight ratio; W X : (W Y + W Z ) is usually in the range of 100: 4 to 100: 25, preferably 100: 5 to 100: 17.5. It is desirable to select within the range of 100: 5 to 100: 15.
  • content and (weight) W X of the cellulose-based resin (X), the ratio of the content (wt) W Z of the plasticizer (Z), the weight ratio; W X: the W Z at least, It is desirable to select in the range of 100: 0 to 100: 17.5, preferably in the range of 100: 5 to 100: 15.
  • the content ratio (by weight) W Y content of the cellulose-based resin (X) (weight) W X and, wherein the olefin-based resin (Y) The weight ratio; W X : W Y is preferably selected in the range of 100: 5 to 100: 17.5, more preferably in the range of 100: 5 to 100: 15.
  • the mechanism by which the impact resistance is improved by the addition of the olefin resin (Y) is not clear.
  • the aliphatic hydrocarbon group in the olefin resin (Y) is a linear hydrocarbon moiety R or R in the “(X1) cardanol or derivative thereof” constituting the cellulose resin (X).
  • the affinity of the “(X2) acyl group” having the structure of —CO— with the aliphatic hydrocarbon group R is excellent.
  • the olefin resin (Y) is added to the cellulose resin (X)
  • the olefin resin (Y) is moderately dispersed with a particle diameter of about several ⁇ m in diameter. Therefore, it is presumed that the particles of the olefin resin (Y) exhibit a stress relaxation effect and improve the impact resistance.
  • the cellulose resin composition according to the present invention may consist only of the cellulose resin (X) and the olefin resin (Y), and further, the cellulose resin (X) and the olefin resin (Y).
  • a form in which the plasticizer (Z) is added can be employed.
  • the cellulose resin composition according to the present invention may contain other additives in addition to the plasticizer (Z). The additive that can be added to the cellulose resin composition according to the present invention will be described later.
  • the cellulose resin (X) contained in the cellulose resin composition according to the present invention is, for example, the reactive carbonization having the “(X1) cardanol or a derivative thereof” or the “(X2) acyl group”. It can be prepared by subjecting a hydrogen compound or a reactive hydrocarbon compound having an acyl group of (X3) above to cellulose or a derivative thereof.
  • a cellulose resin in which “acyl group of (X2)” is added to “cellulose or a derivative thereof” The resin, the “olefin resin (Y)” and the like are exemplified.
  • the following description is an illustration and this invention is not restrict
  • Cellulose or derivatives thereof Cellulose is a heavy product in which ⁇ -glucose ( ⁇ -D-glucopyranose) represented by the following formula (1) is polymerized in a straight chain by ⁇ (1 ⁇ 4) glucoside bonds.
  • the ⁇ -glucose ( ⁇ -D-glucopyranose) unit constituting cellulose has one alcoholic hydroxy group (—OH) on the carbon atoms at the 2nd, 3rd and 5th positions, respectively.
  • the cellulosic resin (X) uses the hydroxyl group (—OH) which can be said to exist in a ⁇ -glucose ( ⁇ -D-glucopyranose) unit, for example, in cellulose or a derivative thereof.
  • the (X1) cardanol or a derivative thereof is preferably “grafted” with respect to the cellulose or the derivative thereof using the alcoholic hydroxy group (—OH), for example.
  • —OH alcoholic hydroxy group
  • the derivative of cellulose is not particularly limited, and examples thereof include those obtained by acylating, etherifying, or grafting a part of these hydroxy groups.
  • organic acid esters such as cellulose acetate, cellulose butyrate, and cellulose propionate
  • inorganic acid esters such as cellulose nitrate, cellulose sulfate, and cellulose phosphate
  • cellulose acetate propionate cellulose acetate butyrate
  • Examples thereof include hybrid esters such as cellulose acetate phthalate and cellulose nitrate acetate
  • etherified celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
  • cellulose derivative examples include cellulose grafted with styrene, (meth) acrylic acid, (meth) acrylic acid ester, ⁇ -caprolactone, lactide, glycolide, and the like. Any one of these cellulose derivatives may be used alone, or two or more of them may be used in combination.
  • lactide has two ester bonds in which two molecules of hydroxycarboxylic acid (HO—R—COOH) are formed by dehydration condensation between a hydroxy group (—OH) and a carboxyl group (—COOH).
  • HO—R—COOH hydroxycarboxylic acid
  • —COOH carboxyl group
  • a typical lactide is dilactide formed from two molecules of lactic acid.
  • Glycolide diglycolic anhydride
  • glycolic acid hydroxyacetic acid
  • acylated cellulose such as cellulose acetate, cellulose propionate, and cellulose butyrate in which a part of the hydroxy group is acylated is preferable.
  • derivative of cellulose includes, for example, any meaning of a cellulose compound and a compound having a cellulose skeleton obtained by introducing a functional group biologically or chemically from cellulose as a raw material. .
  • the degree of polymerization of ⁇ -glucose ( ⁇ -D-glucopyranose) of “cellulose or a derivative thereof” is not particularly limited.
  • the average of the total number of ⁇ -glucose ( ⁇ -D-glucopyranose) units constituting the chain The value is preferably in the range of 50 to 5000, more preferably in the range of 100 to 3000.
  • ⁇ -glucose ⁇ -D-glucopyranose
  • Cellulose is a main component of vegetation, and can be obtained, for example, by separating other components such as lignin from vegetation.
  • cellulose resin composition according to the present invention for example, in addition to the cellulose thus obtained, cotton and pulp having a high cellulose content can be purified or used as they are.
  • Cellulose or its derivative refers to, for example, chitin (poly- ⁇ 1-4-N-acetylglucosamine), chitosan (poly- ⁇ 1 ⁇ 4-glucosamine) or paramylon ( ⁇ -1,3- Similar substances such as glucan) may be mixed.
  • the ratio of the similar substances is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass with respect to the entire mixture. It is as follows.
  • Cardanol is a component contained in the shell of cashew nut and is an organic compound composed of a phenol moiety and a linear hydrocarbon moiety R as shown in the above formula (2).
  • Pure cardanol is a 3-[(8Z, 11Z) -8,11,14-penta in which the linear hydrocarbon moiety R is — (CH 2 ) 7 CH ⁇ CHCH 2 CH ⁇ CHCH 2 CH ⁇ CH 2. Decatrienyl] phenol.
  • (X1) cardanol or a derivative thereof specifically, “cardanol or a derivative thereof” represented by the formula (2), there are four types having different numbers of unsaturated bonds in the linear hydrocarbon portion R. Usually, a mixture of these four components.
  • the “(X1) cardanol or derivative thereof” for example, a cardanol component obtained by extraction and purification from cashew nut shell liquid can be used.
  • R is the following R1, R2, R3 or R4;
  • R1 is a saturated aliphatic hydrocarbon group represented by — (CH 2 ) 14 CH 3 ;
  • R3 is an unsaturated aliphatic hydrocarbon group represented by — (CH 2 ) 7 CH ⁇ CHCH 2 CH ⁇ CH (CH 2 ) 2 CH 3 ;
  • the hydrogen of the hydroxy group (OH) may be substituted.
  • cardanol or a derivative thereof represented by the above formula (2)
  • all unsaturated bonds in “benzene ring and linear aliphatic hydrocarbon group R” constituting cardanol are all hydrogenated.
  • Hydrogenated cardanol that is, a cardanol derivative of the following formula (3) (3-pentadecylcyclohexanol) can also be used as the “(X1) cardanol or a derivative thereof”.
  • Totally hydrogenated cardanol (3-pentadecylcyclohexanol) is represented by the following formula (3):
  • R is a saturated aliphatic hydrocarbon group represented by — (CH 2 ) 14 CH 3 ;
  • the hydrogen of the hydroxy group (—OH) may be substituted with a substituent.
  • the linear hydrocarbon moiety (R) of “(X1) cardanol or a derivative thereof”, for example, “cardanol or a derivative thereof” represented by the formula (2) is, for example, the flexibility and hydrophobicity of the added cellulosic resin.
  • the phenol moiety has, for example, a phenolic hydroxy group that is used for grafting to “cellulose or a derivative thereof”.
  • the all-hydrogenated cardanol represented by the formula (3) that is, the cardanol derivative (3-) in which all unsaturated bonds in the benzene ring and the linear aliphatic hydrocarbon group R are hydrogenated.
  • the linear saturated hydrocarbon portion (pentadecyl group) of pentadecylcyclohexanol contributes to, for example, the flexibility and hydrophobicity of the added cellulose resin, and the hexanol portion is, for example, “cellulose or a derivative thereof. Having a hydroxy group, which is used for grafting to When the “(X1) cardanol or a derivative thereof” is grafted to “cellulose or a derivative thereof”, for example, a cellulose resin to which “(X1) cardanol or a derivative thereof” is imparted in a brush shape is formed.
  • the interaction between the grafted “(X1) cardanol or its derivative” can improve, for example, mechanical properties, particularly toughness, and can impart thermoplasticity. Furthermore, water resistance is improved by the reduction of the alcoholic hydroxy group in “cellulose or its derivative” and the hydrophobicity of “(X1) cardanol or its derivative”.
  • Examples of the cardanol derivative include a derivative in which hydrogen (H) of the phenolic hydroxy group (—OH) in the formula (2) is substituted.
  • the hydrogen (H) of the phenolic hydroxy group (—OH) is substituted with a halogen (X) such as Cl, F, Br, I, etc. OH) is converted to —OX, substituted with —CH 2 —CO—H or —CH 2 —CO—X, and the hydroxy group (—OH) is replaced with —O—CH 2 —CO—H or —O—.
  • a halogen such as Cl, F, Br, I, etc.
  • X includes halogens such as Cl, F, Br, and I, and is preferably Cl.
  • the derivative is, for example, a derivative in which an oxygen halide group (eg, —CH 2 —CO—X) is substituted for oxygen (O) of the phenolic hydroxy group, specifically, —OH is —O—
  • oxygen halide group eg, —CH 2 —CO—X
  • —OH —O—
  • Derivatives converted to CH 2 —CO—X are preferred.
  • an acid chloride group for example, —CH 2 —CO—Cl
  • a derivative in which —OH is converted to —O—CH 2 —CO—Cl is obtained by reacting, for example, monochloroacetic acid (Cl—CH 2 —COOH) with a phenolic hydroxy group (—OH) in cardanol, and O— Carboxymethylation converts —OH to —O—CH 2 —COOH. Subsequently, the carboxyl group (—COOH) in —O—CH 2 —COOH can be synthesized by converting it to a chlorocarbonyl group (—CO—Cl).
  • (X1) cardanol or a derivative thereof used as a starting material is, for example, the hydrogenated cardanol, that is, R is preferably a cardanol derivative (3-pentadecylphenol) having a saturated aliphatic hydrocarbon group R1.
  • the cardanol derivative (3-pentadecylcyclohexanol) of (3) is also used as a starting material “(X1) cardanol used for the preparation of a cardanol derivative in which the —OH is converted to —O—CH 2 —CO—Cl. Alternatively, it can be suitably used as “a derivative thereof”.
  • the “(X1) cardanol or derivative thereof” is obtained by using a diisocyanate compound in the “cellulose or derivative thereof”.
  • the one added is mentioned.
  • the starting material “(X1) cardanol or a derivative thereof” used for the addition reaction using a diisocyanate compound is, for example, the above-mentioned hydrogenated cardanol, that is, a cardanol derivative (3-pentadecylphenol in which R is a saturated aliphatic hydrocarbon group R1). ) Is preferable.
  • the cardanol derivative (3-pentadecylcyclohexanol) of (3) can also be suitably used as the starting material “(X1) cardanol or a derivative thereof” used for the addition reaction using a diisocyanate compound.
  • a urethane bond (—NH—CO—O—) is formed by a reaction between the other isocyanate group (—N ⁇ C ⁇ O) and a hydroxy group (—OH) of “cellulose or a derivative thereof”.
  • the additive amount of the plasticizer to be additionally added is reduced, or the plasticizer It is also possible to add no additives.
  • the cellulose resin composition according to the present invention containing the cellulose resin to which the “(X1) cardanol or derivative thereof” is added as the cellulose resin (X) is, for example, an olefin resin (Y )
  • a decrease in heat resistance and strength (particularly rigidity) can be suppressed as compared with a cellulose resin composition in which a plasticizer is added to the cellulose resin (X), and the cellulose resin composition
  • the “resin homogeneity” can be improved, and the problem of bleeding out can be solved.
  • the addition amount of the plasticizer which consists of petroleum raw materials which are additionally added to the cellulose resin composition can be reduced or not added, as a result, the plant property can be improved as the whole cellulose resin composition.
  • both cellulose and cardanol are non-edible parts of plants, for example, the utilization rate of non-edible parts can be improved as the whole cellulose resin composition.
  • the average value of DS OH is preferably 0.9 or less, more preferably 0. .7 or less.
  • Grafting is, for example, a “dehydration condensation reaction” between a phenolic hydroxy group (—OH) of “(X1) cardanol or a derivative thereof” and an alcoholic hydroxy group (—OH) of “cellulose or a derivative thereof”.
  • a “dehydration catalyst” may be added to the reaction system.
  • the “dehydration catalyst” that can be used in the “dehydration condensation reaction” include sulfuric acid and toluenesulfonic acid.
  • Grafting comprises, for example, a first functional group capable of reacting with a hydroxy group of “cellulose or a derivative thereof” and a second functional group capable of reacting with a phenolic hydroxy group of “(X1) cardanol or a derivative thereof”.
  • the polyfunctional compound can be used.
  • a polyfunctional compound having the first functional group and the second functional group for example, a carbon atom to which a hydroxy group of “cellulose or a derivative thereof” is bonded, and “(X1) cardanol” are used.
  • the carbon atom on the benzene ring to which the phenolic hydroxy group of the “derivative” is bonded is linked through an “organic linking group” (“linker” structure) derived from the polyfunctional compound.
  • linker organic linking group
  • the “organic linking group” is formed by, for example, a reaction between a hydroxy group and a first functional group in the cellulose resin to which the “(X1) cardanol or derivative thereof” is added. And a “second bond” formed by the reaction of a phenolic hydroxy group and a second functional group.
  • the first bond is, for example, an ester bond (—O—CO—), an ether bond (—O—), or a urethane bond that is bonded to the carbon atom to which the hydroxy group of the “cellulose or derivative thereof” was bonded.
  • the polyfunctional compound and “(X1) cardanol or a derivative thereof” are converted into the second functional group.
  • the reaction between the functional group and the phenolic hydroxy group is used to bond through a “second bond” to form a “polyfunctional compound-modified cardanol derivative”.
  • the “polyfunctional compound-modified cardanol derivative” and “cellulose or a derivative thereof” are obtained by utilizing the reaction of the former first functional group (the first functional group derived from the polyfunctional compound) and a hydroxy group. Are coupled through the “first coupling”. Accordingly, “(X1) cardanol or a derivative thereof” can be bonded to “cellulose or a derivative thereof” via the “organic linking group” derived from the polyfunctional compound.
  • a polyfunctional compound comprising the first functional group and the second functional group for example, a hydroxy group of “cellulose or a derivative thereof” and “(X1) cardanol or a derivative thereof”
  • the hydroxy group disappears with the formation of the “first bond” and “second bond”, respectively, to form a graft bond
  • “cellulose or a derivative thereof” contains “(X1) cardanol or Hydrophobic structures derived from “derivatives” can be introduced.
  • Grafting using a phenolic hydroxy group in “cardanol or a derivative thereof” represented by the above formula (2) is, for example, a linear hydrocarbon moiety constituting “cardanol or a derivative thereof” represented by formula (2) Compared with grafting using an unsaturated bond (carbon-carbon double bond) in R, a highly reactive phenolic hydroxy group is used, so that more efficient grafting can be realized.
  • the phenol part of “cardanol or a derivative thereof” represented by formula (2) is “ Since it is immobilized by reacting with "cellulose or a derivative thereof", the interaction between the linear hydrocarbon moieties R of "cardanol or a derivative thereof” shown in the grafted formula (2) is increased, and mechanical properties are improved. A desired improvement effect is obtained. Furthermore, the grafting using the phenolic hydroxy group in the “cardanol or derivative thereof” shown in the above formula (2) is accompanied by the phenolic hydroxy group in the “cardanol or derivative thereof” shown in formula (2) along with the grafting.
  • the hydrogenated cardanol (3-pentadecylphenol) contains no reactive functional group in addition to the phenolic hydroxy group. Accordingly, hydrogenated cardanol (3-pentadecylphenol) is grafted using the phenolic hydroxy group.
  • the interaction between the linear hydrocarbon moieties (n-pentadecyl groups) of the grafted hydrogenated cardanol (3-pentadecylphenol) is enhanced, and a desired improvement in mechanical properties is obtained.
  • the fully hydrogenated cardanol of formula (3) (3-n-pentadecyllohexanol) as “(X1) cardanol or a derivative thereof”
  • the fully hydrogenated cardanol (3-n-pentadecylsillohexanol) is used.
  • a polyfunctional compound comprising the “first functional group” and the “second functional group”, and a polyfunctional compound derived from the polyfunctional compound, with the “first bond” and the “second bond” at both ends
  • the “organic linking group” includes a structure in which “first functional group” and “second functional group” are bonded to both ends of a divalent or higher valent hydrocarbon group, and a divalent or higher hydrocarbon. It is preferable to have a structure including “first bond” and “second bond” at both ends of the group.
  • the number of carbon atoms in the entire “divalent or higher hydrocarbon group” is not particularly limited, and the lower limit of the carbon number is preferably 1 or more, more preferably 2 or more, and the upper limit of the carbon number is For example, the number of carbon atoms is preferably 20 or less, more preferably 14 or less, and still more preferably 8 or less.
  • the “divalent or higher hydrocarbon group” is preferably, for example, a divalent hydrocarbon group.
  • Methylene group (—CH 2 —), ethylene group (—CH 2 CH 2 —), propane-1,3-diyl group (— (CH 2 ) 3 —), butane-1,4-diyl group (— (CH 2) 4 -), pentamethylene group (- (CH 2) 5 -), hexamethylene group (- (CH 2) 6 -), heptamethylene group (- (CH 2) 7 -), octamethylene (- (CH 2 ) 8 —), decamethylene group (— (CH 2 ) 10 —), dodecamethylene group (— (CH 2 ) 12 —), hexadecamethylene group (— (CH 2 ) 16 —), etc.
  • a divalent linear aliphatic hydrocarbon group having bonds at both ends (in particular, an alkylene group derived from a linear alkane is preferred);
  • a divalent alicyclic ring having a bond on two carbon atoms on a ring such as a cycloheptane ring, a cyclohexane ring, a cyclooctane ring, a bicyclopentane ring, a tricyclohexane ring, a bicyclooctane ring, a bicyclononane ring, or a tricyclodecane ring.
  • a hydrocarbon group of formula A divalent aromatic hydrocarbon group having two bonds on an aromatic ring such as benzene, naphthalene, biphenylene, biphenyl; and Examples of the divalent hydrocarbon group include a combination of the above divalent hydrocarbon groups.
  • the divalent aromatic hydrocarbon group or the divalent alicyclic hydrocarbon group is selected as the divalent hydrocarbon group, for example, the ring structure inherent in the divalent hydrocarbon group
  • the rigidity of the resulting cellulose resin can be further improved due to the rigidity.
  • the divalent linear aliphatic hydrocarbon group having bonds at both ends of the chain for example, the divalent linear aliphatic hydrocarbon group Due to the flexibility, the toughness of the obtained cellulose resin can be further improved.
  • the functional groups used as the “first functional group” and the “second functional group” are particularly limited.
  • carboxyl group (—COOH), carboxylic acid anhydride group (—CO—O—CO—), carboxylic acid halide group (—CO—X) (particularly, carboxylic acid chloride group; —CO—Cl)
  • An epoxy group, an isocyanate group (—N ⁇ C ⁇ O), a halogen group (—X) and the like are preferable.
  • carboxyl group (—COOH), carboxylic acid anhydride group (—CO—O—CO—), halogen group (—X) (especially chloride group; —Cl), isocyanate group (—N ⁇ C ⁇ O) and the like are preferable.
  • the “second functional group” to be reacted with the phenolic hydroxy group of “(X1) cardanol or a derivative thereof” is, in particular, a carboxylic acid anhydride group (—CO—O—CO—), a halogen group (particularly a chloride group).
  • isocyanate groups (—N ⁇ C ⁇ O) and the like are preferable.
  • a carboxylic acid halide group (—CO—X) particularly a carboxylic acid chloride group; —CO—Cl
  • the carboxylic acid halide group (—CO—X) is used, for example, prior to grafting, the carboxyl group (C—COOH) linked to the hydrocarbon group constituting the polyfunctional compound is converted into an acid halide. Used for grafting after conversion to the group (C—CO—X).
  • polyfunctional compound including the “first functional group” and the “second functional group” include, for example, dicarboxylic acid, dicarboxylic acid anhydride, dicarboxylic acid halide, monohalogenocarboxylic acid, diisocyanates, and the like. Is mentioned.
  • dicarboxylic acid means an organic dibasic acid having two carboxyl groups (—COOH) in the molecule.
  • a dicarboxylic acid anhydride is an acid anhydride derived from an organic dibasic acid (dicarboxylic acid) in which two carboxyl groups (—COOH) exist in the molecule, and the two carboxy groups (—COOH) are It is converted to a divalent group of —CO—O—CO—.
  • a dicarboxylic acid halide is an acid halide derived from an organic dibasic acid (dicarboxylic acid) in which two carboxyl groups (—COOH) exist in the molecule, and the carboxyl group (—COOH) is converted to a halogenocarbonyl group ( -CO-X).
  • monohalogenocarboxylic acid means a monohalogen-substituted organic monobasic acid (monohalogen-substituted monocarboxylic acid) in which one halogeno group (—X) and one carboxyl group (—COOH) are present in the molecule. .
  • diisocyanate means a bifunctional organic compound in which two isocyanato groups (—N ⁇ C ⁇ O) are present in the molecule.
  • a trifunctional organic compound having three isocyanato groups (—N ⁇ C ⁇ O) in the molecule is generally referred to as triisocyanate.
  • dicarboxylic acid examples include malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, and the like.
  • dicarboxylic acid anhydride examples include cyclic acid anhydrides derived from the listed dicarboxylic acids, and examples of the dicarboxylic acid halide include acid halides of the listed dicarboxylic acids.
  • monohalogenocarboxylic acids include monochloroacetic acid, 3-chloropropionic acid, 4-chlorobutyric acid, 5-chlorovaleric acid, 6-chlorohexanoic acid, 8-chlorooctanoic acid, 12-chlorododecanoic acid, 18-chlorostearic acid An acid etc. are mentioned.
  • diisocyanates examples include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate, and 1,6-hexamethylene diisocyanate (HDI).
  • Isophorone diisocyanate (IPDI) xylylene diisocyanate (XDI), hydrogenated XDI, tetramethylxylene diisocyanate (TMXDI), 1,8-diisocyanate methyloctane, dicyclohexylmethane diisocyanate (HMDI: hydrogenated MDI), and the like.
  • HMDI hydrogenated MDI
  • MDI 4,4'-diphenylmethane diisocyanate
  • HDI 1,6-hexamethylene diisocyanate
  • a functional group having reactivity with a phenolic hydroxy group (—OH) and “(X1) cardanol” are used. Or a phenolic hydroxy group in “or a derivative thereof” is reacted to form a cardanol derivative to which a polyfunctional compound is added.
  • the cardanol derivative added with the polyfunctional compound is bound to “cellulose or a derivative thereof”. Therefore, using the two reactive functional groups present in the polyfunctional compound, “(X1) cardanol or a derivative thereof” is used as a linker with respect to “cellulose or a derivative thereof”. Combined.
  • the above-mentioned polyfunctional compound can also be used when using a fully hydrogenated cardanol of formula (3) (3-n-pentadecylsilrohexanol) as “(X1) cardanol or a derivative thereof”.
  • a fully hydrogenated cardanol of formula (3) (3-n-pentadecylsilrohexanol) as “(X1) cardanol or a derivative thereof”.
  • the polyfunctional compound By using the carboxylic acid-based compound (for example, dicarboxylic acid, carboxylic acid anhydride, or monohalogenocarboxylic acid) as the polyfunctional compound, for example, first, the polyfunctional compound is converted into “(X1) cardanol”. Or a derivative thereof ”, a functional group (for example, a carboxyl group, a carboxylic acid anhydride group or a halogen group (particularly a chloride group)) in the carboxylic acid compound, and“ (X1) cardanol or a derivative thereof ” A cardanol derivative to which the carboxylic acid compound is added is formed by bonding with the phenolic hydroxy group.
  • a functional group for example, a carboxyl group, a carboxylic acid anhydride group or a halogen group (particularly a chloride group)
  • the remaining functional group (carboxyl group) in the carboxylic acid compound is converted into a carboxylic acid halide group (particularly a carboxylic acid chloride group).
  • the converted “cardanol derivative added with a carboxylic acid compound” is reacted with “cellulose or a derivative thereof”, and the converted “cardanol derivative added with a carboxylic acid compound” is a carboxylic acid halide.
  • Grafting can be carried out by linking the group to a hydroxy group in “cellulose or a derivative thereof”. When the carboxylic acid compound is used, for example, grafting can be performed very efficiently.
  • the carbon atom to which the alcoholic hydroxy group (—OH) is bonded and the hydrocarbon group in the polyfunctional compound are for example, an ester bond (—CO—O—), an ether bond (—O—) or a urethane bond (—NH—CO—O—), preferably linked via an ester bond.
  • the carbon atom on the benzene ring to which the phenolic hydroxy group (—OH) in “(X1) cardanol or derivative thereof” and the hydrocarbon group of the polyfunctional compound are, for example, an ester bond (—CO They are bonded via —O—), ether bonds (—O—) or urethane bonds (—NH—CO—O—), preferably ester bonds or ether bonds.
  • (X1) cardanol or a derivative thereof means, for example, when using “cardanol or a derivative thereof” represented by the formula (2), the linear hydrocarbon (R) moiety of cardanol.
  • the conversion rate (hydrogenation rate) of the unsaturated bond of the linear hydrocarbon (R) portion of cardanol by hydrogenation is, for example, preferably 90 mol% or more, and more preferably 95 mol% or more.
  • the method of hydrogenating the cardanol in which the linear hydrocarbon group (R) is unsaturated is not particularly limited as long as hydrogenation to the benzene ring does not proceed, and is present in the chain of the linear unsaturated hydrocarbon.
  • a usual hydrogenation method that can be used for conversion to —CH 2 —CH 3 can be employed.
  • the catalyst used for the hydrogenation reaction include noble metals such as palladium, ruthenium and rhodium, and metals such as nickel.
  • the catalyst for example, a catalyst in which the various metals are supported on a support such as activated carbon, activated alumina, or diatomaceous earth can be used.
  • the hydrogenation reaction method is, for example, a batch method in which a powdered catalyst is added to a reaction solution containing cardanol, and the reaction is carried out while suspending and stirring, using a reaction tower packed with a molded catalyst, It is possible to employ a continuous system in which a reaction liquid containing is allowed to flow through the reaction tower to advance the reaction.
  • the solvent used for preparing the reaction solution containing cardanol does not act as a catalyst poison for the catalyst used, and is not particularly limited as long as cardanol exhibits solubility.
  • a solvent for the preparation of the reaction liquid containing cardanol
  • examples of the usable solvent include solvents such as alcohols, ethers, esters, and saturated hydrocarbons.
  • the reaction temperature of hydrogenation depends on the type of catalyst used, the hydrogen pressure in the reaction system, and the boiling point of the solvent used, but is not particularly limited as long as it is within an allowable range determined depending on the above conditions, For example, it can be set to 20 ° C. to 250 ° C., preferably 50 ° C. to 200 ° C.
  • the reaction temperature By setting the reaction temperature to be equal to or higher than the lower limit value, for example, the hydrogenation rate can be sufficiently maintained, and by setting the reaction temperature to be equal to or lower than the upper limit value, for example, generation of decomposition products can be sufficiently suppressed.
  • the hydrogen pressure in the reaction system in the hydrogenation reaction is, for example, 10 to 80 kgf / cm 2 (9.8 ⁇ 10 3 to 78.4 ⁇ 10 3 hPa), preferably 20 to 50 kgf / cm 2 (19 .6 ⁇ 10 3 to 49.0 ⁇ 10 3 hPa).
  • Hydrogenation to cardanol is, for example, grafting of a cardanol derivative to which a polyfunctional compound is added before forming a cardanol derivative to which the polyfunctional compound is added, after forming a cardanol derivative to which a polyfunctional compound is added, and before grafting. It can be done at any later time.
  • hydrogenation to cardanol is carried out, for example, from the viewpoint of hydrogenation and grafting reaction efficiency, before forming a cardanol derivative to which a polyfunctional compound is added, and before grafting of a cardanol derivative to which a polyfunctional compound is added. It is preferable to carry out the step before forming the cardanol derivative to which the polyfunctional compound is added.
  • the ratio of the “(X1) cardanol or derivative thereof” bound to the “cellulose or derivative thereof” to the “cellulose or derivative thereof”, that is, the grafting rate is, for example, ⁇ -glucose of “cellulose or a derivative thereof” ( ⁇ -D-glucopyranose) number of “(X1) cardanol or derivative thereof” added (average value), that is, the number of hydroxy groups bonded to “(X1) cardanol or derivative thereof (degree of hydroxy group substitution) , DS CD ).
  • the DS CD is, for example, preferably 0.1 or more, more preferably 0.2 or more, and can be set to 0.4 or more, for example.
  • the DS CD by setting more than the lower limit, for example, it is possible to secure sufficiently the effect of the grafting.
  • the ⁇ -glucose ( ⁇ -D-glucopyranose) unit constituting cellulose has three hydroxy groups (—OH) at the 2-position, 3-position and 6-position. Accordingly, the DS CD per unit of ⁇ -glucose ( ⁇ -D-glucopyranose) constituting cellulose is theoretically “3” or less.
  • the upper limit of DS CD is preferably set to, for example, 2.5 or less, more preferably 2 or less, from the viewpoint of ease of production (grafting). More preferably, it is set to 1.5 or less. Further, the upper limit value of the DS CD may be set to 1 or less, for example, and in this case, a sufficient improvement effect can be obtained.
  • DS CD in a cellulose resin to be produced is between the upper limit value and the lower limit value of DS CD of the DS CD, for example, depending on the desired properties, can be set as appropriate.
  • the DS CD in the cellulosic resin to be produced is, for example, not more than the upper limit of the DS CD , for example, sufficiently suppressing the improvement in tensile fracture strain (toughness) and having the maximum strength (tensile strength, bending). The decrease in strength can be sufficiently suppressed.
  • (X1) cardanol or a derivative thereof is grafted to “cellulose or a derivative thereof”, for example, a specific “reactive hydrocarbon compound” may be further grafted to “cellulose or a derivative thereof”. Good. Thereby, for example, the obtained cellulose resin can be further improved to desired characteristics.
  • the “reactive hydrocarbon compound” to be grafted is, for example, a compound having at least one functional group capable of reacting with a hydroxy group of “cellulose or a derivative thereof”.
  • the “reactive hydrocarbon compound” is, for example, a compound in which a reactive functional group is substituted on a “hydrocarbon” skeleton, and one of the reactive functional groups is a hydroxy group (—OH) and It is a functional group that can react.
  • a functional group capable of reacting with the hydroxy group (—OH) includes a carboxyl group (—COOH), a carboxylic acid halide group (—CO—X), or a carboxylic acid anhydride group.
  • at least one compound selected from monocarboxylic acids such as aliphatic monocarboxylic acids, aromatic monocarboxylic acids, and alicyclic monocarboxylic acids, acid halides or acid anhydrides thereof can be mentioned.
  • the aliphatic monocarboxylic acid include fatty acids having a linear or branched side chain.
  • Aromatic monocarboxylic acids are, for example, those in which a carboxyl group is directly bonded to an aromatic ring, those in which a carboxyl group is bonded to an aromatic ring via an alkylene group (for example, a methylene group, an ethylene group) (or an aliphatic ring having an aliphatic ring Group monocarboxylic acid group).
  • the alicyclic monocarboxylic acid is, for example, one having a carboxyl group directly bonded to the alicyclic ring, one having a carboxyl group bonded to the alicyclic ring via an alkylene group (for example, methylene group, ethylene group) (or to the alicyclic ring).
  • alkylene group for example, a methylene group, an ethylene group
  • fatty acid is defined as an aliphatic monocarboxylic acid having 4 or more carbon atoms that constitutes natural fat.
  • aliphatic monocarboxylic acids having 4 or more carbon atoms that constitute natural fat there are those having a hydroxy group (—OH) in addition to a carboxyl group (—COOH). Hydroxy-substituted aliphatic monocarboxylic acids having 4 or more carbon atoms derived from are also included in the fatty acids.
  • fatty acids derived from natural fat are aliphatic monocarboxylic acids having biodegradability.
  • Aliphatic monocarboxylic acid means a monocarboxylic acid represented by R—COOH, usually composed of a monovalent aliphatic hydrocarbon group R and a carboxyl group (—COOH).
  • “Aromatic monocarboxylic acid” means a monocarboxylic acid represented by R—COOH, usually composed of a monovalent aromatic hydrocarbon group R and a carboxyl group (—COOH).
  • the number of carbon atoms of the “hydrocarbon” skeleton constituting the “reactive hydrocarbon compound” is preferably selected in the range of 1 to 32, for example, and more preferably in the range of 1 to 20.
  • the “reactive hydrocarbon compound” is added to the hydroxy group of “cellulose or a derivative thereof”.
  • the “reactive hydrocarbon compound” is effective in improving characteristics, for example, when it is arranged so as to fill a gap portion of a three-dimensional structure composed of grafted “(Xi) cardanol or a derivative thereof”. is there.
  • an aromatic hydrocarbon group or an alicyclic hydrocarbon group is selected as the hydrocarbon group of the “reactive hydrocarbon compound”, for example, it is particularly effective for improving the rigidity and heat resistance of the resulting cellulose resin. is there. Further, when an aliphatic hydrocarbon group, particularly a linear aliphatic hydrocarbon group, is selected as the hydrocarbon group of the “reactive hydrocarbon compound”, for example, particularly to improve the toughness of the resulting cellulose resin. It is more effective.
  • aliphatic monocarboxylic acid used as the “reactive hydrocarbon compound” for example, Acetic acid, propionic acid; Butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearin Saturated fatty acids such as acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccellic acid; Unsaturated fatty acids such as 2-butenoic acid, 2-pentenoic acid, 2-hexenoic acid, 2-octenoic acid, 2-undecylenic acid, ole
  • the aromatic monocarboxylic acid used as the “reactive hydrocarbon compound” is, for example, An aromatic monocarboxylic acid in which a carboxyl group (—COOH) is directly bonded to a monocyclic or polycyclic aromatic ring (eg, benzene ring) such as benzoic acid (Ph—COOH); An aromatic monocarboxylic acid in which a carboxyl group (—COOH) is directly bonded to a monocyclic or polycyclic aromatic ring (eg, benzene ring) substituted with an alkyl group such as toluic acid (CH 3 —Ph—COOH) acid; A monocyclic or polycyclic aromatic ring (eg, benzene ring) such as phenylacetic acid (Ph—CH 2 COOH), phenylpropionic acid (Ph— (CH 2 ) 2 —COOH), etc.
  • a monocyclic or polycyclic aromatic ring eg, benzene ring
  • An aromatic monocarboxylic acid to which COOH) is bound An aromatic monocarboxylic acid having an aromatic polycyclic structure composed of two or more benzene rings such as biphenylcarboxylic acid (C 6 H 5 -C 6 H 5 -COOH), biphenylacetic acid; Examples thereof include aromatic monocarboxylic acids having a condensed ring structure containing a benzene ring such as naphthalenecarboxylic acid and tetralincarboxylic acid; and derivatives of the above-mentioned aromatic monocarboxylic acids.
  • the alicyclic monocarboxylic acid used as the “reactive hydrocarbon compound” is, for example, An alicyclic monocarboxylic acid in which a carboxyl group (—COOH) is directly bonded to a monocyclic or polycyclic alicyclic hydrocarbon ring such as cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid; An alicyclic monocarboxylic acid in which an aliphatic monocarboxylic acid group (—R—COOH) is bonded to a monocyclic or polycyclic alicyclic hydrocarbon ring such as cyclohexylacetic acid; and the above alicyclic monocarboxylic acid Derivatives of acids are mentioned.
  • an organic silicone compound or an organic fluorine compound may be added to the “reactive hydrocarbon compound” in the structure of the “hydrocarbon moiety” to which the reactive functional group is bonded.
  • an organosilicone compound or an organofluorine compound may be added to the structure of these “hydrocarbon moieties”, for example, the water resistance of the resulting cellulose resin can be further improved.
  • the reactive functional group of the “reactive hydrocarbon compound” is, for example, a functional group capable of reacting with a hydroxy group of cellulose.
  • the reactive functional group capable of reacting with an alcoholic hydroxy group include a carboxyl group (—COOH), a carboxylic acid halide group (—CO—X) (particularly, a carboxylic acid chloride group (—CO—Cl)), a carboxylic acid group.
  • a carboxyl group —COOH
  • a carboxylic acid halide group —CO—X
  • an epoxy group an isocyanate group (—N ⁇ C ⁇ O)
  • a halogen group (—X) particularly a chloride group (—Cl)
  • a carboxyl group (—COOH) or a carboxylic acid halide group (—CO—X) is preferably selected.
  • Examples of the “reactive hydrocarbon compound” having the carboxylic acid halide group (—CO—X) (particularly the carboxylic acid chloride group (—CO—Cl)) include, for example, the above-mentioned various monocarboxylic acids (R—COOH).
  • epoxy means a structure in which a group “—O—” forms a bridge structure between two carbon atoms present in a molecule.
  • a “1,2-epoxide structure” derived from a carbon-carbon double bond (> C ⁇ C ⁇ ) is a representative “epoxy structure”.
  • 1,8-epoxy-p-menthane (1 , 8-cineole) and a bridge structure with a group “—O—” different from “1,2-epoxide structure” is also included in the “epoxy” structure.
  • the “reactive hydrocarbon compound” is, for example, at least one selected from aromatic monocarboxylic acids or alicyclic monocarboxylic acids, particularly from the viewpoint of improving the rigidity (such as bending strength) of the obtained cellulose resin.
  • the monocarboxylic acid (R—COOH), its carboxylic acid halide (R—CO—Cl) or its acid anhydride ((RCO) 2 O) is preferred.
  • R—CO— acyl group
  • the average number of additions of the “reactive hydrocarbon compound” per unit of ⁇ -glucose ( ⁇ -D-glucopyranose) of “cellulose or its derivative” (addition number of acyl group (R—CO—)
  • the average value of the number of hydroxy groups bonded to the “reactive hydrocarbon compound” (hydroxy group substitution degree, DS XX ) is, for example, in the range of 0.1 or more and 0.6 or less from the viewpoint of obtaining a desired effect. Preferably, it selects in the range of 0.1 or more and 0.5 or less.
  • ⁇ - of “cellulose or a derivative thereof” obtained by grafting the “reactive hydrocarbon compound” The average value of the number of hydroxy groups remaining per unit of glucose ( ⁇ -D-glucopyranose) (hydroxy group residual degree, DS OH ) ensures, for example, sufficient water resistance of the finally obtained cellulose resin.
  • DS OH is preferably selected to be 0.9 or less, more preferably 0.7 or less.
  • the “reactive hydrocarbon compound” is obtained, for example, in the step of grafting “(Xi) cardanol or a derivative thereof” by a reaction with a hydroxy group (—OH) of “cellulose or a derivative thereof”.
  • “Reactive hydrocarbon compounds” can be grafted by reaction with (OH). By adopting the above procedure, for example, more homogeneous grafting becomes possible.
  • the “reactive hydrocarbon compound” and “(Xi) cardanol or a derivative thereof” may be added to the reaction system simultaneously or separately.
  • step of grafting “(Xi) cardanol or a derivative thereof”, for example, “cellulose or a derivative thereof”, “(Xi) cardanol or a derivative thereof”, or optionally added “reactive hydrocarbon compound” is added.
  • “Cellulose or a derivative thereof” is added to a soluble solvent, and the reaction can be carried out using the reaction system in the liquid phase.
  • the reaction temperature is not particularly limited as long as the grafting reaction of “(Xi) cardanol or a derivative thereof” proceeds.
  • the reaction is performed in a uniform solution state by heating to an appropriate temperature. Can proceed.
  • Solvents capable of dissolving “cellulose or derivatives thereof” used for the preparation of the reaction solution include, for example, dimethyl sulfoxide-amine solvents, dimethylformamide-chloral-pyridine solvents, dimethylacetamide-lithium chloride solvents, imidazo Examples thereof include a lithium-based ionic liquid, and a solvent other than the exemplified solvents can be used as long as “cellulose or a derivative thereof” can be uniformly dissolved.
  • a part of the hydroxy group (—OH) of the starting material “cellulose or a derivative thereof” is previously subjected to O-acylation and O-alkylation to form an ester structure (—O—CO—R), an ether structure ( -O-R), and the solubility is changed (improved) by reducing the intermolecular force caused by the hydroxy group (-OH) between the chains of "cellulose or its derivative”
  • a “derivative” may be used.
  • Examples of the “cellulose derivative” partially subjected to O-acylation and O-alkylation include, for example, an acyl group such as acetyl group, propionyl group, butyryl group, etc. on the hydroxy group (—OOH) of “cellulose”. It is preferable to use an acylated cellulose that has been O-acylated with (R—CO—) and converted to an ester structure (—O—CO—R). In particular, the hydroxy group (—OOH) is converted to an acetate structure (—O—CO—CH 3 ) using acetic acid (CH 3 —COOH) or acetic acid chloride (CH 3 —CO—Cl) ( O-acetylation is preferred) and cellulose acetate is preferably used.
  • an acyl group such as acetyl group, propionyl group, butyryl group, etc. on the hydroxy group (—OOH) of “cellulose”. It is preferable to use an acylated cellulose that has been O-acy
  • the “acylating agent” compound used for the O-acylation that is, for example, acetic acid, propionic acid, butyric acid, or acid halides or acid anhydrides derived from these monoalkanoic acids is the above-mentioned “reactive carbonization”. It is also an example of an aliphatic monocarboxylic acid, an acid halide or an acid anhydride derived from an aliphatic monocarboxylic acid that can be used as a “hydrogen compound”.
  • the remaining hydroxy groups in “cellulose or a derivative thereof” that are not used for grafting of “(X1) cardanol or a derivative thereof” are, for example, those that remain as a hydroxy group, as described above, O-acetylation, etc. Or modified (grafted) with the above-mentioned “reactive hydrocarbon compound”.
  • the conversion rate of the hydroxy group in the finally obtained cellulose resin is not particularly limited and can be determined as appropriate.
  • the conversion rate of the hydroxy group in the finally obtained cellulose resin is not particularly limited.
  • the average number of remaining hydroxy groups per unit of ⁇ -glucose ( ⁇ -D-glucopyranose) (hydroxy group residual degree, DS OH ) is, for example, From the viewpoint of sufficiently ensuring the water resistance of the finally obtained cellulose resin, it is preferably selected in the range of 0.9 or less, more preferably in the range of 0.7 or less.
  • a part of the hydroxy group in the “cellulose or derivative thereof” of the starting material is, for example, from the viewpoint of making the water absorption, mechanical strength, and heat resistance in a predetermined range in the cellulose resin finally obtained, O-acylated by reaction with the above-mentioned “reactive hydrocarbon compound” is preferable. Further, for example, from the viewpoint of the grafting reaction efficiency of “(X1) cardanol or a derivative thereof”, “(X1 Prior to the grafting of “) cardanol or a derivative thereof”, it is preferably appropriately O-acylated (particularly O-acetylated).
  • the average value of the degree of group substitution, DS AC ) is preferably selected in the range of 0.5 or more, more preferably in the range of 1.0 or more, and further preferably, from the viewpoint of obtaining a sufficient acylation effect, for example. Is selected in the range of 1.5 or more.
  • the hydroxy group substitution degree DS AC by the acylation is, for example, in the range of 2.7 or less. It is preferable to select, more preferably, the range is 2.5 or less, and further preferably, the range is 2.2 or less.
  • the acyl group to be added is, for example, an acetyl group (CH 3 —CO—), a propionyl group (CH 3 CH 2 —CO—) or a butyryl group (CH 3 — (CH 2 ) 2 —CO It is preferably at least one selected from-).
  • the degree of substitution is indicated as DS Ace
  • the degree of substitution is indicated as DS Pro
  • the degree of substitution is indicated as DS Bu .
  • the cellulose resin (X) contained in the cellulose resin composition according to the present invention includes, for example, a cellulose component and a cardanol component with respect to the entire cellulose resin after grafting from the viewpoint of ensuring sufficient plant utilization.
  • the total mass ratio (plant component ratio) is preferably selected to be, for example, 50% by mass or more, and more preferably 60% by mass or more.
  • the “plant component ratio” means that the cellulose component corresponds to, for example, the structure represented by the formula (1) in which the hydroxy group is not acylated or grafted, and the cardanol component is, for example, the formula (1) It is calculated as corresponding to the structure shown in 2).
  • the cellulose resin (X) to which the “acyl group represented by (X3) R—CO— and R is an aromatic hydrocarbon group having 6 to 12 carbon atoms” is added as described above.
  • the hydroxy group (—OH) in “cellulose or a derivative thereof” is an acyl group represented by the above “(X3) R—CO—, wherein R is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • an aroyl group (Ar—CO—) derived from allyl carboxylic acid (Ar—COOH) is an aroyl group (Ar—CO—) derived from allyl carboxylic acid (Ar—COOH).
  • acyl group represented by (X2) R—CO— wherein R is an aliphatic hydrocarbon group having 12 to 29 carbon atoms” or the above for the hydroxy group (—OH) in “cellulose or a derivative thereof” or
  • acyl group represented by (X3) R—CO— wherein R is an aromatic hydrocarbon group having 6 to 12 carbon atoms” includes, for example, an alcoholic hydroxy group (“cellulose or a derivative thereof”) It can be carried out by grafting a reactive hydrocarbon compound capable of forming an ester bond (—O—CO—) with respect to —OH).
  • the “reactive hydrocarbon compound” that can be bonded (grafted) to “cellulose or a derivative thereof” using the alcoholic hydroxy group (—OH) of “cellulose or a derivative thereof” will be described below. .
  • the “reactive hydrocarbon compound” is, for example, a compound having at least one functional group capable of reacting with a hydroxy group of “cellulose or a derivative thereof”.
  • At least one compound selected from monocarboxylic acids such as aliphatic monocarboxylic acid, aromatic monocarboxylic acid, and alicyclic monocarboxylic acid, its acid halide or acid anhydride
  • monocarboxylic acids such as aliphatic monocarboxylic acid, aromatic monocarboxylic acid, and alicyclic monocarboxylic acid, its acid halide or acid anhydride
  • aliphatic At least one compound selected from monoisocyanate, aromatic monoisocyanate, and alicyclic monoisocyanate mono (chloroformyl) oxy group-substituted aliphatic hydrocarbon, mono (chloroformyl) oxy group-substituted aromatic hydrocarbon, mono (chloro And at least one compound selected from formyl) oxy group-substituted alicyclic hydrocarbons, acrylic acid esters, and methacrylic acid esters.
  • aliphatic monocarboxylic acid examples include fatty acids having a linear or branched side chain.
  • Aromatic monocarboxylic acids are, for example, those in which a carboxyl group is directly bonded to an aromatic ring, or those in which a carboxyl group is bonded to an aromatic ring via an alkylene group (for example, a methylene group or an ethylene group) (an aliphatic carboxylic acid is bonded to an aromatic ring.
  • Acid group (bonded with —R—COOH)).
  • the alicyclic monocarboxylic acid is, for example, one in which a carboxyl group is directly bonded to the alicyclic ring, one in which a carboxyl group is bonded to the alicyclic ring via an alkylene group (for example, methylene group, ethylene group) (aliphatic to the alicyclic ring.
  • alkylene group for example, methylene group, ethylene group
  • Carboxylic acid groups (bonded with —R—COOH)).
  • aliphatic monoisocyanate examples include those in which one isocyanate group (—N ⁇ C ⁇ O) is bonded to an aliphatic hydrocarbon having a linear or branched side chain.
  • the alicyclic monoisocyanate is, for example, one in which an isocyanate group (—N ⁇ C ⁇ O) is directly bonded to the alicyclic ring, and one isocyanate group (for example, methylene group, ethylene group) via the alkylene group (for example, methylene group or ethylene group).
  • the mono (chloroformyl) oxy group-substituted aliphatic hydrocarbon (R—O—CO—Cl) is, for example, an aliphatic hydrocarbon having a linear or branched side chain and a single (chloroformyl) oxy group (— O-CO-Cl) substituted.
  • Mono (chloroformyl) oxy group-substituted aromatic hydrocarbons are, for example, those in which one (chloroformyl) oxy group (—O—CO—Cl) is directly bonded to the aromatic ring, and alkylene groups (for example, , A (chloroformyl) oxy group (—O—CO—Cl) bonded via a methylene group or an ethylene group (mono (chloroformyl) oxy group-substituted aliphatic hydrocarbon group ( -R-O-CO-Cl)).
  • Mono (chloroformyl) oxy group-substituted alicyclic hydrocarbons include, for example, those in which one (chloroformyl) oxy group (—O—CO—Cl) is directly bonded to the alicyclic ring, and alkylene groups ( For example, one (chloroformyl) oxy group (—O—CO—Cl) bonded via a methylene group or ethylene group (mono (chloroformyl) oxy group-substituted aliphatic hydrocarbon group on the alicyclic ring) (Where R—O—CO—Cl) is bonded).
  • the number of carbon atoms of the “hydrocarbon” to which the reactive functional group is bonded is preferably selected, for example, in the range of 1 to 30, more preferably 1 to 20.
  • the range is more preferably selected in the range 2-20, particularly preferably in the range 14-20.
  • the number of carbon atoms of the “hydrocarbon” to which the reactive functional group is bonded exceeds 30, for example, the molecular size of the “reactive hydrocarbon compound” itself becomes too large. The reaction efficiency decreases due to steric hindrance, and as a result, it becomes difficult to improve the grafting rate.
  • an aromatic hydrocarbon group or alicyclic hydrocarbon group as the hydrocarbon group constituting the "reactive hydrocarbon compound"
  • it is particularly effective for improving the rigidity and heat resistance of the resulting cellulose resin.
  • an aliphatic hydrocarbon group when selected, it is particularly effective for improving the toughness of the obtained cellulose resin.
  • aliphatic monocarboxylic acid used as a “reactive hydrocarbon compound”, Acetic acid, propionic acid; Butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearin Saturated fatty acids such as acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccellic acid; Unsaturated fatty acids such as butenoic acid, pentenoic acid, hexenoic acid, octenoic acid, undecylenic acid, oleic acid, sorbic
  • aromatic monocarboxylic acid used as a “reactive hydrocarbon compound” An aromatic monocarboxylic acid in which a carboxyl group (—COOH) is directly bonded to a monocyclic or polycyclic aromatic ring (eg, benzene ring) such as benzoic acid (Ph—COOH); An aromatic monocarboxylic acid in which a carboxyl group (—COOH) is directly bonded to a monocyclic or polycyclic aromatic ring (eg, benzene ring) substituted with an alkyl group such as toluic acid (CH 3 —Ph—COOH) acid; A monocyclic or polycyclic aromatic ring (eg, benzene ring) such as phenylacetic acid (Ph—CH 2 COOH), phenylpropionic acid (Ph— (CH 2 ) 2 —COOH), etc.
  • a monocyclic or polycyclic aromatic ring eg, benzene ring
  • phenylacetic acid Ph
  • An aromatic monocarboxylic acid to which COOH) is bound An aromatic monocarboxylic acid having an aromatic polycyclic structure composed of two or more benzene rings such as biphenylcarboxylic acid (C 6 H 5 -C 6 H 5 -COOH), biphenylacetic acid; Examples thereof include aromatic monocarboxylic acids having a condensed ring structure containing a benzene ring such as naphthalenecarboxylic acid and tetralincarboxylic acid; and derivatives of the above-mentioned aromatic monocarboxylic acids.
  • alicyclic monocarboxylic acid used as the “reactive hydrocarbon compound” for example, An alicyclic monocarboxylic acid in which a carboxyl group (—COOH) is directly bonded to a monocyclic or polycyclic alicyclic hydrocarbon ring such as cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid; An alicyclic monocarboxylic acid in which an aliphatic monocarboxylic acid group (—R—COOH) is bonded to a monocyclic or polycyclic alicyclic hydrocarbon ring such as cyclohexylacetic acid; and the above alicyclic monocarboxylic acid Derivatives of acids are mentioned.
  • aliphatic monoisocyanate used as the “reactive hydrocarbon compound”
  • examples of the aliphatic monoisocyanate (RN—C ⁇ O) used as the “reactive hydrocarbon compound” include, for example, Saturated aliphatic monoisocyanates such as methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, decyl isocyanate, dodecyl isocyanate, octadecyl isocyanate (monoisocyanate group substitution) Saturated aliphatic hydrocarbons); Unsaturated aliphatic monoisocyanates (monoisocyanate group-substituted unsaturated aliphatic hydrocarbons) such as but
  • aromatic monoisocyanate used as the “reactive hydrocarbon compound” for example, An aromatic monoisocyanate in which one isocyanate group (—N ⁇ C ⁇ O) is directly bonded to a monocyclic or polycyclic aromatic ring (eg, benzene ring) such as phenyl isocyanate; An aromatic monoisocyanate in which one isocyanate group (—N ⁇ C ⁇ O) is directly bonded to a monocyclic or polycyclic aromatic ring (eg, benzene ring) substituted with an alkyl group such as tolyl isocyanate; An aromatic monoisocyanate in which an aliphatic isocyanate group (—RN—C ⁇ O) is bonded to a monocyclic or polycyclic aromatic ring (for example, benzene ring) such as phenylmethyl isocyanate and phenylethyl isocyanate; Aromatic isocyanate in which one isocyanate group (—RN—C ⁇ O) is bonded
  • One isocyanate group (—R—N ⁇ C) for an aromatic hydrocarbon having a condensed ring structure containing one benzene ring in an aromatic hydrocarbon having a condensed ring structure containing a benzene ring such as naphthalene isocyanate or tetralin isocyanate.
  • Aromatic isocyanates to which O) is bound; as well as derivatives of these aromatic isocyanates.
  • alicyclic monoisocyanate used as the “reactive hydrocarbon compound” for example, Cyclopentyl isocyanate, cyclohexyl isocyanate, cyclooctyl isocyanate, and other monocyclic or polycyclic alicyclic hydrocarbon rings having one isocyanate group (—RN—C ⁇ O) directly bonded thereto Isocyanates;
  • Examples include alicyclic monoisocyanate derivatives.
  • Examples of the mono (chloroformyl) oxy group-substituted aliphatic hydrocarbon (RO—CO—Cl) used as the “reactive hydrocarbon compound” include, for example, Methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, butyl chloroformate, pentyl chloroformate, hexyl chloroformate, heptyl chloroformate, octyl chloroformate, nonyl chloroformate, decyl chloroformate, dodecyl chloroformate, chloroformate Mono (chloroformyl) oxy group-substituted saturated aliphatic hydrocarbons such as octadecyl; Mono (chloroformyl) oxy group-substituted unsaturated aliphatic hydrocarbons such as butenyl chloroformate, pentenyl chloroformate, he
  • the mono (chloroformyl) oxy group-substituted aromatic hydrocarbon used as the “reactive hydrocarbon compound” for example, Mono (chloroformyl) oxy group-substituted aromatic carbonization in which one mono (chloroformyl) oxy group (ClCOO-) is directly bonded to a monocyclic or polycyclic aromatic ring such as phenyl chloroformate (for example, benzene ring) hydrogen; Mono (chloroformyl) in which one mono (chloroformyl) oxy group (ClCOO-) is directly bonded to a monocyclic or polycyclic aromatic ring (eg, benzene ring) substituted with an alkyl group such as tolyl chloroformate ) Oxy-substituted aromatic hydrocarbons; Mono- or chloro-formate (Cl—COO—CH 2 —Ph), phenethyl chloroformate (Cl—COO—CH 2 CH 2 —
  • One mono (chloroformyl) oxy group (ClCOO-) is bonded to an aromatic hydrocarbon having a condensed ring structure containing a benzene ring, such as mono (chloroformyl) oxynaphthalene and mono (chloroformyl) oxytetralin.
  • the mono (chloroformyl) oxy group-substituted alicyclic hydrocarbon used as the “reactive hydrocarbon compound” for example, A mono (chloroformyl) oxy group (ClCOO-) directly bonded to a monocyclic or polycyclic alicyclic hydrocarbon ring such as cyclopentyl chloroformate, cyclohexyl chloroformate, cyclooctyl chloroformate, etc.
  • Chloroformyl) oxy-substituted alicyclic hydrocarbons Mono (chloroformyl) oxy group-substituted aliphatic hydrocarbons in monocyclic or polycyclic alicyclic hydrocarbon rings such as (cyclohexyl) methyl chloroformate (Cl—COO—CH 2 —C 6 H 11 ) Mono (chloroformyl) oxy group-substituted alicyclic hydrocarbons to which the group (—R—O—CO—Cl) is bound; and derivatives of these mono (chloroformyl) oxy group-substituted alicyclic hydrocarbons .
  • an organic silicone compound or an organic fluorine compound may be added to the structure of the “hydrocarbon” portion of the “reactive hydrocarbon compound”.
  • the “hydrocarbon” structure to which these organosilicone compounds or organofluorine compounds are added, for example, the water resistance of the resulting cellulose resin can be further improved.
  • the reactive functional group of the “reactive hydrocarbon compound” is, for example, a functional group capable of reacting with a hydroxy group (—OH) of cellulose.
  • the reactive functional group include a carboxyl group (—COOH), a carboxylic acid halide group (—CO—X) (particularly a carboxylic acid chloride group (—CO—Cl)), a carboxylic acid anhydride group (—CO—).
  • isocyanate groups (—N ⁇ C ⁇ O), (chloroformyl) oxy groups (—O—CO—Cl), epoxy groups and halogen groups (particularly chloride groups) may be mentioned.
  • a carboxyl group (—COOH), a carboxylic acid halide group (—CO—X), an isocyanate group (—N ⁇ C ⁇ O), a (chloroformyl) oxy group (—O—).
  • CO—Cl is preferable, and a carboxylic acid chloride group (—CO—Cl), an isocyanate group (—N ⁇ C ⁇ O), and a (chloroformyl) oxy group (—O—CO—Cl) are particularly preferable.
  • the carboxylic acid halide group (—CO—X) (particularly, the carboxylic acid chloride group (—CO—Cl)) is, for example, an acid halide group obtained by acid-halogenating the carboxyl group (—COOH) of the above-mentioned various monocarboxylic acids.
  • —CO—X an acid chloride group (—CO—Cl)) may be mentioned.
  • epoxy means a structure in which a group “—O—” forms a bridge structure between two carbon atoms present in a molecule.
  • a “1,2-epoxide structure” derived from a carbon-carbon double bond (> C ⁇ C ⁇ ) is a representative “epoxy structure”.
  • 1,8-epoxy-p-menthane (1 , 8-cineole) and a bridge structure with a group “—O—” different from “1,2-epoxide structure” is also included in the “epoxy” structure.
  • the “reactive hydrocarbon compound” is, for example, at least one selected from aromatic monocarboxylic acids and alicyclic monocarboxylic acids, particularly from the viewpoint of improving the rigidity (bending strength, etc.) of the resulting cellulose resin.
  • Monocarboxylic acid (R—COOH), its acid halide R—CO—X) or its acid anhydride (R—CO—O—CO—R) aromatic monoisocyanate (RN—C ⁇ O), Alicyclic monoisocyanate (RN—C ⁇ O), mono (chloroformyl) oxy group-substituted aromatic hydrocarbon (R—O—CO—Cl), mono (chloroformyl) oxy group-substituted alicyclic hydrocarbon (R—O—CO—Cl) is preferred.
  • the “reactive hydrocarbon compound” By adding the “reactive hydrocarbon compound” to the hydroxy group of “cellulose or a derivative thereof”, for example, it is derived from at least one monocarboxylic acid selected from aromatic monocarboxylic acids and alicyclic monocarboxylic acids. Substitution of carbamoyl group (O—CO—NH—R) derived from at least one monoisocyanate selected from acyl group (O—CO—R), aromatic monoisocyanate and alicyclic monoisocyanate, mono (chloroformyl) oxy group Substitution of at least one mono (chloroformyl) oxy group selected from aromatic hydrocarbons (R—O—CO—Cl) and mono (chloroformyl) oxy group-substituted alicyclic hydrocarbons (R—O—CO—Cl) The hydrocarbon group derived from hydrocarbon (—O—CO—O—R) is The “hydrocarbon moiety R” derived from the “reactive hydrocarbon compound” is added to
  • the number of addition of the “reactive hydrocarbon compound” per ⁇ -glucose ( ⁇ -D-glucopyranose) unit of “cellulose or its derivative” (ester bond (—O—CO—R), urethane bond (—O—) CO—NH—R) or carbonic acid ester bond (—O—CO—O—R) addition number, DS XX ) average value, that is, with the bond with the “reactive hydrocarbon compound”, the substitution
  • the average value of the number of received hydroxy groups (hydroxy group substitution degree) is preferably 0.1 or more and 0.6 or less, and more preferably 0.1 or more and 0.5 or less, for example, from the viewpoint of obtaining a desired effect. It is.
  • At least one acyl group selected from, for example, an acetyl group, a propionyl group or a butyryl group may be added to the hydroxy group of “cellulose or a derivative thereof”.
  • the average value of the number of acyl groups added (DS AC ) per ⁇ -glucose ( ⁇ -D-glucopyranose) unit of “cellulose or a derivative thereof” can be set to 0.5 or more, for example.
  • a “second acyl group” derived from at least one selected monocarboxylic acid may be added.
  • the average value of the number of “first acyl groups” added (DS AC ) per ⁇ -glucose ( ⁇ -D-glucopyranose) unit of “cellulose or a derivative thereof” can be set to 0.5 or more, for example.
  • the average value of the number of added “second acyl groups” (DS XX ) can be set to 0.1 or more, for example.
  • the “(X1) cardanol or a derivative thereof” is added as the cellulose resin (X) to be used
  • the “(X1) cardanol or its Average number of additions (DS CD ) of “(X1) cardanol or a derivative thereof” per ⁇ -glucose ( ⁇ -D-glucopyranose) unit constituting the cellulosic resin to which the “derivative” is added
  • the average value of the number of hydroxyl groups (—OH) (DS OH ), the above-mentioned “O-acylation, O-alkylation”, or a hydroxy group to which a specific “reactive hydrocarbon compound” is added the number of sum of the average value of (DS OX);
  • the average value of the addition number (DS CD) derivatives thereof ", the sum of the average value of the number of remaining to have hydroxy group (-OH) (DS OH) ( DS CD + DS OH) is generally from 0.2 to
  • the average value of the number of additions (DS CD ) of “(X1) cardanol or a derivative thereof” is usually 0 in the range of 1.5, preferably in the range of 0.3 to 1.0. It is desirable to select in the range of 1 to 0.8, preferably in the range of 0.2 to 0.6.
  • the cellulose resin (X) used is an acyl represented by “(X2) R—CO—, wherein R is an aliphatic hydrocarbon group having 12 to 29 carbon atoms.
  • the “acyl group represented by (X2) R—CO—, wherein R is an aliphatic hydrocarbon group having 12 to 29 carbon atoms” is added.
  • acyl group represented by (X2) R—CO— wherein R is an aliphatic hydrocarbon group having 12 to 29 carbon atoms.
  • the cellulose resin (X) used is an acyl represented by “(X3) R—CO—, wherein R is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • the “acyl group represented by (X3) R—CO—, wherein R is an aromatic hydrocarbon group having 6 to 12 carbon atoms” is added.
  • the average number of added groups (DS X3 ), the average number of remaining hydroxy groups (—OH) (DS OH ), the aforementioned “O-acylation, O-alkylation”, or a specific Hydrode added with "reactive hydrocarbon compound”
  • the number of alkoxy groups sum of the average value of (DS OX); (DS X3 + DS OH + DS OX) is substantially the (DS X3 + DS OH + DS OX) 3.
  • acyl group represented by (X3) R-CO-, wherein R is an aromatic hydrocarbon group having 6 to 12 carbon atoms mean value of the additional number (DS X3) of "generally in the range of 0.1-0.8, preferably 0.2-0.6 It is desirable to select the range.
  • the olefin resin (Y) includes polyethylene (— (CH 2 CH 2 ) n —), polyethylene having a polar group in a part of the structure, and polypropylene (— (CH (CH 3 ) CH 2 ). n- ), polypropylene having a polar group in a part of its structure, olefinic thermoplastic elastomer, and the like.
  • the ratio of the “comonomer” unit having the “polar group” and the “ethylene” unit or the “propylene” unit introduced into the “polyethylene” chain or the “polypropylene” chain is, for example,
  • the ratio “comonomer” unit number / “ethylene” unit number ranges from 0.5 / 100 to 10/100
  • the ratio “comonomer” unit number / “propylene” unit number ranges from 0.5 / 100 to 10/100. It is preferable to select each in the range.
  • polyethylene for example, Low density comonomer and rich ethylene, linear high density polyethylene; Linear low density polyethylene with high comonomer content and crystallization inhibition; Low density polyethylene using a metallocene catalyst and having a narrow molecular distribution controlled is preferred.
  • polyethylene synthesized using the lowest density metallocene catalyst because the effect of improving impact resistance is high.
  • polyethylene having a polar group introduced into a part of the structure is preferably polyethylene modified with maleic anhydride.
  • the “polar group” introduced by the “maleic anhydride modification” is “—CO—O—CO—” derived from maleic anhydride.
  • polypropylene having a polar group introduced into a part of the structure is preferably polypropylene modified with maleic anhydride.
  • the “polar group” introduced by the “maleic anhydride modification” is “—CO—O—CO—” derived from maleic anhydride.
  • the “olefinic thermoplastic elastomer” consists of polypropylene as the hard segment and ethylene propylene rubber as the soft segment.
  • the hard segment and the soft segment are simply mechanically kneaded and blended, and only the soft segment is organically oxidized. A type crosslinked with a product is preferred.
  • the “olefin resin (Y)” may be, for example, only one type or a combination of two or more types.
  • the content ratio of the cellulose resin (X) and the olefin resin (Y) is such that the content of the cellulose resin (X) is the content of the olefin resin (Y).
  • the ratio of the content (wt) W Y of the olefin resin (Y) is, for example, the weight ratio W X : W Y is selected in the range of at least 100: 1 to 100: 100.
  • the weight ratio; W X : W Y is usually in the range of 100: 2 to 100: 50, preferably in the range of 100: 3 to 100: 30, and more preferably. Is preferably in the range of 100: 4 to 100: 25, more preferably in the range of 100: 5 to 100: 17.5, and particularly in the range of 100: 5 to 100: 15.
  • the cellulose resin composition according to the present invention contains a plasticizer (Z) in addition to the cellulose resin (X) and the olefin resin (Y).
  • a plasticizer (Z) in addition to the cellulose resin (X) and the olefin resin (Y).
  • the ratio of (weight) W Z is, for example, the weight ratio; W X : (W Y + W Z ) is usually in the range of 100: 4 to 100: 25, preferably 100: 5 to 100: 17.5. It is desirable to select within the range of 100: 5 to 100: 15.
  • content and (weight) W X of the cellulose-based resin (X), the ratio of the content (wt) W Z of the plasticizer (Z), the weight ratio; W X: the W Z at least, It is desirable to select in the range of 100: 0 to 100: 17.5, preferably in the range of 100: 5 to 100: 15.
  • the content ratio (by weight) W Y content of the cellulose-based resin (X) (weight) W X and, wherein the olefin-based resin (Y) The weight ratio; W X : W Y is preferably selected in the range of 100: 5 to 100: 17.5, more preferably in the range of 100: 5 to 100: 15.
  • Plasticizer in addition to the cellulose resin (X) and the olefin resin (Y), a form containing a plasticizer (Z) can be adopted.
  • a plasticizer (Z) for example, various plasticizers used for the purpose of improving impact resistance can be used in preparing the cellulose resin composition.
  • plasticizer (Z) examples include the plasticizers exemplified below because the cellulose-based resin composition according to the present invention has an effect of further improving the thermoplasticity and elongation at break.
  • the plasticizer that can be added to the cellulose resin composition according to the present invention is, for example, Phthalic acid esters such as dibutyl phthalate, diaryl phthalate, diethyl phthalate, dimethyl phthalate, di-2-methoxyethyl phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate; Tartrate esters such as dibutyl tartrate; Adipic acid esters such as dioctyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate; Polyhydric alcohol esters such as triacetin (1-O, 2-O, 3-O-triacetylglycerol), diacetylglycerol, tripropanoylglycerol (glyceryl tripropionate), glycerol monostearate; Phosphate esters such as triethyl phosphate
  • the plasticizer can more effectively improve the impact resistance in addition to thermoplasticity and elongation at break, so that dioctyl adipate, benzyl-2-butoxy adipate are used. Ethoxyethyl, tricresyl phosphate, diphenyl cresyl phosphate and diphenyl octyl phosphate are preferred.
  • Cyclohexanedicarboxylic acid esters such as dihexylcyclohexanedicarboxylate, dioctylcyclohexanedicarboxylate, di-2-methyloctylcyclohexanedicarboxylate; Trimellitic acid esters such as dihexyl trimellitic acid, diethylhexyl trimellitic acid, and dioctyl trimellitic acid; Examples include pyromellitic esters such as dihexyl pyromellitic acid, diethylhexyl pyromellitic acid, and dioctyl pyromellitic acid.
  • plasticizer examples include a reactive functional group (a carboxylic acid group, a group derived from a carboxylic acid group, and other functional groups) in the plasticizer, and a hydroxy group or a non-functional group of “(X1) cardanol or a derivative thereof”.
  • a modified plasticizer to which “(X1) cardanol or a derivative thereof” is added by reacting with a saturated bond (carbon-carbon double bond) may be used.
  • the cellulosic resin to which the “(X1) cardanol or derivative thereof” is added or the “(X2) R—CO— is represented, and R is a carbon number of 12 It is possible to improve the compatibility between the cellulose resin to which “acyl group as an aliphatic hydrocarbon group of ⁇ 29” is added and the modified plasticizer to which “(X1) cardanol or a derivative thereof” is added. The effect of adding the modified plasticizer in the cellulosic resin composition can be further improved.
  • additives for example, an additive may be further included in addition to the plasticizer (Z).
  • the additive for example, various additives used in ordinary thermoplastic resin compositions can be applied.
  • a filler may be added as necessary.
  • the “filler” include inorganic or organic particulate or fibrous fillers.
  • filler that can be added to the cellulose resin composition according to the present invention, for example, Mineral particles (talc, mica, calcined siliceous clay, 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, magnesium aluminosilicate, 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 carb
  • fibrous filler examples include organic fibers (natural fibers, papers, etc.), inorganic fibers (glass fibers, carbon fibers, silica fibers, silica / alumina fibers, wollastonite, zirconia fibers, potassium titanate). Fibers), metal fibers, and the like.
  • fibers natural fibers, papers, etc.
  • inorganic fibers glass fibers, carbon fibers, silica fibers, silica / alumina fibers, wollastonite, zirconia fibers, potassium titanate). Fibers), metal fibers, and the like.
  • fibers for example, any one type may be used, or two or more types may be used in combination.
  • the addition ratio of the “filler” is the total volume V Total of the cellulose resin composition to which the “filler” is added.
  • the volume ratio of V filler , the total volume of added “fillers”, V Total : V filler is usually in the range of 100: 1 to 100: 50, preferably 100: 2 to 100: Select a range of 40.
  • a flame retardant may be added as necessary.
  • the flame retardant include phosphorus compounds such as phosphate esters and phosphazenes; metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and hydrotalcite.
  • General flame retardants such as basic magnesium carbonate, calcium carbonate, silica, alumina, talc, clay, zeolite, bromine flame retardant, antimony trioxide, melamine flame retardant and the like. Any one kind of these flame retardants may be used, or two or more kinds may be used in combination.
  • a rubber component or a silicone compound may be added as an “impact resistance improver” as necessary.
  • the “rubber component” that can be used in the cellulose resin composition according to the present invention include natural rubber, epoxidized natural rubber, and synthetic rubber.
  • Examples of the “silicone compound” that can be used in the cellulose resin composition according to the present invention include, for example, an organic polysiloxane formed by polymerization of alkylsiloxane, alkylphenylsiloxane, or the like, or a side chain of the organic polysiloxane, Ends are polyether, methylstyryl (Ph—C (CH 3 ) ⁇ CH—), alkyl group, higher fatty acid ester, alkoxy group, fluorine, amino group, epoxy group (epoxy ring), carboxyl group, carbinol group ( Modified with hydroxymethyl group: —CH 2 —OH), methacryl group (CH 2 ⁇ CH (CH 3 ) —), mercapto group (sulfanyl group: —SH), phenol group (—C 6 H 4 —OH), etc. Examples thereof include modified silicone compounds.
  • the “impact resistance improver” for example, any one kind may be used, or two or more kinds may be used
  • additives that are applied to ordinary resin compositions such as a colorant, an antioxidant, and a heat stabilizer may be added.
  • thermoplastic resin (Y ′) other than the “olefin resin (Y)” may be added as necessary.
  • thermoplastic resin (Y ′) other than the “olefin resin (Y)” is not particularly limited.
  • a thermoplastic resin excellent in flexibility such as a thermoplastic polyurethane elastomer (TPU) is used. Can be mentioned.
  • TPU thermoplastic polyurethane elastomer
  • the content of the “thermoplastic resin (Y ′)” (particularly TPU) is not particularly limited.
  • the “cellulose” the content of the system resin (X) "(by weight) and W X, the 'content' (by weight) W Y" thermoplastic resin (Y) 'ratio, by weight; W X: W Y', the lower limit Is preferably selected to be 100: 1 or higher, more preferably 100: 5 or higher.
  • the weight ratio; W X : W Y ′ is the upper limit, and 100: 20 It is preferable to select below, and more preferably 100: 15 or below.
  • W X: (W Y + W Y ′ ) is usually in the range of 100: 2 to 100: 50, preferably in the range of 100: 3 to 100: 30, more preferably in the range of 100: 4 to 100: 25, Preferably, it is selected in the range of 100: 5 to 100: 17.5, particularly in the range of 100: 5 to 100: 15.
  • thermoplastic polyurethane elastomer that can be used as a general “thermoplastic resin (Y ′)” is not particularly limited.
  • polyol polyol
  • diisocyanate polyisocyanate
  • chain extender chain extender
  • polyol polyol
  • examples of the “polyol” used for the preparation of “re-urethane elastomer (TPU)” include polyester polyol, polyester ether polyol, polycarbonate polyol, and polyether polyol.
  • polyester polyol for example, Aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, azelaic acid, etc.), aromatic dicarboxylic acids (phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.), alicyclic dicarboxylic acids (hexahydrophthalic acid, Polyvalent carboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, etc., or their acid esters or anhydrides, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3- Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,3-octane
  • polyester ether polyol for example, Aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, azelaic acid, etc.), aromatic dicarboxylic acids (phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.), alicyclic dicarboxylic acids (hexahydrophthalic acid, Polyhydric carboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid, etc., or acid esters or anhydrides thereof, glycols such as diethylene glycol or alkylene oxide adducts (such as propylene oxide adducts), etc., or mixtures thereof And a compound obtained by a dehydration condensation reaction.
  • aromatic dicarboxylic acids phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.
  • polycarbonate polyol for example, Ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1 , 5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol and other polyhydric alcohols, and diethylene carbonate, dimethyl carbonate, diethyl carbonate, etc.
  • the polycarbonate polyol obtained by making it react is mentioned. Further, it may be a copolymer of polycaprolactone polyol (PCL) and polyhexamethylene carbonate (PHL).
  • polyether polyol for example, Polyethylene glycol (H— (O—CH 2 CH 2 ) n —OH) and polypropylene glycol (H— (O—CH) obtained by polymerizing (ring-opening polymerization) cyclic ethers such as ethylene oxide, propylene oxide, and tetrahydrofuran, respectively. 2 CH (CH 3 )) n —OH), polytetramethylene ether glycol (H— (O—CH 2 CH 2 CH 2 CH 2 ) n —OH) and the like, and copolyethers thereof.
  • the diisocyanate used for forming the TPU for example, Tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) Xylylene diisocyanate (XDI), hydrogenated XDI, tetramethylxylene diisocyanate (TMXDI), 1,8-diisocyanate methyloctane, lysine ester triisocyanate, dicyclohexylmethane diisocyanate (hydrogenated MDI; HMDI), and the like.
  • TDI Tolylene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • NDI 1,5-naphthylene diis
  • Examples of the “chain extender” used for forming the TPU include a low molecular weight polyol.
  • the “low molecular weight polyol” for example, Ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1 , 5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, 1,4-cyclohexanedimethanol (1,4-di (hydroxymethyl) cyclohexane), fats such as glycerin Group polyols; 1,4-dimethylolbenzene (1,4-di (hydroxymethyl) benzene), bisphenol A (2,2-di (p-hydroxyphenyl)
  • the TPU may be further copolymerized with a silicone compound. Thereby, further excellent impact resistance can be obtained.
  • any one type of TPU may be used, or two or more types may be used in combination.
  • the method for producing the cellulose resin composition according to the present invention is not particularly limited.
  • the cellulose resin composition according to the present invention can be obtained, for example, by mixing the cellulose resin (X) and the olefin resin (Y).
  • the mixing method is not particularly limited, and it is preferable to perform melt mixing using, for example, hand mixing or a known mixer.
  • a compounding device such as a tumbler mixer, a ribbon blender, a single screw mixing extruder, a multi-screw mixing extruder, a kneading kneader, a kneading roll, or the like can be used.
  • the melt-mixed mixture may be further granulated, for example, in an appropriate shape as necessary, and this may be used as the cellulose resin composition according to the present invention.
  • Another method for producing the cellulose resin composition according to the present invention is, for example, a method in which the cellulose resin (X) and the olefin resin (Y) are dispersed and mixed in a solvent such as an organic solvent. Is mentioned.
  • the mixed mixture may further include, for example, a coagulation solvent as needed, and then evaporate the solvent, which may be used as the cellulose resin composition according to the present invention.
  • a production method in which a mixed composition of the various additives and the resin is obtained and then the solvent is evaporated.
  • plasticizer (Z) and the “thermoplastic resin” are added as needed when mixing the “cellulose-based resin (X)” and the “olefin-based resin (Y)”. (Y ′) ”and the like are added to prepare a mixed composition.
  • the total content (weight) W X of the cellulose resin (X) is, for example, the cellulose resin composition according to the present invention.
  • the weight ratio; W total: the W X the lower limit is 100: preferably 50 or more, more preferably, 100: 60 or more, the upper limit is 100: 95 or more preferably More preferably, it is 100: 99 or more.
  • the content (weight) W X of the cellulose resin (X) and the content (weight) of the olefin resin (Y) contained in the cellulose resin composition is, for example, weight ratio; W X : W Y is usually in the range of 100: 2 to 100: 50, preferably in the range of 100: 3 to 100: 30, more preferably It is desirable to select in the range of 100: 4 to 100: 25, more preferably in the range of 100: 5 to 100: 17.5, and particularly in the range of 100: 5 to 100: 15.
  • content and (weight) W X of the cellulose-based resin (X), the ratio of the content (wt) W Z of the plasticizer (Z), the weight ratio; W X: the W Z at least, It is desirable to select in the range of 100: 0 to 100: 17.5, preferably in the range of 100: 5 to 100: 15.
  • the content ratio (by weight) W Y content of the cellulose-based resin (X) (weight) W X and, wherein the olefin-based resin (Y) The weight ratio; W X : W Y is preferably selected in the range of 100: 5 to 100: 17.5, more preferably in the range of 100: 5 to 100: 15.
  • the “thermoplastic resin (Y ′)” (particularly, TPU) having excellent flexibility is added.
  • W X : W Y ′ is preferably selected to have a lower limit of 100: 1 or more, and more preferably 100: 5 or more.
  • the weight ratio; W X : W Y ′ is the upper limit, and 100: 20 It is preferable to select below, and more preferably 100: 15 or below.
  • W X : (W Y + W Y ′ ) is usually in the range of 100: 2 to 100: 50, preferably in the range of 100: 3 to 100: 30, more preferably in the range of 100: 4 to 100: 25. More preferably, it is desirable to select in the range of 100: 5 to 100: 17.5, particularly in the range of 100: 5 to 100: 15.
  • the impact resistance of the cellulose-based resin composition is the “cellulosic resin used for the preparation of the cellulose-based resin composition”. "It is desirable that it exceeds at least 1.25 times, usually 1.5 times, based on its own impact resistance. Further, in the cellulose resin composition according to the present invention, when the “filler” is not added, the strength of the cellulose resin composition, in particular, the bending strength, is used for the preparation of the cellulose resin composition. It is desirable that the “cellulosic resin” is maintained within a range not less than 1 ⁇ 2 on the basis of the bending strength of the cellulosic resin itself.
  • the impact resistance of the cellulose resin composition, and the bending strength are within a range that does not fall below the target level.
  • the content (weight) W X of the cellulose-based resin (X) wherein the olefinic content of the resin (Y) (weight) W Y, the content of the "plasticizer (Z)" (by weight) W Z, Content (weight) W Y ′ ratio of the “thermoplastic resin (Y ′)”, for example, weight ratio; W X : W Y , weight ratio; W X : (W Y + W Z ), weight ratio; W X : It is desirable to select (W Y + W Y ′ ), respectively.
  • the impact resistance of the cellulose resin composition according to the present invention is further improved with the addition of the “filler”. At that time, a decrease in strength, particularly bending strength, is further suppressed. Accordingly, in the cellulose resin composition according to the present invention, even when the “filler” is added, the content of the olefin resin (Y) with respect to the content (weight) W X of the cellulose resin (X).
  • the amount (by weight) W Y, the ratio of the content of the "plasticizer (Z)" (by weight) W Z, the "thermoplastic resin (Y ')" content (wt) W Y' for example, the weight ratio W X : W Y , weight ratio; W X : (W Y + W Z ), weight ratio; W X : (W Y + W Y ′ ) are preferably selected in the above ranges, respectively.
  • the form of the cellulose resin composition according to the present invention is not particularly limited, and may be, for example, a solid such as a solution, pellet, powder, particle, or block.
  • the molding material according to the present invention is a molding material containing a resin component exhibiting thermoplasticity, and includes the cellulose resin composition according to the present invention as the resin component exhibiting thermoplasticity.
  • the molding material according to the present invention includes, for example, the cellulose resin composition according to the present invention in a form in which no “filler” is added as a “base resin”, and a desired “filler” or the like depending on the application. Are added to the “base resin” and mixed uniformly.
  • the molding material according to the present invention is useful as a raw material for various molded products such as casings for exteriors for electronic devices, which are produced by applying a molding method under pressure and heating such as an injection molding method.
  • the “base resin” means, for example, a main component in the molding material, and means that other components are allowed to be contained within a range not impeding the function of the main component.
  • the content ratio of the “base resin” that is the main component is not particularly limited, and is, for example, 50% by mass or more of the entire molding material. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more.
  • the molding material according to the present invention may contain, for example, a binder, a solvent and the like in addition to the cellulose resin composition according to the present invention.
  • the form of the molding material according to the present invention is not particularly limited, and may be, for example, a solid such as a solution, pellet, powder, particle, or block.
  • the molded article according to the present invention is a molded article produced using a molding material containing a thermoplastic resin component, and the thermoplastic resin component contained in the molding material is It is a cellulose resin composition according to the invention.
  • the molded article according to the present invention is not limited as long as the cellulosic resin composition according to the present invention is used as the thermoplastic resin component contained in the molding material.
  • Examples of the “molded product” to which the molded product according to the present invention is applied include a housing such as an exterior for an electronic device, an internal part of an electronic device, a sheet, a film, a packaging container, and the like.
  • cellulose resin (X) contained in the cellulose resin composition according to the present invention
  • cellulose resin 1 and cellulose resin 2 grafted with hydrogenated cardanol are preferably used. The procedure is described below.
  • the carboxyl group of the carboxylated hydrogenated cardanol was chlorinated with oxalyl chloride and converted to an acid chloride group to obtain a chloride of monochloroacetic acid-modified cardanol (chlorinated hydrogenated cardanol).
  • the chlorinated hydrogenated cardanol is a derivative in which R is R1 and —OH is substituted with —O—CH 2 —CO—Cl in the formula (1). A specific method is shown below.
  • To the reaction solution adjusted to pH 1, 250 mL of methanol and 500 mL of diethyl ether are added, and 200 mL of distilled water is further added. Since O-carboxymethylated hydrogenated cardanol is not acid dissociated, it migrates into the ether layer. This mixed solution is separated into a water layer and an ether layer using a separatory funnel, and the water layer is discarded. The ether layer is then washed twice with 400 mL of distilled water. To the ether layer after washing, anhydrous magnesium sulfate is added and dried. Thereafter, the magnesium sulfate is filtered off.
  • the obtained filtrate (ether layer) is concentrated under reduced pressure with an evaporator (90 ° C./3 mmHg), and a yellowish brown powdery crude product is recovered as a residue.
  • the recovered crude product is recrystallized from n-hexane.
  • the purified product recovered by recrystallization (O-carboxymethylated hydrogenated cardanol) is vacuum dried and recovered as a white powder. 46 g (0.12 mol) of a white powder of the recrystallized and purified product (carboxymethylated hydrogenated cardanol) was recovered.
  • hydrogenated cardanol-grafted cellulose is formed by the reaction of an acid chloride group (—CO—Cl) and a hydroxy group (—OH) to form —O—CO— (ester bond) according to the following procedure.
  • Acetate (cellulose resin 1) is prepared.
  • Cellulose acetate manufactured by Daicel Chemical Industries, Ltd., trade name L-70, addition number of acetic acid per unit of ⁇ -glucose ( ⁇ -D-glucopyranose) of cellulose (acetylation substitution degree: DS Ace ) 2 .4 is used. 15.8 g of cellulose acetate (hydroxy group content: 0.036 mol) is dissolved in 200 mL of dehydrated dioxane, and 5.0 mL (0.036 mol) of triethylamine functioning as a reaction catalyst and an acid scavenger is added to the solution.
  • reaction solution is slowly dropped into 3 L of methanol while stirring to precipitate a reaction product (hydrogenated cardanol-grafted cellulose acetate).
  • the solid (fine powder) of the precipitated reaction product (hydrogenated cardanol grafted cellulose acetate) is filtered off.
  • the solid (fine powder) separated by filtration is air-dried overnight, and further dried under vacuum at 105 ° C. for 5 hours, whereby the dried fine powder of the cellulose resin 1 is recovered. 19 g of dried fine powder of cellulose resin 1 (hydrogenated cardanol grafted cellulose acetate) was recovered.
  • FIG. 1 shows a process chart (Synthesis Example A (1) ⁇ Synthesis Example A (2)) from the starting raw material cardanol until the cellulose resin 1 (hydrogenated cardanol-grafted cellulose acetate) is obtained.
  • the amount (mole unit) of chlorinated hydrogenated cardanol used in the reaction is selected with respect to the hydroxy group amount (mole unit) present in the cellulose acetate.
  • the synthesized hydrogenated cardanol-grafted cellulose acetate (cellulose-based resin 2 ') is purified, and a dried fine powder of the cellulose-based resin 2' is recovered.
  • reaction solution is slowly dropped into 3 L of methanol while stirring to precipitate a reaction product (hydrogenated cardanol-grafted cellulose acetate).
  • the solid (fine powder) of the precipitated reaction product (hydrogenated cardanol grafted cellulose acetate) is filtered off.
  • the solid (fine powder) separated by filtration is air-dried overnight, and further vacuum-dried at 105 ° C. for 5 hours to recover the dried fine powder of the cellulose resin 2 ′. 18 g of dried fine powder of cellulosic resin 2 '(hydrogenated cardanol-grafted cellulose acetate) was recovered.
  • the amount (mol unit) of benzoyl chloride used in the reaction is selected with respect to the hydroxy group amount (mole unit) present in the cellulose resin 2 ′ as the intermediate raw material.
  • the synthesized benzoyl / hydrogenated cardanol-grafted cellulose acetate (cellulose-based resin 2) is purified, and the dried fine powder of the cellulose-based resin 2 is recovered.
  • reaction solution is slowly dropped into 3 L of methanol while stirring to precipitate a reaction product (benzoyl / hydrogenated cardanol-grafted cellulose acetate).
  • the solid (fine powder) of the precipitated reaction product (benzoyl / hydrogenated cardanol grafted cellulose acetate) is filtered off.
  • the solid (fine powder) separated by filtration is air-dried overnight, and further dried under vacuum at 105 ° C. for 5 hours, whereby the dried fine powder of the cellulose resin 2 is recovered. 17 g of dried fine powder of cellulose resin 2 (benzoyl / hydrogenated cardanol grafted cellulose acetate) was recovered.
  • ⁇ -glucose ( ⁇ -D-glucopyranose) unit in purified polymer (benzoyl / hydrogenated cardanol-grafted cellulose acetate) by 1 H-NMR (manufactured by Bruker, product name: AV-400, 400 MHz)
  • the signal intensity derived from per-O—CO—CH 3 , —O—CO—C 6 H 5 , —OH, —O—CO—CH 2 —O— is measured.
  • Synthesis Example A-2 Synthesis of Cellulose Resin 3 Grafted with Stearoyl Group (Octadecanoyl Group: CH 3 — (CH 2 ) 16 —CO—)
  • Synthesis Example A-2 Stearic Acid Graft Synthesis of cellulose acetate (cellulose-based resin 3) Stearic acid chloride (CH 3 — (CH 2 ) 16 —CO—Cl; manufactured by Tokyo Chemical Industry Co., Ltd.) was converted into cellulose by the same procedure as in Synthesis Example A (2).
  • the amount (mole unit) of stearic acid chloride used in the reaction is selected with respect to the hydroxy group amount (mole unit) present in the cellulose acetate.
  • the synthesized stearic acid grafted cellulose acetate (cellulose resin 3) is purified, and the dried fine powder of the cellulose resin 3 is recovered.
  • reaction solution is slowly added dropwise to 3 L of methanol with stirring to precipitate a reaction product (stearic acid grafted cellulose acetate).
  • the precipitated reaction product (stearic acid grafted cellulose acetate) solid (fine powder) is filtered off.
  • the solid (fine powder) separated by filtration is air-dried overnight, and further dried under vacuum at 105 ° C. for 5 hours, whereby the dried fine powder of the cellulose resin 3 is recovered. 20 g of dried fine powder of cellulose resin 3 (stearic acid grafted cellulose acetate) was recovered.
  • the resulting Wet crystal is slurried in 125 ml of acetonitrile and stirred at room temperature for 1 hour. After standing at ⁇ 15 ° C. overnight, the crystals are filtered (5A, 185 mm ⁇ ). Wet crystals are dried under vacuum ( ⁇ 0.4 kPa) at 30 ° C. for 6 hours. 22.61 g of a white powder (Dry crystal) of a diisocyanate-added cardanol derivative in which HDI and hydrogenated cardanol are combined at a ratio of 1: 1 through —O—CO—NH— (urethane bond) is recovered.
  • a white powder (Dry crystal) of the recovered product (diisocyanate-added fully hydrogenated cardanol derivative) was measured by a liquid chromatograph (manufactured by Shimadzu Corporation, product name: LC-10ADVP). In the white powder (Dry crystal) The purity (content rate) of the diisocyanate-added fully hydrogenated cardanol derivative contained in is calculated. The calculated purity (content ratio) was 91% by mass.
  • the 43.9 g of the recovered Dry polymer and 600 ml of methyl ethyl ketone are stirred at a liquid temperature of 70 to 80 ° C. for 1 hour to dissolve the polymer. Thereafter, the polymer solution is cooled to 30 ° C. to precipitate insolubles. The polymer solution is centrifuged to separate the precipitated insoluble matter by sedimentation (3500 rpm ⁇ 15 minutes). Next, 1 L of hexane is added to the polymer solution recovered as a supernatant to precipitate the polymer. The precipitated polymer is filtered and washed twice with 1 L of hexane. Repeat the same operation twice. Thereafter, it is dried under reduced pressure ( ⁇ 0.8 kPa) at 50 ° C. for 14 hours to recover the purified polymer (fully hydrogenated cardanol-grafted cellulose acetate). 36.4 g of purified polymer (total hydrogenated cardanol grafted cellulose acetate) was recovered.
  • the recovered polymer After washing, the recovered polymer is dried and then dissolved in 250 ml of chloroform at a liquid temperature of 60 ° C. After cooling, 1.3 L of methanol is added while stirring the solution to precipitate the polymer. The precipitated polymer is filtered and the recovered polymer is washed twice with 100 ml of methanol. After washing, the recovered polymer is dried under vacuum ( ⁇ 0.7 kPa) at 105 ° C. for 16 hours to recover the purified polymer (fully hydrogenated cardanol grafted cellulose acetate propionate). 35.8 g of purified polymer (total hydrogenated cardanol grafted cellulose acetate propionate) was recovered.
  • the cellulosic resin 1, the cellulosic resin 2, the cellulosic resin 3, the cellulosic resin 4, the commercially available cellulosic resin 5, the olefinic resin and the plasticizer are described in Tables 3-1 to 3-1 below. After kneading with the combination (composition) shown in 3-7, a molded product is produced using the prepared cellulose resin composition.
  • compositions shown in Table 3-1 to Table 3-7, the content of each cellulose resin, olefin resin and plasticizer is expressed using “parts by mass” as a unit.
  • Impact resistance evaluation Notch is made on one side of the central part of a test piece having a thickness of 2.5 mm, a width of 12.8 mm, and a length of 80 mm, and the Izod impact strength with a notch is measured in accordance with JIS K7110. .
  • the measuring device used for measuring the notched Izod impact strength is an impact test device manufactured by Toyo Seiki.
  • the cellulose resin composition according to the present invention by combining the cellulose resin (X) and the olefin resin (Y), for example, the raw material of the non-edible part is used, and good Thermoplastic (formability) and impact resistance can be realized. For this reason, according to the present invention, for example, it is possible to provide a molding material and a molded product such as a durable product such as an electronic device by using the raw material of the non-edible part.
  • the cellulose resin (X) is a cellulose resin obtained by adding the following (X1), the following (X2), or the following (X3) to cellulose or cellulose derivative;
  • the olefin resin (Y) is selected from the group consisting of polyethylene, polyethylene having a polar group in part of its structure, polypropylene, polypropylene having a polar group in part of its structure, and an olefinic thermoplastic elastomer.
  • a cellulosic resin composition characterized in that
  • the cellulose resin (X) is a cellulose resin obtained by adding the following (X1), the following (X2), or the following (X3) to cellulose or a cellulose derivative; (X1) Cardanol or a derivative thereof; (X2) an acyl group represented by R—CO—, wherein R is an aliphatic hydrocarbon group having 12 to 29 carbon atoms; (X3) an acyl group represented by R—CO—, wherein R is an aromatic hydrocarbon group having 6 to 12 carbon atoms,
  • the olefin resin (Y) is selected from the group consisting of polyethylene, polyethylene having a polar group in part of its structure, polypropylene, polypropylene having a polar group in part of its structure, and olefinic thermoplastic elastomer. Is; The cellulose resin composition further comprising a plasticizer (Z) in addition to the cellulose resin (X)
  • (Appendix 3) Cellulosic resin (X) to which (X1) cardanol or a derivative thereof is added, A hydroxy group of the (X1) cardanol or a derivative thereof or a substituent thereof; By reaction between the hydroxy group of the cellulose or cellulose derivative or a substituent thereof, The cellulose resin composition according to appendix 1 or appendix 2, wherein the cellulose or cellulose derivative is a cellulose resin in which the (X1) cardanol or a derivative thereof is added via a covalent bond.
  • R is a saturated aliphatic hydrocarbon group represented by — (CH 2 ) 14 CH 3 ;
  • the hydrogen of the hydroxy group (—OH) may be substituted by a substituent;
  • the cellulose resin composition according to any one of Appendix 1, Appendix 2, and Appendix 3.
  • R1 is a saturated aliphatic hydrocarbon group represented by — (CH 2 ) 14 CH 3 ;
  • R3 is an unsaturated aliphatic hydrocarbon group represented by — (CH 2 ) 7 CH ⁇ CHCH 2 CH ⁇ CH (CH 2 ) 2 CH 3 ;
  • R4 is an unsaturated aliphatic hydrocarbon group represented by — (CH 2 ) 7 CH ⁇ CHCH 2 CH ⁇ CHCH 2 CH ⁇ CH 2 ;
  • the hydrogen of the phenolic hydroxy group (—OH) may be substituted by a substituent;
  • the cellulose resin composition according to any one of Appendix 1, Appendix 2, and Appendix 3.
  • the cellulose resin (X) is 6.
  • the cellulose resin (X) is A cellulose resin in which (X1) cardanol or a derivative thereof is added to the cellulose or cellulose derivative via a urethane bond (—O—CO—NH—); Any one of appendix 2, appendix 11, and appendix 12, wherein the plasticizer (Z) includes a compound having a structure in which two ester bonds (—O—CO—) are contained in the molecule.
  • Cellulosic resin composition according to item.
  • Appendix 15 A molding material containing a resin component exhibiting thermoplasticity, 15.
  • a molding material comprising the cellulose resin composition according to any one of appendices 1 to 14 as the resin component exhibiting thermoplasticity.
  • Appendix 16 A molded article produced using a molding material containing a resin component exhibiting thermoplasticity, 15. A molded product, wherein the resin component exhibiting thermoplasticity contained in the molding material is the cellulose resin composition according to any one of appendix 1 to appendix 14.

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Abstract

La présente invention concerne une composition de résine de cellulose ayant une bonne thermoplasticité, c'est-à-dire, une aptitude au moulage, une excellente résistance au choc, et un taux d'utilisation élevé de matières premières non comestibles. La composition de résine de cellulose comprend la résine de cellulose (X) suivante et la résine oléfinique (Y) suivante. (X) est une résine de cellulose à laquelle les composés (X1), (X2), ou (X3) suivants ont été ajoutés : (X1) cardanol ou un de ses dérivés ; (X2) un groupe acyle représenté par R-CO- dans lequel R est un groupe hydrocarboné aliphatique en C12-C29 ; ou (X3) un groupe acyle représenté par R-CO- dans lequel R est un groupe hydrocarboné aromatique en C6-C12. (Y) est une résine oléfinique sélectionnée dans le groupe constitué d'un polyéthylène, d'un polyéthylène ayant un groupe polaire dans une partie de la structure, d'un polypropylène, d'un polypropylène ayant un groupe polaire dans une partie de la structure, et d'un élastomère thermoplastique à base d'oléfine.
PCT/JP2013/080285 2012-12-07 2013-11-08 Composition de résine de cellulose et son utilisation WO2014087801A1 (fr)

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JP2019183022A (ja) * 2018-04-12 2019-10-24 東洋インキＳｃホールディングス株式会社 樹脂組成物および成形体
CN110483695A (zh) * 2019-08-28 2019-11-22 福建师范大学泉港石化研究院 一种反应挤出合成腰果酚接枝高密度聚乙烯及其在竹塑复合材料中的应用
CN110872392A (zh) * 2018-08-31 2020-03-10 富士施乐株式会社 树脂组合物和树脂成型品
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CN112745533A (zh) * 2019-10-31 2021-05-04 富士施乐株式会社 树脂组合物和树脂成型体
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CN112745533B (zh) * 2019-10-31 2023-10-31 富士胶片商业创新有限公司 树脂组合物和树脂成型体

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