WO2011078289A1 - Molding material, molded article and process for production thereof, and housing for electric/electronic device - Google Patents

Molding material, molded article and process for production thereof, and housing for electric/electronic device Download PDF

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Publication number
WO2011078289A1
WO2011078289A1 PCT/JP2010/073244 JP2010073244W WO2011078289A1 WO 2011078289 A1 WO2011078289 A1 WO 2011078289A1 JP 2010073244 W JP2010073244 W JP 2010073244W WO 2011078289 A1 WO2011078289 A1 WO 2011078289A1
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group
molding material
cellulose
material according
cellulose derivative
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PCT/JP2010/073244
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French (fr)
Japanese (ja)
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俊英 芳谷
茂生 上平
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富士フイルム株式会社
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08Cellulose derivatives
    • C08L1/32Cellulose ether-esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00Preparation of cellulose ethers
    • C08B11/02Alkyl or cycloalkyl ethers
    • C08B11/04Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/08Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with hydroxylated hydrocarbon radicals; Esters, ethers, or acetals thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B13/00Preparation of cellulose ether-esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08Cellulose derivatives
    • C08L1/26Cellulose ethers
    • C08L1/28Alkyl ethers
    • C08L1/284Alkyl ethers with hydroxylated hydrocarbon radicals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005Stabilisers against oxidation, heat, light, ozone
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08Cellulose derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to a molding material, a molded body, a manufacturing method thereof, and a casing for electrical and electronic equipment.
  • PC Polycarbonate
  • ABS Acrylonitrile-butadiene-styrene resin
  • PC / ABS etc.
  • These resins are produced by reacting compounds obtained from petroleum as a raw material.
  • fossil resources such as oil, coal, and natural gas are mainly composed of carbon that has been fixed in the ground for many years.
  • fossil resources or products made from fossil resources are burned and carbon dioxide is released into the atmosphere, carbon that was originally not deep in the atmosphere but fixed deep in the ground Is rapidly released as carbon dioxide, and carbon dioxide in the atmosphere greatly increases, which causes global warming.
  • polymers such as ABS and PC made from petroleum, which is a fossil resource, have excellent characteristics as materials for electrical and electronic equipment, but are made from petroleum, which is a fossil resource. Therefore, it is desirable to reduce the amount used from the viewpoint of preventing global warming.
  • a plant-derived resin is originally produced by a photosynthesis reaction using carbon dioxide and water in the atmosphere as raw materials. Therefore, even if plant-derived resin is incinerated to generate carbon dioxide, the carbon dioxide is equivalent to carbon dioxide originally in the atmosphere, so the balance of carbon dioxide in the atmosphere is plus or minus zero After all, there is an idea that the total amount of CO 2 in the atmosphere is not increased. Based on this idea, plant-derived resins are referred to as so-called “carbon neutral” materials. The use of carbon-neutral materials in place of petroleum-derived resins is an urgent need to prevent global warming in recent years.
  • hydroxypropylmethylacetylcellulose is described in Patent Document 3 and Patent Document 4.
  • Patent Document 3 and Patent Document 4 describe that this hydroxypropylmethylacetylcellulose is useful as an additive for reducing the vapor pressure of an organic solvent that easily volatilizes.
  • the substitution degree of each substituent in hydroxypropylmethylacetylcellulose described in Patent Document 3 and Patent Document 4 is, for example, a molar substitution degree (MS) of hydroxypropyl group in a range of about 2 to 8, a substitution degree of methyl group Is in the range of about 0.1 to 1 and the degree of substitution of the acetyl group is in the range of about 0.8 to 2.5.
  • MS molar substitution degree
  • Patent Document 5 hydroxypropylmethylpropylcellulose, hydroxypropylmethylbutylcellulose and the like
  • Patent Document 6 hydroxypropylmethylserose phthalate and the like
  • Patent Document 7 discloses an example of a film containing butyl cellulose acetate and an aromatic polyester resin.
  • the inventors of the present invention focused on using cellulose as a carbon neutral resin.
  • cellulose since cellulose generally does not have thermoplasticity, it is difficult to mold by heating or the like, and thus is not suitable for molding. Further, even if thermoplasticity can be imparted, there is a problem that strength such as impact resistance is greatly reduced.
  • the cellulose derivatives described in Patent Documents 3, 4, and 6 are water-soluble or swellable and lack strength, which is not preferable as a molding material.
  • the cellulose derivative described in Patent Document 5 is described as being poorly water-soluble, but only described in the text, and its synthesis method and usage form are specifically disclosed in Examples and the like. Absent.
  • membrane formed using the cellulose derivative and aromatic polyester resin of patent document 7 can be used for a specific use as a coating film, it is not suitable for the use as a general molding material. Moreover, even if it can be set as a molded object, it is thought that it is inferior to impact resistance. In general, it is preferable that the molded bodies or the molded body and other members are not rubbed (not excellent in slidability) when the molded body is rubbed. However, a resin composition using a conventional cellulose derivative is preferred in this respect. It was also necessary to improve.
  • the object of the present invention is to achieve performance such as rigidity (flexural modulus), bending strength, and heat resistance (thermal deformation temperature), and even better impact resistance (Charpy impact strength), excellent moldability, and slidability. It is providing the molding material and molded object which have these. Another object of the present invention is to provide a method for producing the molded body and a housing for electrical and electronic equipment composed of the molded body.
  • the present inventors pay attention to the molecular structure of cellulose, make cellulose a cellulose derivative having a specific structure having an ether structure and an ester structure, and a molding material containing the cellulose derivative having the specific structure and an aromatic polyester, The inventors have found that it is possible to provide a molding material and a molded body having excellent impact resistance, molding processability, and slidability as well as performance such as good rigidity, bending strength, and heat resistance, and completed the present invention. It was. That is, the said subject can be achieved by the following means.
  • R C1 represents a hydrocarbon group
  • R C2 represents an alkylene group having 2 to 4 carbon atoms
  • n represents an integer of 1 or more.
  • [14] [13] The molding material according to [13], wherein the compatibilizer is a carboxylic acid anhydride or a compound having at least one selected from the group consisting of an epoxy group, an isocyanate group, and an oxazoline group.
  • [15] [1] A molded product obtained by thermoforming the molding material according to any one of [14].
  • [16] [1] A method for producing a molded body, comprising a step of heating and molding the molding material according to any one of [14].
  • [17] [15] A casing for an electric and electronic device comprising the molded article according to [15].
  • the molding material of the present invention has excellent thermoplasticity, it can be molded by heat molding or the like. Further, the molding material and the molded body of the present invention are excellent in performance such as rigidity, bending strength, and heat resistance, and have good impact resistance, molding processability, and sliding property. It can be suitably used as a component part such as an electric / electronic device, a machine part, a house / building material, and the like. Moreover, since the molding material of this invention uses the cellulose derivative obtained from the cellulose which is plant-derived resin, it can substitute for the conventional petroleum-derived resin as a raw material which can contribute to global warming prevention.
  • the hydrogen atom of the hydroxyl group contained in cellulose is A cellulose derivative (hereinafter also referred to as “cellulose derivative”) comprising at least one group substituted with A) below and at least one group substituted with B) below;
  • the present invention relates to a molding material containing an aromatic polyester.
  • R B represents a hydrocarbon group.
  • the cellulose derivative contained in the molding material of the present invention has a hydrogen atom of a hydroxyl group contained in cellulose. It is a cellulose derivative (hereinafter also referred to as “cellulose derivative”) containing at least one group substituted by A) below and at least one group substituted by B) below.
  • R 2 , R 3 and R 6 are each independently a hydrogen atom, A) hydrocarbon group: —R A , B) acyl group: —CO—R B (R B is carbon Represents a hydrogen group) or other substituents. However, at least a part of R 2 , R 3 , and R 6 represents A) a hydrocarbon group, and at least a part of R 2 , R 3 , and R 6 represents B) an acyl group.
  • the cellulose derivative in the present invention has thermoplasticity because at least part of the hydroxyl group of the ⁇ -glucose ring is etherified and esterified with A) a hydrocarbon group and B) an acyl group. It can be expressed and is suitable for molding. Furthermore, since cellulose is a completely plant-derived component, it is carbon neutral and can greatly reduce the burden on the environment.
  • the “cellulose” referred to in the present invention is a polymer compound in which a large number of glucoses are bonded by ⁇ -1,4-glycosidic bonds, and the carbon atoms at the 2nd, 3rd and 6th positions in the glucose ring of cellulose. Means that the hydroxyl group bonded to is unsubstituted. Further, “hydroxyl group contained in cellulose” refers to a hydroxyl group bonded to carbon atoms at the 2nd, 3rd and 6th positions in the glucose ring of cellulose.
  • the cellulose derivative only needs to contain the A) hydrocarbon group and B) acyl group in any part of the whole, and may be composed of the same repeating unit, or a plurality of types. It may consist of repeating units.
  • the cellulose derivative does not need to contain all of the A) hydrocarbon group and B) acyl group in one repeating unit. More specific embodiments include the following embodiments, for example. (1) At least one of R 2 , R 3 and R 6 is A) a repeating unit substituted with a hydrocarbon group, and at least one of R 2 , R 3 and R 6 is substituted with B) an acyl group A cellulose derivative composed of repeating units.
  • At least one of R 2 , R 3 and R 6 of one repeating unit is substituted with A) a hydrocarbon group, and at least one of the other is substituted with B) an acyl group ( That is, a cellulose derivative composed of the same type of repeating units having the substituents A) and B) in one repeating unit.
  • the cellulose derivative may contain an unsubstituted repeating unit (that is, a repeating unit in which R 2 , R 3 and R 6 are all hydrogen atoms in the general formula (A)).
  • the cellulose derivative may have other substituents other than a hydrogen atom, A) a hydrocarbon group, and B) an acyl group.
  • R A may be an aliphatic group or an aromatic group.
  • R A When R A is an aliphatic group, it may be linear, branched, or cyclic, and may have an unsaturated bond. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
  • R A When R A is an aromatic group, it may be either a single ring or a condensed ring. In the case where R A is an aromatic group, the preferred carbon number is 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10.
  • the aromatic group examples include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
  • the hydrocarbon group is preferably an aliphatic group because the resulting molding material (hereinafter sometimes referred to as “cellulose resin composition” or “resin composition”) has excellent impact resistance. From the viewpoint of excellent moldability such as melt flow rate, an alkyl group is more preferable, and an alkyl group having 1 to 4 carbon atoms (lower alkyl group) is more preferable.
  • Specific examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, tert-butyl group, isoheptyl group, and the like.
  • a group or an ethyl group is particularly preferred.
  • R B represents a hydrocarbon group.
  • R B is an aliphatic group, and may be any aromatic group. If R B is an aliphatic group, straight chain, branched, and may be any of circular, it may have an unsaturated bond. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group. If R B is an aromatic group may be either monocyclic and condensed. Examples of the aromatic group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. R B is preferably an alkyl group or an aryl group.
  • R B is more preferably an alkyl group having 1 to 12 carbon atoms or an aryl group, still more preferably an alkyl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms (preferably a methyl group).
  • R B it is also preferably a hydrocarbon group having a branched structure having 3 to 10 carbon atoms, more preferably an alkyl group having a branched structure having 3 to 10 carbon atoms, having 7-9 carbon atoms More preferably, it is an alkyl group having a branched structure.
  • the R B specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, 3-heptyl, 2-ethylhexyl group, tert- butyl Group, isoheptyl group, and the like.
  • R B is a methyl group, an ethyl group, a propyl group, a 3-heptyl group, or a 2-ethylhexyl group, and more preferably a methyl group, an ethyl group, a 3-heptyl group, or a 2-ethylhexyl group.
  • the cellulose derivative in the molding material of the present invention is a cellulose derivative in which the hydrogen atom of the hydroxyl group contained in cellulose contains at least one group substituted with A) and at least one group substituted with B).
  • it is preferable from the viewpoint of impact resistance that it further contains at least one group in which the hydrogen atom of the hydroxyl group contained in cellulose is substituted by the following C).
  • C) a group containing an alkyleneoxy group: —R C2 —O— and an acyl group: —CO—R C1 (R C1 represents a hydrocarbon group, and R C2 represents an alkylene group having 2 to 4 carbon atoms. )
  • R C1 represents a hydrocarbon group.
  • R C1 the same groups as those described above for R B can be applied.
  • the preferred range of R C1 is the same as R B.
  • R C2 represents an alkylene group having 2 to 4 carbon atoms.
  • R C2 may be linear, branched or cyclic, but is preferably linear or branched, and more preferably branched.
  • the alkyleneoxy group (—R C2 —O—) is preferably an alkyleneoxy group having 2 or 3 carbon atoms. Specific examples of the alkyleneoxy group preferably include the following structures.
  • a group represented by the following formula (1) or (2) in which —R C2 —O— is branched is preferable because the obtained resin composition has excellent bending elastic modulus.
  • the group of C) may contain a plurality of alkyleneoxy groups or may contain only one.
  • the group of C) can be represented by the following general formula (3).
  • R C1 represents a hydrocarbon group
  • R C2 represents an alkylene group having 2 to 4 carbon atoms.
  • the preferred ranges of R C1 and R C2 are the same as those described above.
  • n is an integer of 1 or more.
  • the upper limit of n is not particularly limited, and varies depending on the amount of alkyleneoxy group introduced, but is about 10, for example.
  • n is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1.
  • R C2 When a plurality of R C2 are present, they may be the same or different, but are preferably the same.
  • the cellulose derivative in the present invention is a group of C) containing only one alkyleneoxy group (a group in which n is 1 in the general formula (3)) and C) containing two or more alkyleneoxy groups. And a group (a group in which n is 2 or more in the above general formula (3)).
  • the bonding direction of the alkyleneoxy group to the cellulose derivative in the group C) is not particularly limited, but it is preferable that the alkylene group part (R C2 ) of the alkyleneoxy group is bonded to the ⁇ -glucose ring structure side.
  • R A in A), R B in B ), R C1 and R C2 in C) may have a further substituent or may be unsubstituted, but are preferably unsubstituted.
  • R A in the A), R B in the B), in the case where the where R C1 and R C2 in the C) has a further substituent examples of the further substituent include a halogen atom (e.g. fluorine atom, chlorine atom, bromine Atoms, iodine atoms), hydroxy groups, alkoxy groups (the alkyl group preferably has 1 to 5 carbon atoms), alkenyl groups, and the like.
  • R C2 has 2 or 3 carbon atoms. Note that when R A , R B , and R C1 are other than an alkyl group, they may have an alkyl group (preferably having a carbon number of 1 to 5) as a substituent.
  • R B and R C1 have a further substituent, it is preferable that they substantially have no carboxyl group, sulfonic acid group, and salts thereof.
  • the molding material of the present invention can be made water-insoluble and the moldability can be further improved.
  • the cellulose derivative has a carboxyl group, a sulfonic acid group, and a salt thereof, it is known that the compound stability is deteriorated, and in particular, thermal decomposition may be promoted. It is preferable.
  • substantially free of carboxyl groups, sulfonic acid groups, and salts thereof means only when the cellulose derivative in the present invention has no carboxyl groups, sulfonic acid groups, and salts thereof.
  • the case where the cellulose derivative in the present invention has a trace amount of carboxyl groups, sulfonic acid groups, and salts thereof in a range insoluble in water is included.
  • the cellulose as a raw material may contain a carboxyl group
  • the cellulose derivative using the above-described substituents A) to C) introduced therein may contain a carboxyl group.
  • a sulfonic acid group, and a cellulose derivative substantially free of salts thereof may contain 1% by mass or less, more preferably 0.5% by mass or less, based on the cellulose derivative.
  • the cellulose derivative in the present invention is preferably insoluble in water.
  • “being insoluble in water” means that the solubility in 100 parts by mass of water at 25 ° C. is 5 parts by mass or less.
  • cellulose derivative in the present invention examples include acetyl methyl cellulose, acetyl ethyl cellulose, acetyl propyl cellulose, acetyl butyl cellulose, acetyl pentyl cellulose, acetyl hexyl cellulose, acetyl cyclohexyl cellulose, acetyl phenyl cellulose, acetyl naphthyl cellulose, propionyl methyl cellulose, and propionyl ethyl cellulose.
  • the molding material of the present invention may contain only one kind of the specific cellulose derivative or two or more kinds.
  • substitution degree are not particularly limited.
  • a hydrocarbon group the degree of substitution DS A of —R A (the number of RA for the hydroxyl groups at the 2nd, 3rd and 6th positions of the ⁇ -glucose ring in the repeating unit) is 1.0 ⁇ DS A It is preferable that 1.0 ⁇ DS A ⁇ 2.5. Further, DS A is preferably 1.1 or more.
  • the number of unsubstituted hydroxyl groups present in the cellulose derivative is not particularly limited.
  • the degree of substitution DS H of hydrogen atoms (ratio in which the hydroxyl groups at the 2nd, 3rd and 6th positions in the repeating unit are unsubstituted) can be in the range of 0 to 1.5, preferably 0 to 0.6. And it is sufficient. By the DS H and 0.6 or less, or to improve the fluidity of the molding material, the foaming and the like due to water absorption of the molding material during acceleration and molding of the pyrolysis can or is suppressed.
  • the cellulose derivative in the present invention may have a substituent other than A) a hydrocarbon group, B) an acyl group, and C) a group containing an alkyleneoxy group and an acyl group.
  • substituents examples include a hydroxyethyl group, a hydroxypropyl group, a hydroxyethoxyethyl group, a hydroxypropoxypropyl group, a hydroxyethoxyethoxyethyl group, and a hydroxypropoxypropoxypropyl group. Therefore, the sum of the degree of substitution of all the substituents of the cellulose derivative is 3, but (DS A + DS B + DS C + DS H ) is 3 or less.
  • the amount of alkyleneoxy group introduced in the group C) is expressed in terms of molar substitution (MS: number of moles of substituent introduced per glucose residue) (edited by Cellulose Society, Cellulose Dictionary P142).
  • the molar substitution degree MS of the alkyleneoxy group is preferably 0 ⁇ MS, more preferably 0 ⁇ MS ⁇ 1.5, and still more preferably 0 ⁇ MS ⁇ 1.0. When MS is 1.5 or less (MS ⁇ 1.5), heat resistance, moldability and the like can be improved, and a cellulose derivative suitable for a molding material can be obtained.
  • the cellulose derivative in the molding material of the present invention is a cellulose derivative in which the hydrogen atom of the hydroxyl group contained in cellulose contains at least one group substituted with A) and at least one group substituted with B).
  • a hydrogen atom of a hydroxyl group contained in cellulose is substituted, from the viewpoint of moldability, it is substituted only by A) and B) or A), B), and C.
  • the hydrogen atom of the hydroxyl group contained in the cellulose is not substituted with a group other than the above A), B), and C).
  • the molecular weight of the cellulose derivative in the present invention is preferably such that the number average molecular weight (Mn) is in the range of 5 ⁇ 10 3 to 1000 ⁇ 10 3 , more preferably in the range of 10 ⁇ 10 3 to 500 ⁇ 10 3 , and 10 ⁇ 10 3 to A range of 200 ⁇ 10 3 is most preferred.
  • the weight average molecular weight (Mw) is preferably in the range of 7 ⁇ 10 3 to 10000 ⁇ 10 3 , more preferably in the range of 15 ⁇ 10 3 to 5000 ⁇ 10 3 , and in the range of 100 ⁇ 10 3 to 3000 ⁇ 10 3 . Is most preferred.
  • the molecular weight distribution is preferably in the range of 1.1 to 10.0, and more preferably in the range of 1.5 to 8.0. By setting the molecular weight distribution within this range, moldability and the like can be improved.
  • the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (MWD) can be measured using gel permeation chromatography (GPC).
  • N-methylpyrrolidone is used as a solvent
  • a polystyrene gel is used, and the molecular weight can be determined using a conversion molecular weight calibration curve obtained in advance from a standard monodisperse polystyrene constituent curve.
  • the method for producing a cellulose derivative in the present invention is not particularly limited, and the cellulose derivative in the present invention can be produced by using cellulose as a raw material and etherifying and esterifying cellulose.
  • the raw material for cellulose is not limited, and examples thereof include cotton, linter, and pulp.
  • a preferred embodiment of a method for producing a cellulose derivative having the above A) hydrocarbon group: —R A and B) acyl group: —CO—R B includes cellulose ether, base It includes a step of esterification by reacting acid chloride or acid anhydride in the presence.
  • R B represents a hydrocarbon group
  • the cellulose ether for example, those in which at least a part of the hydrogen atoms of the hydroxyl groups at the 2nd, 3rd and 6th positions of the ⁇ -glucose ring contained in cellulose are substituted with hydrocarbon groups can be used. Specific examples include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, allyl cellulose, and benzyl cellulose.
  • a preferred embodiment of a method for producing a cellulose derivative having a group containing —CO—R C1 (R C1 represents a hydrocarbon group and R C2 represents an alkylene group having 2 to 4 carbon atoms) is a hydrocarbon group.
  • hydroxyethyl cellulose ether having a hydroxyethyl group or hydroxypropyl cellulose ether having a hydroxypropyl group are reacted by an acid chloride or an acid anhydride to react with the esterification (acylation). is there.
  • alkyl chloride such as methyl chloride or ethyl chloride / alkylene oxide having 3 carbon atoms or the like is allowed to act on cellulose.
  • a method including a step of esterification by reacting an acid chloride or an acid anhydride is also included.
  • a method for reacting acid chloride for example, the method described in Cellulose 10; 283-296, 2003 can be used.
  • the cellulose ether having a hydrocarbon group and a hydroxyethyl group include hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxyethyl propyl cellulose, hydroxyethyl allyl cellulose, and hydroxyethyl benzyl cellulose. Preferred are hydroxyethyl methyl cellulose and hydroxyethyl ethyl cellulose.
  • Specific examples of the cellulose ether having a hydrocarbon group and a hydroxypropyl group include hydroxypropylmethylcellulose, hydroxypropylethylcellulose, hydroxypropylpropylcellulose, hydroxypropylallylcellulose, hydroxypropylbenzylcellulose, and the like. Preferred are hydroxypropylmethylcellulose and hydroxypropylethylcellulose.
  • acyl group and carboxylic acid chloride corresponding to the acyl group contained in C) can be used.
  • carboxylic acid chloride include acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, pentanoyl chloride, 2-methylbutanoyl chloride, 3-methylbutanoyl chloride, pivaloyl chloride, hexanoyl chloride, 2-methylpentanoyl chloride, 3-methylpentanoyl chloride, 4-methylpentanoyl chloride, 2,2-dimethylbutanoyl chloride, 2,3-dimethylbutanoyl chloride, 3,3-dimethylbutanoyl chloride, 2- Ethylbutanoyl chloride, heptanoyl chloride, 2-methylhexanoyl chloride, 3-methylhexanoyl chloride, 4-methylhexanoyl chloride, 5-methylhex
  • carboxylic acid anhydrides corresponding to the acyl group contained in the above B) acyl group and C
  • carboxylic anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride, octanoic anhydride, 2-ethylhexanoic acid.
  • An anhydride, nonanoic acid anhydride, etc. are mentioned.
  • the cellulose derivative in the present invention preferably has no carboxylic acid as a substituent, for example, a dicarboxylic acid such as phthalic anhydride, maleic anhydride, or the like, and a compound that generates a carboxyl group by reacting with cellulose. It is preferable not to use.
  • a dicarboxylic acid such as phthalic anhydride, maleic anhydride, or the like
  • a compound that generates a carboxyl group by reacting with cellulose It is preferable not to use.
  • Aromatic polyester contains an aromatic polyester.
  • Aromatic polyester has crystallinity and has a hard structure, so by mixing with a specific cellulose derivative in the present invention to form a molding material, it is more slidable than when a specific cellulose derivative is used alone. Can be improved.
  • the specific cellulose derivative in the present invention includes an ether structure and an ester structure, it has an ether bond having a higher degree of freedom around the main chain than a conventional cellulose ester and the like, and thus has an excellent affinity with an aromatic polyester. . Therefore, the aromatic polyester is excellent in dispersibility with respect to the specific cellulose derivative in the present invention, and both are mixed well. Therefore, the impact resistance and moldability are further improved when the specific cellulose derivative is used alone. improves. Moreover, it is excellent also in performance, such as rigidity, bending strength, and heat resistance.
  • the aromatic polyester referred to in the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising an aromatic dicarboxylic acid and a diol or an ester derivative thereof.
  • the aromatic polyester in the present invention preferably has a flexural modulus larger than 1.5 GPa (measured value according to JIS K-7203) because it imparts slidability without impairing the rigidity of the cellulose derivative. More preferably, it is 0 GPa to 3.5 GPa.
  • Aromatic dicarboxylic acids may be used as a mixture of two or more. In addition, if it is a small amount, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanediic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid together with the dicarboxylic acid. .
  • diol that is a raw material constituting the aromatic polyester of the present invention examples include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, and triethylene glycol.
  • Alicyclic diols such as 1,4-cyclohexanedimethanol, and mixtures thereof.
  • Specific aromatic polyesters include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2
  • PET polyethylene terephthalate
  • PBT polypropylene terephthalate
  • PEN polyethylene naphthalate
  • PBN polybutylene naphthalate
  • copolyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, etc.
  • polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate having a good balance of mechanical properties and the like can be preferably used, and polyethylene terephthalate and polybutylene terephthalate can be more preferably used. In the present invention, these may be used alone or in combination of two or more.
  • the molecular weight of the aromatic polyester in the present invention is preferably a number average molecular weight (Mn) in the range of 5 ⁇ 10 3 to 1000 ⁇ 10 3 , more preferably in the range of 10 ⁇ 10 3 to 500 ⁇ 10 3 , and 10 ⁇ 10 3. A range of ⁇ 200 ⁇ 10 3 is most preferred.
  • the weight average molecular weight (Mw) is preferably in the range of 7 ⁇ 10 3 to 10000 ⁇ 10 3 , more preferably in the range of 15 ⁇ 10 3 to 5000 ⁇ 10 3 , and in the range of 100 ⁇ 10 3 to 3000 ⁇ 10 3 . Is most preferred.
  • the molecular weight distribution (MWD) is preferably in the range of 1.1 to 10.0, and more preferably in the range of 1.5 to 8.0. By setting the molecular weight distribution within this range, dispersibility with the matrix resin, moldability, and the like can be improved.
  • the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (MWD) can be measured using gel permeation chromatography (GPC). Specifically, it can be determined using a converted molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene using pentafluorophenol as a solvent and using polystyrene gel.
  • aromatic polyester commercially available products may be used, and examples thereof include polyethylene terephthalate resin (Mitsui PET J005, manufactured by Mitsui Pet Resin Co., Ltd.), polybutylene terephthalate resin (Juranex 2002, manufactured by Nippon Polyplastics Co., Ltd.), and the like. .
  • the dicarboxylic acid component and the diol component are polymerized while heating, and water produced as a by-product.
  • it is carried out by discharging lower alcohol out of the system.
  • the molding material of the present invention preferably further contains a compatibilizer.
  • a compatibilizer As a result, the aromatic polyester further improves dispersibility with respect to the cellulose derivative in the present invention. Therefore, the aromatic polyester is superior in performance such as rigidity, bending strength, and heat resistance as compared with the case where a specific cellulose derivative is used alone. .
  • the compatibilizing agent in the present invention may be a low molecular compound or a high molecular compound, but has reactivity with chain extension such as an epoxy group, a carbodiimide group, an isocyanate group, an oxazoline group, and an acid anhydride group.
  • a polymer having a carboxylic acid anhydride group, an epoxy group, an isocyanate group, or an oxazoline group is particularly preferable.
  • Preferred compatibilizers include polymers modified with carboxylic acid anhydrides, epoxy groups, isocyanate groups, and oxazoline groups, block copolymers, graft polymers, random copolymers, and various nonionic surfactants. Agents, coupling agents, and crosslinking agents.
  • the compatibilizing agent is not particularly limited as long as it satisfies the above conditions, and specifically, Nippon Oil & Fats Modiper Series, Sumitomo Chemical Co., Ltd., Bond First, Bondine Series, Nippon Oil Commercially available such as Lexpearl series manufactured by Co., Ltd., Reseda series manufactured by Toagosei Co., Ltd., Alfon series, Epocross series manufactured by Nippon Shokubai Co., Ltd., Duranate series manufactured by Asahi Kasei Chemicals Co., Ltd. The product is preferably used.
  • the compatibilizer is not limited to these, and the compatibilizer described in “Plastic compatibilizer development / evaluation / recycling” (CMC Publishing Co., Ltd.) can also be suitably used.
  • the molding material of the present invention contains the cellulose derivative described above and an aromatic polyester, and optionally contains a compatibilizing agent. Moreover, another additive can be contained as needed.
  • the content rate of the component contained in the molding material of this invention is not specifically limited.
  • the content ratio of the cellulose derivative contained in the molding material of the present invention is not particularly limited.
  • the cellulose derivative is contained in an amount of 35% by mass or more, more preferably 45% by mass or more and 99% by mass or less, still more preferably 60% by mass or more and 95% by mass or less based on the total solid content.
  • the content ratio of the aromatic polyester contained in the molding material of the present invention is not particularly limited.
  • the aromatic polyester is contained in an amount of 1 to 70% by mass, more preferably 5 to 50% by mass, based on the total solid content.
  • the mass composition ratio of the cellulose derivative to the aromatic polyester is 20/80 to 95/5. Is more preferable, more preferably 40/60 to 90/10, still more preferably 60/40 to 90/10.
  • the molding material of the present invention contains a compatibilizing agent
  • the content is not limited, but is preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight in total of the cellulose derivative and the aromatic polyester. 0.5 to 20 parts by mass. By setting it within this range, a sufficient compatibility improvement effect can be obtained, and problems such as an increase in the viscosity of the molding material are unlikely to occur.
  • the molding material of the present invention may contain various additives such as an antioxidant, a filler (reinforcing material), a flame retardant, etc., as necessary, in addition to the cellulose derivative and the aromatic polyester.
  • the molding material of the present invention contains an antioxidant
  • its content is not limited, but it is usually 30% by mass or less, preferably 0.01 to 10% by mass in the molding material. By setting it within this range, the resin can obtain a sufficient stability improving effect against heating in the kneading or molding process, which is preferable.
  • the antioxidant include phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like, and phenol-based antioxidants are preferable.
  • the phenolic antioxidant Irganox 1010, Irganox 1076, Irganox 3114, etc. manufactured by Ciba Specialty Chemicals Co., Ltd. can be suitably used.
  • the molding material of the present invention can reinforce the mechanical properties of the molded body formed of the molding material.
  • a well-known thing can be used as a filler.
  • the shape of the filler may be any of fibrous, plate-like, granular, powdery and the like. Further, it may be inorganic or organic.
  • the inorganic filler glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, slag fiber, zonolite, Elastadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, and other inorganic fillers; glass flakes, non-swellable mica, carbon black, graphite, metal foil , Ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silicate, feldspar, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide Beam, aluminum oxide, titanium oxide, magnesium oxide, aluminum silicate, silicon oxide, aluminum hydroxide, magnesium hydroxide, gy
  • Organic fillers include synthetic fibers such as polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, and acetate fiber, and natural fibers such as kenaf, ramie, cotton, jute, hemp, sisal, Manila hemp, flax, linen, silk, and wool. Examples thereof include fibrous organic fillers obtained from microcrystalline cellulose, sugar cane, wood pulp, paper waste, waste paper and the like, and granular organic fillers such as organic pigments.
  • the content is not limited, but is usually 30 parts by mass or less, preferably 5 to 10 parts by mass with respect to 100 parts by mass in total of the cellulose derivative and the aromatic polyester. .
  • the molding material of the present invention may contain a flame retardant.
  • the flame retardant is not particularly limited, and a conventional flame retardant can be used.
  • a conventional flame retardant can be used.
  • brominated flame retardants, chlorine-based flame retardants, phosphorus-containing flame retardants, silicon-containing flame retardants, nitrogen compound-based flame retardants, inorganic flame retardants and the like can be mentioned.
  • hydrogen halides are not generated by thermal decomposition during resin compounding or molding, and do not corrode processing machines or molds or deteriorate the working environment.
  • Phosphorus-containing flame retardants and silicon-containing flame retardants are preferred because they are less likely to adversely affect the environment through the generation of harmful substances such as dioxins when they are diffused or decomposed.
  • the phosphorus-containing flame retardant is not particularly limited, and a commonly used one can be used. Examples thereof include organic phosphorus compounds such as phosphate esters, phosphate condensation esters, and polyphosphates.
  • phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) Phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl Acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl -2-acryloyloxye
  • Examples of the phosphoric acid condensed ester include resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and condensates thereof. Aromatic phosphoric acid condensed ester and the like.
  • polyphosphates composed of salts of phosphoric acid, polyphosphoric acid and metals of Groups 1 to 14 of the periodic table, ammonia, aliphatic amines, and aromatic amines can also be mentioned.
  • lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts and the like as metal salts, methylamine salts as aliphatic amine salts examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts and triazines.
  • halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris ( ⁇ -chloropropyl) phosphate), and structures in which a phosphorus atom and a nitrogen atom are connected by a double bond Phosphazene compounds having phosphoric acid and phosphoric ester amides.
  • phosphorus-containing flame retardants may be used singly or in combination of two or more.
  • silicon-containing flame retardant examples include an organic silicon compound having a two-dimensional or three-dimensional structure, polydimethylsiloxane, or a methyl group at a side chain or a terminal of polydimethylsiloxane, a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, Examples thereof include those substituted or modified with an aromatic hydrocarbon group, so-called silicone oils, or modified silicone oils.
  • Examples of the substituted or unsubstituted aliphatic hydrocarbon group and aromatic hydrocarbon group include an alkyl group, a cycloalkyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, a polyether group, a carboxyl group, a mercapto group, Examples include a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group.
  • These silicon-containing flame retardants may be used alone or in combination of two or more.
  • Examples of the flame retardant other than the phosphorus-containing flame retardant or the silicon-containing flame retardant include, for example, magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, Metastannic acid, tin oxide, tin oxide salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, ammonium borate, ammonium octamolybdate, tungsten Inorganic flame retardants such as acid metal salts, complex oxides of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, fluorine compounds, graphite, and swellable graphite can be used. . These other flame retardants may be used alone or in combination of two or more.
  • the content is not limited, but is usually 30 parts by mass or less, preferably 2 to 10 parts by mass with respect to a total of 100 parts by mass of the cellulose derivative and the aromatic polyester. And it is sufficient. By setting it as this range, a sufficient flame retardancy improving effect can be obtained, and the occurrence of pellet blocking can be suppressed.
  • the molding material of the present invention may contain other components other than those described above for the purpose of further improving various properties such as moldability and flame retardancy within the range not impairing the object of the present invention.
  • other components include polymers other than the cellulose derivative and the aromatic polyester, plasticizers, stabilizers (ultraviolet absorbers, etc.), mold release agents (fatty acids, fatty acid metal salts, oxyfatty acids, fatty acid esters, aliphatics.
  • any of a thermoplastic polymer and a thermosetting polymer other than the aromatic polyester can be used, but a thermoplastic polymer is preferable from the viewpoint of moldability.
  • Specific examples of polymers other than cellulose derivatives and aromatic polyesters include low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, Ethylene-butene-1 copolymer, polypropylene homopolymer, polypropylene copolymer (such as ethylene-propylene block copolymer), polyolefins such as polybutene-1 and poly-4-methylpentene-1, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 6T, nylon 12 and other polyamides, polystyrene, high impact polystyrene, polyacetal (including homopolymers and copolymers), poly
  • Various acrylic rubbers ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers and alkali metal salts thereof (so-called ionomers), ethylene-acrylic acid alkyl ester copolymers (for example, ethylene-ethyl acrylate copolymer) Copolymer, ethylene-butyl acrylate copolymer), diene rubber (for example, 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (for example, Styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, sty
  • a multi-layer structure polymer called a so-called core-shell rubber which is composed of one or more shell layers to be covered and whose adjacent layers are composed of different types of polymers, can also be used, and further a core-shell rubber containing a silicone compound Can also be used.
  • These polymers may be used alone or in combination of two or more.
  • the molding material of the present invention contains a polymer other than the cellulose derivative and the aromatic polyester
  • the content thereof is preferably 30 parts by mass or less with respect to 100 parts by mass in total of the cellulose derivative and the aromatic polyester. Part by mass is more preferable.
  • the molding material of the present invention may contain a plasticizer.
  • a plasticizer those commonly used for polymer molding can be used. Examples thereof include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.
  • polyester plasticizer examples include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, propylene glycol, 1,3-butanediol, 1,4 -Polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.
  • acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, propylene glycol, 1,3-butanediol, 1,4
  • glycerin plasticizer examples include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.
  • polycarboxylic acid plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, and trimellitic acid.
  • Trimellitic acid esters such as tributyl, trioctyl trimellitic acid, trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, adipic acid
  • Adipic acid esters such as benzylbutyl diglycol, citrate esters such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebashi Dibutyl, and include di-2-ethylhexyl sebacate and the like.
  • polyalkylene glycol plasticizer examples include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, and bisphenols.
  • a polyalkylene glycol such as a propylene oxide addition polymer, a tetrahydrofuran addition polymer of bisphenol, or a terminal epoxy-modified compound thereof, a terminal ester-modified compound, a terminal ether-modified compound, and the like.
  • the epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.
  • plasticizers include benzoate esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid
  • aliphatic carboxylic acid esters such as butyl, oxy acid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, and various sorbitols.
  • the content thereof is usually 30 parts by mass or less, preferably 0.005 to 20 parts by mass with respect to 100 parts by mass in total of the cellulose derivative and the aromatic polyester, More preferably, it is 0.01 to 10 parts by mass.
  • the molded body of the present invention can be obtained by molding a molding material containing the cellulose derivative and the aromatic polyester. More specifically, the step of heating the cellulose derivative and the aromatic polyester, or the molding material containing the cellulose derivative and the aromatic polyester and various additives as necessary, and molding them by various molding methods. It is obtained by the manufacturing method containing.
  • the method for producing a molded body of the present invention includes a step of heating and molding the molding material. Examples of the molding method include injection molding, extrusion molding, blow molding and the like.
  • the heating temperature is usually 160 to 300 ° C, preferably 180 to 260 ° C.
  • the use of the molded product of the present invention is not particularly limited.
  • interior or exterior parts of electrical and electronic equipment home appliances, OA / media related equipment, optical equipment, communication equipment, etc.
  • automobiles mechanical parts, etc.
  • materials for housing and construction for example, from the viewpoint of having excellent heat resistance and impact resistance and low environmental load, for example, exterior parts for electric and electronic devices such as copiers, printers, personal computers, televisions (especially casings) ) Can be suitably used.
  • reaction solution was returned to room temperature and quenched by adding 200 mL of methanol under ice cooling.
  • methanol methanol
  • a white solid was precipitated.
  • the white solid was filtered off by suction filtration and washed 3 times with a large amount of methanol solvent.
  • the resulting white solid was vacuum-dried at 100 ° C. for 6 hours to obtain methylcellulose-2-ethylhexanoate (C-5).
  • the solubility of this cellulose derivative (C-5) in water at 25 ° C. was less than 0.1% by mass (insoluble).
  • the degree of substitution of the hydrocarbon group is the number of moles of the hydrocarbon group substituted on the glucose ring unit, and takes a value of 0 or more and less than 3.
  • the molar substitution degree of the alkyleneoxy group is the number of moles of the alkyleneoxy group substituted on the glucose ring unit, and takes a value of 0 or more.
  • the degree of acylation indicates the degree of substitution with an acyl group by esterifying a hydroxyl group present in the glucose ring or ether substituent of cellulose, and is represented by 0 or more and 100 or less. Further, a colloid titration method is performed, and the degree of substitution of carboxyl groups or sulfonic acid groups in the cellulose derivatives (C-1) to (C-7) is less than 0.02 (that is, the content of carboxyl groups or sulfonic acid groups is It was confirmed that it was less than 0.5% by mass with respect to the cellulose derivative.
  • aromatic polyesters, compatibilizers and antioxidants are as follows.
  • PET Polyethylene terephthalate resin (Mitsui PET J005, manufactured by Mitsui Pet Resin Co., Ltd.)
  • PBT Polybutylene terephthalate resin (Duranex 2002, manufactured by Nippon Polyplastics Co., Ltd.)
  • Compatibilizer Modiper A4400, manufactured by NOF Corporation (ethylene-glycidyl methacrylate-graft-acrylonitrile-styrene resin)
  • Antioxidant Phenolic antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals)
  • HDT Heat deformation temperature
  • ISO75 a constant bending load (1.8 MPa) is applied to the center of the test piece (in the flatwise direction), the temperature is increased at a constant speed, and the temperature when the strain at the center reaches 0.34 mm ( ° C).
  • HDT tester 6M-2 manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. The measurement is an average of three measurements.
  • the moldability evaluation shows the moldability in an injection molding machine.
  • a resin composition that is excellent in both mold transportability and injection property is indicated by ⁇ , a resin composition that has a problem in either one, and a problem in both.
  • a certain resin composition was set as x.
  • the moldability is considered to be a problem when a measurement failure such as abnormal noise occurs at the time of resin measurement, and is excellent if measurement can be performed without any problem.
  • Injectability is considered to be a problem if molding defects such as burrs, sink marks, silver skin, and bubbles occur in the molded product, and excellent if it can be molded without problems.
  • test piece made of the molding material of the cellulose derivative alone (Comparative Example 1) and In comparison, the slidability is improved. Moreover, it is excellent also in rigidity, bending strength, impact resistance, and heat resistance.
  • the test pieces of Comparative Examples 2 and 3 made of a molding material containing no cellulose derivative in the present invention were inferior in impact resistance.
  • the test piece (Comparative Example 4) made of a molding material containing cellulose ester and aromatic polyester was inferior in impact resistance to the test piece of the example.
  • the molding material of the present invention has excellent thermoplasticity, it can be molded by heat molding or the like. Further, the molding material and the molded body of the present invention are excellent in performance such as rigidity, bending strength, and heat resistance, and have good impact resistance, molding processability, and sliding property. It can be suitably used as a component part such as an electric / electronic device, a machine part, a house / building material, and the like. Moreover, since the molding material of this invention uses the cellulose derivative obtained from the cellulose which is plant-derived resin, it can substitute for the conventional petroleum-derived resin as a raw material which can contribute to global warming prevention.

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Abstract

Disclosed is a molding material having stiffness, bending strength and heat resistance and also having good impact resistance, excellent moldability and sliding properties. The molding material comprises: a cellulose derivative which contains at least one group that is produced by substituting a hydrogen atom in a hydroxy group contained in a cellulose by a group (A) and at least one group that is produced by substituting a hydrogen atom in a hydroxy group contained in the cellulose by a group (B); and an aromatic polyester. (A) A hydrocarbon group: -RA. (B) An acyl group: -CO-RB (wherein RB represents a hydrocarbon group).

Description

成形材料、成形体、及びその製造方法、並びに電気電子機器用筐体MOLDING MATERIAL, MOLDED BODY, ITS MANUFACTURING METHOD, AND ELECTRIC ELECTRONIC DEVICE CASE
 本発明は、成形材料、成形体、及びその製造方法、並びに電気電子機器用筐体に関する。 The present invention relates to a molding material, a molded body, a manufacturing method thereof, and a casing for electrical and electronic equipment.
 コピー機、プリンター等の電気電子機器を構成する部材には、その部材に求められる特性、機能等を考慮して、各種の素材が使用されている。例えば、電気電子機器の駆動機等を収納し、当該駆動機を保護する役割を果たす部材(筐体)にはPC(Polycarbonate)、ABS(Acrylonitrile-butadiene-styrene)樹脂、PC/ABS等が一般的に多量に使用されている(特許文献1)。これらの樹脂は、石油を原料として得られる化合物を反応させて製造されている。 Various materials are used for members constituting electrical and electronic devices such as copiers and printers in consideration of the characteristics and functions required of the members. For example, PC (Polycarbonate), ABS (Acrylonitrile-butadiene-styrene) resin, PC / ABS, etc. are generally used as a member (housing) that stores a drive machine for electrical and electronic equipment and protects the drive machine. In large amounts (Patent Document 1). These resins are produced by reacting compounds obtained from petroleum as a raw material.
 ところで、石油、石炭、天然ガス等の化石資源は、長年月の間、地中に固定されてきた炭素を主成分とするものである。このような化石資源、又は化石資源を原料とする製品を燃焼させて、二酸化炭素が大気中に放出された場合には、本来、大気中に存在せずに地中深くに固定されていた炭素を二酸化炭素として急激に放出することになり、大気中の二酸化炭素が大きく増加し、これが地球温暖化の原因となっている。したがって、化石資源である石油を原料とするABS、PC等のポリマーは、電気電子機器用部材の素材としては、優れた特性を有するものであるものの、化石資源である石油を原料とするものであるため、地球温暖化の防止の観点からは、その使用量の低減が望ましい。 By the way, fossil resources such as oil, coal, and natural gas are mainly composed of carbon that has been fixed in the ground for many years. When such fossil resources or products made from fossil resources are burned and carbon dioxide is released into the atmosphere, carbon that was originally not deep in the atmosphere but fixed deep in the ground Is rapidly released as carbon dioxide, and carbon dioxide in the atmosphere greatly increases, which causes global warming. Therefore, polymers such as ABS and PC made from petroleum, which is a fossil resource, have excellent characteristics as materials for electrical and electronic equipment, but are made from petroleum, which is a fossil resource. Therefore, it is desirable to reduce the amount used from the viewpoint of preventing global warming.
 一方、植物由来の樹脂は、元々、植物が大気中の二酸化炭素と水とを原料として光合成反応によって生成したものである。そのため、植物由来の樹脂を焼却して二酸化炭素が発生しても、その二酸化炭素は元々、大気中にあった二酸化炭素に相当するものであるから、大気中の二酸化炭素の収支はプラスマイナスゼロとなり、結局、大気中のCOの総量を増加させない、という考え方がある。このような考えから、植物由来の樹脂は、いわゆる「カーボンニュートラル」な材料と称されている。石油由来の樹脂に代わって、カーボンニュートラルな材料を用いることは、近年の地球温暖化を防止する上で急務となっている。 On the other hand, a plant-derived resin is originally produced by a photosynthesis reaction using carbon dioxide and water in the atmosphere as raw materials. Therefore, even if plant-derived resin is incinerated to generate carbon dioxide, the carbon dioxide is equivalent to carbon dioxide originally in the atmosphere, so the balance of carbon dioxide in the atmosphere is plus or minus zero After all, there is an idea that the total amount of CO 2 in the atmosphere is not increased. Based on this idea, plant-derived resins are referred to as so-called “carbon neutral” materials. The use of carbon-neutral materials in place of petroleum-derived resins is an urgent need to prevent global warming in recent years.
 このため、PCポリマーにおいて、石油由来の原料の一部としてデンプン等の植物由来資源を使用することにより石油由来資源を低減する方法が提案されている(特許文献2)。
 しかし、より完全なカーボンニュートラルな材料を目指す観点から、さらなる改良が求められている。
For this reason, in PC polymer, the method of reducing petroleum origin resources is proposed by using plant origin resources, such as starch, as some raw materials derived from petroleum (patent documents 2).
However, further improvements are required from the perspective of aiming for a more complete carbon neutral material.
 公知のセルロース誘導体として、ヒドロキシプロピルメチルアセチルセルロースが特許文献3及び特許文献4に記載されている。特許文献3及び特許文献4では、このヒドロキシプロピルメチルアセチルセルロースは、揮発しやすい有機溶剤の蒸気圧を低減するための添加剤として有用であることが記載されている。また、特許文献3及び特許文献4に記載のヒドロキシプロピルメチルアセチルセルロースにおける各置換基の置換度は、例えばヒドロキシプロピル基のモル置換度(MS)が約2から8の範囲、メチル基の置換度が約0.1から1の範囲、アセチル基の置換度は約0.8から2.5の範囲であることが記載されている。 As known cellulose derivatives, hydroxypropylmethylacetylcellulose is described in Patent Document 3 and Patent Document 4. Patent Document 3 and Patent Document 4 describe that this hydroxypropylmethylacetylcellulose is useful as an additive for reducing the vapor pressure of an organic solvent that easily volatilizes. In addition, the substitution degree of each substituent in hydroxypropylmethylacetylcellulose described in Patent Document 3 and Patent Document 4 is, for example, a molar substitution degree (MS) of hydroxypropyl group in a range of about 2 to 8, a substitution degree of methyl group Is in the range of about 0.1 to 1 and the degree of substitution of the acetyl group is in the range of about 0.8 to 2.5.
 また、薬剤のコーティング等用途として、ヒドロキシプロピルメチルプロピルセルロース、ヒドロキシプロピルメチルブチルセルロース等(特許文献5)、ヒドロキシプロピルメチルセロースフタレート等(特許文献6)が開示されている。 Further, hydroxypropylmethylpropylcellulose, hydroxypropylmethylbutylcellulose and the like (Patent Document 5), hydroxypropylmethylserose phthalate and the like (Patent Document 6) are disclosed as uses such as drug coating.
 更に、特許文献7には、ブチルセルロースアセテートと芳香族ポリエステル樹脂を含む膜の例が開示されている。 Furthermore, Patent Document 7 discloses an example of a film containing butyl cellulose acetate and an aromatic polyester resin.
日本国特開昭56-55425号公報Japanese Unexamined Patent Publication No. 56-55425 日本国特開2008-24919号公報Japanese Unexamined Patent Publication No. 2008-24919 米国特許第3979179号明細書US Pat. No. 3,979,179 米国特許第3940384号明細書U.S. Pat. No. 3,940,384 国際公開第09/010837号International Publication No. 09/010837 日本国特許第3017412号明細書Japanese Patent No. 3017412 specification 日本国特開2008-73618号公報Japanese Unexamined Patent Publication No. 2008-73618
 本発明者らは、カーボンニュートラルな樹脂として、セルロースを使用することに着目した。しかし、セルロースは一般的に熱可塑性を持たないため、加熱等により成形することが困難であるため、成形加工に適さない。また、たとえ熱可塑性を付与できたとしても、耐衝撃性等の強度が大きく衰える問題がある。例えば、上記特許文献3、4、及び6に記載のセルロース誘導体は水可溶性又は膨潤性であり、強度が不足しており成形材料として好ましくない。また、特許文献5に記載のセルロース誘導体は水難溶性であることが記載されているが、本文中に記載があるのみでその合成方法及び使用形態等については実施例等で具体的に開示されていない。
 更に、特許文献7に記載のセルロース誘導体と芳香族ポリエステル樹脂を用いて形成された膜は、塗膜として特定の用途には使用できるが、一般的な成形材料としての使用には適さない。また、成形体とすることができたとしても、耐衝撃性に劣ると考えられる。
 また、一般的に、成形体どうし又は成形体と他の部材とが擦れた際に傷つきが生じない(摺動性に優れる)ほうが好ましいが、従来のセルロース誘導体を用いた樹脂組成物はこの点からも改良する必要があった。
The inventors of the present invention focused on using cellulose as a carbon neutral resin. However, since cellulose generally does not have thermoplasticity, it is difficult to mold by heating or the like, and thus is not suitable for molding. Further, even if thermoplasticity can be imparted, there is a problem that strength such as impact resistance is greatly reduced. For example, the cellulose derivatives described in Patent Documents 3, 4, and 6 are water-soluble or swellable and lack strength, which is not preferable as a molding material. In addition, the cellulose derivative described in Patent Document 5 is described as being poorly water-soluble, but only described in the text, and its synthesis method and usage form are specifically disclosed in Examples and the like. Absent.
Furthermore, although the film | membrane formed using the cellulose derivative and aromatic polyester resin of patent document 7 can be used for a specific use as a coating film, it is not suitable for the use as a general molding material. Moreover, even if it can be set as a molded object, it is thought that it is inferior to impact resistance.
In general, it is preferable that the molded bodies or the molded body and other members are not rubbed (not excellent in slidability) when the molded body is rubbed. However, a resin composition using a conventional cellulose derivative is preferred in this respect. It was also necessary to improve.
 本発明の目的は、剛性(曲げ弾性率)、曲げ強度、及び耐熱性(熱変形温度)といった性能と、更に良好な耐衝撃性(シャルピー衝撃強度)、優れた成形加工性、及び摺動性とを有する成形材料及び成形体を提供することである。また、本発明の別の目的は、該成形体の製造方法、及び該成形体から構成される電気電子機器用筐体を提供することである。 The object of the present invention is to achieve performance such as rigidity (flexural modulus), bending strength, and heat resistance (thermal deformation temperature), and even better impact resistance (Charpy impact strength), excellent moldability, and slidability. It is providing the molding material and molded object which have these. Another object of the present invention is to provide a method for producing the molded body and a housing for electrical and electronic equipment composed of the molded body.
 本発明者らは、セルロースの分子構造に着目し、セルロースをエーテル構造とエステル構造を有する特定構造のセルロース誘導体とし、該特定構造のセルロース誘導体と、更に芳香族ポリエステルとを含有する成形材料により、良好な剛性、曲げ強度、及び耐熱性といった性能とともに、更に耐衝撃性、成形加工性、及び摺動性に優れた成形材料及び成形体を提供しうることを見出し、本発明を完成するに至った。
 すなわち、上記課題は以下の手段により達成することができる。
The present inventors pay attention to the molecular structure of cellulose, make cellulose a cellulose derivative having a specific structure having an ether structure and an ester structure, and a molding material containing the cellulose derivative having the specific structure and an aromatic polyester, The inventors have found that it is possible to provide a molding material and a molded body having excellent impact resistance, molding processability, and slidability as well as performance such as good rigidity, bending strength, and heat resistance, and completed the present invention. It was.
That is, the said subject can be achieved by the following means.
[1]
 セルロースに含まれる水酸基の水素原子が、
 下記A)で置換された基を少なくとも1つ、及び
 下記B)で置換された基を少なくとも1つ含むセルロース誘導体と、
 芳香族ポリエステルとを含有する成形材料。
 A)炭化水素基:-R
 B)アシル基:-CO-R(Rは炭化水素基を表す。)
[2]
 前記セルロース誘導体が、更に、セルロースに含まれる水酸基の水素原子が下記C)で置換された基を少なくとも1つ含む、[1]に記載の成形材料。
 C)アルキレンオキシ基:-RC2-O-とアシル基:-CO-RC1とを含む基(RC1は炭化水素基を表し、RC2は炭素数が2~4のアルキレン基を表す。)
[3]
 前記C)アルキレンオキシ基とアシル基とを含む基が、下記一般式(3)で表される構造を含む基である、[2]に記載の成形材料。
[1]
The hydrogen atom of the hydroxyl group contained in cellulose
A cellulose derivative comprising at least one group substituted in A) below and at least one group substituted in B) below;
A molding material containing an aromatic polyester.
A) Hydrocarbon group: —R A
B) Acyl group: —CO—R B (R B represents a hydrocarbon group.)
[2]
The molding material according to [1], wherein the cellulose derivative further contains at least one group in which a hydrogen atom of a hydroxyl group contained in cellulose is substituted by the following C).
C) a group containing an alkyleneoxy group: —R C2 —O— and an acyl group: —CO—R C1 (R C1 represents a hydrocarbon group, and R C2 represents an alkylene group having 2 to 4 carbon atoms. )
[3]
[Claim 2] The molding material according to [2], wherein the group containing C) an alkyleneoxy group and an acyl group is a group containing a structure represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
(式中、RC1は炭化水素基を表し、RC2は炭素数が2~4のアルキレン基を表す。nは1以上の整数を表す。)
[4]
 前記Rが炭素数1~4のアルキル基である、[1]~[3]のいずれか一項に記載の成形材料。
[5]
 前記Rがメチル基又はエチル基である、[1]~[4]のいずれか一項に記載の成形材料。
[6]
 前記R及びRC1が、それぞれ独立に、アルキル基又はアリール基である、[2]~[5]のいずれか一項に記載の成形材料。
[7]
 前記R及びRC1が、それぞれ独立に、メチル基、エチル基又はプロピル基である、[2]~[6]のいずれか一項に記載の成形材料。
[8]
 前記Rが、炭素数3~10の分岐構造を有する炭化水素基である、[1]~[6]のいずれか一項に記載の成形材料。
[9]
 前記アルキレンオキシ基が下記式(1)又は(2)で表される基である、[2]~[8]のいずれか一項に記載の成形材料。
(Wherein R C1 represents a hydrocarbon group, R C2 represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 1 or more.)
[4]
The molding material according to any one of [1] to [3], wherein R A is an alkyl group having 1 to 4 carbon atoms.
[5]
The molding material according to any one of [1] to [4], wherein R A is a methyl group or an ethyl group.
[6]
The molding material according to any one of [2] to [5], wherein R B and R C1 are each independently an alkyl group or an aryl group.
[7]
The molding material according to any one of [2] to [6], wherein R B and R C1 are each independently a methyl group, an ethyl group, or a propyl group.
[8]
The molding material according to any one of [1] to [6], wherein R B is a hydrocarbon group having a branched structure having 3 to 10 carbon atoms.
[9]
The molding material according to any one of [2] to [8], wherein the alkyleneoxy group is a group represented by the following formula (1) or (2).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
[10]
 前記セルロース誘導体が、カルボキシル基、スルホン酸基、及びこれらの塩を実質的に有さない、[1]~[9]のいずれか一項に記載の成形材料。
[11]
 前記セルロース誘導体が水に不溶である、[1]~[10]のいずれか一項に記載の成形材料。
[12]
 前記芳香族ポリエステルが、ポリエチレンテレフタレート(PET)又はポリブチレンテレフタレート(PBT)である[1]~[11]のいずれか一項に記載の成形材料。
[13]
 更に、相溶化剤を含有する[1]~[12]のいずれか一項に記載の成形材料。
[14]
 前記相溶化剤が、カルボン酸無水物、又は、エポキシ基、イソシアネート基及びオキサゾリン基からなる群より選ばれる少なくとも1種を有する化合物である、[13]に記載の成形材料。
[15]
 [1]~[14]のいずれか一項に記載の成形材料を加熱成形して得られる成形体。
[16]
 [1]~[14]のいずれか一項に記載の成形材料を加熱し、成形する工程を含む、成形体の製造方法。
[17]
[15]に記載の成形体から構成される電気電子機器用筐体。
[10]
The molding material according to any one of [1] to [9], wherein the cellulose derivative is substantially free of carboxyl groups, sulfonic acid groups, and salts thereof.
[11]
The molding material according to any one of [1] to [10], wherein the cellulose derivative is insoluble in water.
[12]
The molding material according to any one of [1] to [11], wherein the aromatic polyester is polyethylene terephthalate (PET) or polybutylene terephthalate (PBT).
[13]
The molding material according to any one of [1] to [12], further comprising a compatibilizing agent.
[14]
[13] The molding material according to [13], wherein the compatibilizer is a carboxylic acid anhydride or a compound having at least one selected from the group consisting of an epoxy group, an isocyanate group, and an oxazoline group.
[15]
[1] A molded product obtained by thermoforming the molding material according to any one of [14].
[16]
[1] A method for producing a molded body, comprising a step of heating and molding the molding material according to any one of [14].
[17]
[15] A casing for an electric and electronic device comprising the molded article according to [15].
 本発明の成形材料は、優れた熱可塑性を有するため、加熱成形などにより成形することができる。また、本発明の成形材料、及び成形体は、剛性、曲げ強度、耐熱性といった性能に優れ、かつ良好な耐衝撃性、成形加工性、及び摺動性を有しており、例えば自動車、家電、電気電子機器等の構成部品、機械部品、住宅・建築用材料等として好適に使用することができる。また、本発明の成形材料は、植物由来の樹脂であるセルロースから得られるセルロース誘導体を使用しているため、温暖化防止に貢献できる素材として、従来の石油由来の樹脂に代替できる。 Since the molding material of the present invention has excellent thermoplasticity, it can be molded by heat molding or the like. Further, the molding material and the molded body of the present invention are excellent in performance such as rigidity, bending strength, and heat resistance, and have good impact resistance, molding processability, and sliding property. It can be suitably used as a component part such as an electric / electronic device, a machine part, a house / building material, and the like. Moreover, since the molding material of this invention uses the cellulose derivative obtained from the cellulose which is plant-derived resin, it can substitute for the conventional petroleum-derived resin as a raw material which can contribute to global warming prevention.
 本発明は、セルロースに含まれる水酸基の水素原子が、
 下記A)で置換された基を少なくとも1つ、及び
 下記B)で置換された基を少なくとも1つ含むセルロース誘導体(以下、「セルロース誘導体」ともいう)と、
 芳香族ポリエステルとを含有する成形材料に関する。
 A)炭化水素基:-R
 B)アシル基:-CO-R(Rは炭化水素基を表す。)
 以下、本発明について詳細に説明する。
In the present invention, the hydrogen atom of the hydroxyl group contained in cellulose is
A cellulose derivative (hereinafter also referred to as “cellulose derivative”) comprising at least one group substituted with A) below and at least one group substituted with B) below;
The present invention relates to a molding material containing an aromatic polyester.
A) Hydrocarbon group: —R A
B) Acyl group: —CO—R B (R B represents a hydrocarbon group.)
Hereinafter, the present invention will be described in detail.
1.セルロース誘導体
 本発明の成形材料に含まれるセルロース誘導体は、セルロースに含まれる水酸基の水素原子が、
 下記A)で置換された基を少なくとも1つ、及び
 下記B)で置換された基を少なくとも1つ含むセルロース誘導体(以下、「セルロース誘導体」ともいう)である。
 A)炭化水素基:-R
 B)アシル基:-CO-R(Rは炭化水素基を表す。)
 すなわち、本発明におけるセルロース誘導体は、セルロースエーテルエステルであり、セルロース{(C10}に含まれる水酸基の水素原子の少なくとも一部が、A)炭化水素基:-R、B)アシル基:-CO-R(Rは炭化水素基を表す。)により置換されている。
 より詳細には、本発明におけるセルロース誘導体は、下記一般式(A)で表される繰り返し単位を有する。
1. Cellulose derivative The cellulose derivative contained in the molding material of the present invention has a hydrogen atom of a hydroxyl group contained in cellulose.
It is a cellulose derivative (hereinafter also referred to as “cellulose derivative”) containing at least one group substituted by A) below and at least one group substituted by B) below.
A) Hydrocarbon group: —R A
B) Acyl group: —CO—R B (R B represents a hydrocarbon group.)
That is, the cellulose derivative in the present invention is a cellulose ether ester, and at least a part of the hydrogen atoms of the hydroxyl group contained in cellulose {(C 6 H 10 O 5 ) n } is A) a hydrocarbon group: —R A , B) Substituted by an acyl group: —CO—R B (R B represents a hydrocarbon group).
More specifically, the cellulose derivative in the present invention has a repeating unit represented by the following general formula (A).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
 上記一般式(A)において、R、R及びRは、それぞれ独立に、水素原子、A)炭化水素基:-R、B)アシル基:-CO-R(Rは炭化水素基を表す。)、又はその他の置換基を表す。ただし、R、R、及びRの少なくとも一部がA)炭化水素基を表し、かつR、R、及びRの少なくとも一部がB)アシル基を表す。 In the general formula (A), R 2 , R 3 and R 6 are each independently a hydrogen atom, A) hydrocarbon group: —R A , B) acyl group: —CO—R B (R B is carbon Represents a hydrogen group) or other substituents. However, at least a part of R 2 , R 3 , and R 6 represents A) a hydrocarbon group, and at least a part of R 2 , R 3 , and R 6 represents B) an acyl group.
 本発明におけるセルロース誘導体は、上記のようにβ-グルコース環の水酸基の少なくとも一部がA)炭化水素基、及びB)アシル基によって、エーテル化、及びエステル化されていることにより、熱可塑性を発現することができ、成形加工に適したものとなる。
 更には、セルロースは完全な植物由来成分であるため、カーボンニュートラルであり、環境に対する負荷を大幅に低減することができる。
As described above, the cellulose derivative in the present invention has thermoplasticity because at least part of the hydroxyl group of the β-glucose ring is etherified and esterified with A) a hydrocarbon group and B) an acyl group. It can be expressed and is suitable for molding.
Furthermore, since cellulose is a completely plant-derived component, it is carbon neutral and can greatly reduce the burden on the environment.
 なお、本発明にいう「セルロース」とは、多数のグルコースがβ-1,4-グリコシド結合によって結合した高分子化合物であって、セルロースのグルコース環における2位、3位、6位の炭素原子に結合している水酸基が無置換であるものを意味する。また、「セルロースに含まれる水酸基」とは、セルロースのグルコース環における2位、3位、6位の炭素原子に結合している水酸基を指す。 The “cellulose” referred to in the present invention is a polymer compound in which a large number of glucoses are bonded by β-1,4-glycosidic bonds, and the carbon atoms at the 2nd, 3rd and 6th positions in the glucose ring of cellulose. Means that the hydroxyl group bonded to is unsubstituted. Further, “hydroxyl group contained in cellulose” refers to a hydroxyl group bonded to carbon atoms at the 2nd, 3rd and 6th positions in the glucose ring of cellulose.
 前記セルロース誘導体は、その全体のいずれかの部分に前記A)炭化水素基、及びB)アシル基とを含んでいればよく、同一の繰り返し単位からなるものであってもよいし、複数の種類の繰り返し単位からなるものであってもよい。また、前記セルロース誘導体は、ひとつの繰り返し単位において前記A)炭化水素基、及びB)アシル基をすべて含有する必要はない。
 より具体的な態様としては、例えば以下の態様が挙げられる。
(1)R、R及びRの少なくとも1つが、A)炭化水素基で置換されている繰り返し単位と、R、R及びRの少なくとも1つが、B)アシル基で置換されている繰り返し単位と、から構成されるセルロース誘導体。
(2)ひとつの繰り返し単位のR、R及びRのいずれか少なくとも1つがA)炭化水素基で置換され、それとは別のいずれか少なくとも1つがB)アシル基で置換されている(すなわち、ひとつの繰り返し単位中に前記A)及びB)の置換基を有する)同種の繰り返し単位から構成されるセルロース誘導体。
(3)置換位置や置換基の種類が異なる繰り返し単位が、ランダムに結合しているセルロース誘導体。
 また、セルロース誘導体には、無置換の繰り返し単位(すなわち、前記一般式(A)において、R、R及びRすべてが水素原子である繰り返し単位)を含んでいてもよい。
 また、セルロース誘導体は、水素原子、A)炭化水素基、及びB)アシル基以外のその他の置換基を有していても良い。
The cellulose derivative only needs to contain the A) hydrocarbon group and B) acyl group in any part of the whole, and may be composed of the same repeating unit, or a plurality of types. It may consist of repeating units. The cellulose derivative does not need to contain all of the A) hydrocarbon group and B) acyl group in one repeating unit.
More specific embodiments include the following embodiments, for example.
(1) At least one of R 2 , R 3 and R 6 is A) a repeating unit substituted with a hydrocarbon group, and at least one of R 2 , R 3 and R 6 is substituted with B) an acyl group A cellulose derivative composed of repeating units.
(2) At least one of R 2 , R 3 and R 6 of one repeating unit is substituted with A) a hydrocarbon group, and at least one of the other is substituted with B) an acyl group ( That is, a cellulose derivative composed of the same type of repeating units having the substituents A) and B) in one repeating unit.
(3) A cellulose derivative in which repeating units having different substitution positions and different types of substituents are bonded at random.
The cellulose derivative may contain an unsubstituted repeating unit (that is, a repeating unit in which R 2 , R 3 and R 6 are all hydrogen atoms in the general formula (A)).
Moreover, the cellulose derivative may have other substituents other than a hydrogen atom, A) a hydrocarbon group, and B) an acyl group.
 A)炭化水素基:-Rは、脂肪族基、及び芳香族基のいずれでもよい。
 Rが脂肪族基である場合は、直鎖、分岐、及び環状のいずれでもよく、不飽和結合を持っていてもよい。脂肪族基としては、例えば、アルキル基、シクロアルキル基、アルケニル基、アルキニル基等が挙げられる。
 Rが芳香族基である場合は、単環、及び縮環のいずれでもよい。Rが芳香族基である場合の好ましい炭素数は6~18であり、より好ましくは6~14、更に好ましくは6~10である。芳香族基としては、例えば、フェニル基、ナフチル基、フェナントリル基、アントリル基等が挙げられる。
 A)炭化水素基は、得られる成形材料(以下「セルロース樹脂組成物」又は「樹脂組成物」と称する場合がある。)の耐衝撃性が優れることから、脂肪族基であることが好ましく、メルトフローレート等の成形加工性が優れることから、より好ましくはアルキル基であり、更に好ましくは炭素数1~4のアルキル基(低級アルキル基)である。具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、ヘキシル基、ヘプチル基、2-エチルヘキシル基、tert-ブチル基、イソヘプチル基等が挙げられ、メチル基又はエチル基が特に好ましい。
A) Hydrocarbon group: —R A may be an aliphatic group or an aromatic group.
When R A is an aliphatic group, it may be linear, branched, or cyclic, and may have an unsaturated bond. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
When R A is an aromatic group, it may be either a single ring or a condensed ring. In the case where R A is an aromatic group, the preferred carbon number is 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. Examples of the aromatic group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
A) The hydrocarbon group is preferably an aliphatic group because the resulting molding material (hereinafter sometimes referred to as “cellulose resin composition” or “resin composition”) has excellent impact resistance. From the viewpoint of excellent moldability such as melt flow rate, an alkyl group is more preferable, and an alkyl group having 1 to 4 carbon atoms (lower alkyl group) is more preferable. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, tert-butyl group, isoheptyl group, and the like. A group or an ethyl group is particularly preferred.
 B)アシル基:-CO-Rにおいて、Rは炭化水素基を表す。Rは、脂肪族基、及び芳香族基のいずれでもよい。
 Rが脂肪族基である場合は、直鎖、分岐、及び環状のいずれでもよく、不飽和結合を持っていてもよい。脂肪族基としては、例えば、アルキル基、シクロアルキル基、アルケニル基、アルキニル基等が挙げられる。
 Rが芳香族基である場合は、単環、及び縮環のいずれでもよい。芳香族基としては、フェニル基、ナフチル基、フェナントリル基、アントリル基等が挙げられる。
 Rは、好ましくはアルキル基又はアリール基である。Rは、より好ましくは炭素数1~12のアルキル基又はアリール基であり、更に好ましくは炭素数1~12のアルキル基であり、特に好ましくは炭素数1~4のアルキル基(好ましくはメチル基、エチル基、プロピル基)であり、最も好ましくは炭素数1又は2のアルキル基(すなわち、メチル基又はエチル基)である。
 また、Rは、炭素数3~10の分岐構造を有する炭化水素基であることも好ましく、炭素数3~10の分岐構造を有するアルキル基であることがより好ましく、炭素数7~9の分岐構造を有するアルキル基であることが更に好ましい。
 Rとしては、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、ヘキシル基、ヘプチル基、3-ヘプチル基、2-エチルヘキシル基、tert-ブチル基、及びイソヘプチル基等が挙げられる。好ましくは、Rはメチル基、エチル基、プロピル基、3-ヘプチル基、又は2-エチルヘキシル基であり、より好ましくはメチル基、エチル基、3-ヘプチル基、又は2-エチルヘキシル基である。
B) Acyl group: In —CO—R B , R B represents a hydrocarbon group. R B is an aliphatic group, and may be any aromatic group.
If R B is an aliphatic group, straight chain, branched, and may be any of circular, it may have an unsaturated bond. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
If R B is an aromatic group may be either monocyclic and condensed. Examples of the aromatic group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
R B is preferably an alkyl group or an aryl group. R B is more preferably an alkyl group having 1 to 12 carbon atoms or an aryl group, still more preferably an alkyl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms (preferably a methyl group). Group, ethyl group, propyl group), and most preferably an alkyl group having 1 or 2 carbon atoms (that is, a methyl group or an ethyl group).
Also, R B, it is also preferably a hydrocarbon group having a branched structure having 3 to 10 carbon atoms, more preferably an alkyl group having a branched structure having 3 to 10 carbon atoms, having 7-9 carbon atoms More preferably, it is an alkyl group having a branched structure.
The R B, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, 3-heptyl, 2-ethylhexyl group, tert- butyl Group, isoheptyl group, and the like. Preferably, R B is a methyl group, an ethyl group, a propyl group, a 3-heptyl group, or a 2-ethylhexyl group, and more preferably a methyl group, an ethyl group, a 3-heptyl group, or a 2-ethylhexyl group.
 本発明の成形材料におけるセルロース誘導体は、セルロースに含まれる水酸基の水素原子が、前記A)で置換された基を少なくとも1つ、及び前記B)で置換された基を少なくとも1つ含むセルロース誘導体であるが、更に、セルロースに含まれる水酸基の水素原子が下記C)で置換された基を少なくとも1つ含むことが耐衝撃性の観点から好ましい。
 C)アルキレンオキシ基:-RC2-O-とアシル基:-CO-RC1とを含む基(RC1は炭化水素基を表し、RC2は炭素数が2~4のアルキレン基を表す。)
The cellulose derivative in the molding material of the present invention is a cellulose derivative in which the hydrogen atom of the hydroxyl group contained in cellulose contains at least one group substituted with A) and at least one group substituted with B). However, it is preferable from the viewpoint of impact resistance that it further contains at least one group in which the hydrogen atom of the hydroxyl group contained in cellulose is substituted by the following C).
C) a group containing an alkyleneoxy group: —R C2 —O— and an acyl group: —CO—R C1 (R C1 represents a hydrocarbon group, and R C2 represents an alkylene group having 2 to 4 carbon atoms. )
 前記C)に含まれるアシル基(-CO-RC1)において、RC1は炭化水素基を表す。RC1が表す炭化水素基としては、前記Rで挙げたものと同様のものを適用することができる。RC1の好ましい範囲も前記Rと同様である。 In the acyl group (—CO—R C1 ) contained in C), R C1 represents a hydrocarbon group. As the hydrocarbon group represented by R C1, the same groups as those described above for R B can be applied. The preferred range of R C1 is the same as R B.
 前記C)に含まれるアルキレンオキシ基(-RC2-O-)において、RC2は炭素数が2~4のアルキレン基を表す。RC2は、直鎖状、分岐状、又は環状のいずれでもよいが、直鎖状、又は分岐状が好ましく、分岐状がより好ましい。
 アルキレンオキシ基(-RC2-O-)としては、炭素数2又は3のアルキレンオキシ基が好ましい。アルキレンオキシ基としては具体的には下記構造が好ましく挙げられる。
In the alkyleneoxy group (—R C2 —O—) contained in C), R C2 represents an alkylene group having 2 to 4 carbon atoms. R C2 may be linear, branched or cyclic, but is preferably linear or branched, and more preferably branched.
The alkyleneoxy group (—R C2 —O—) is preferably an alkyleneoxy group having 2 or 3 carbon atoms. Specific examples of the alkyleneoxy group preferably include the following structures.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
 上記の中でも、得られる樹脂組成物の曲げ弾性率が優れることから、-RC2-O-が分岐状である下記式(1)又は(2)で表される基が好ましい。 Among them, a group represented by the following formula (1) or (2) in which —R C2 —O— is branched is preferable because the obtained resin composition has excellent bending elastic modulus.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
 前記C)の基は、アルキレンオキシ基を複数含んでいてもよいし、1つだけ含むものであってもよい。好ましくは、前記C)の基は、下記一般式(3)で表すことができる。 The group of C) may contain a plurality of alkyleneoxy groups or may contain only one. Preferably, the group of C) can be represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
 前記一般式(3)中、RC1は炭化水素基を表し、RC2は炭素数が2~4のアルキレン基を表す。RC1及びRC2の好ましい範囲は、前記したものと同様である。nは1以上の整数である。nの上限は特に限定されず、アルキレンオキシ基の導入量等により変わるが、例えば10程度である。nは好ましくは1~5であり、より好ましくは1~3であり、更に好ましくは1である。RC2は複数存在する場合は各々同じでも異なってもよいが、同じであることが好ましい。
 また、本発明におけるセルロース誘導体は、アルキレンオキシ基を1つだけ含む前記C)の基(上記一般式(3)においてnが1である基)と、アルキレンオキシ基を2以上含む前記C)の基(上記一般式(3)においてnが2以上である基)とを含んでいてもよい。
In the general formula (3), R C1 represents a hydrocarbon group, and R C2 represents an alkylene group having 2 to 4 carbon atoms. The preferred ranges of R C1 and R C2 are the same as those described above. n is an integer of 1 or more. The upper limit of n is not particularly limited, and varies depending on the amount of alkyleneoxy group introduced, but is about 10, for example. n is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1. When a plurality of R C2 are present, they may be the same or different, but are preferably the same.
In addition, the cellulose derivative in the present invention is a group of C) containing only one alkyleneoxy group (a group in which n is 1 in the general formula (3)) and C) containing two or more alkyleneoxy groups. And a group (a group in which n is 2 or more in the above general formula (3)).
 また、前記C)の基におけるアルキレンオキシ基のセルロース誘導体に対する結合向きは特に限定されないが、アルキレンオキシ基のアルキレン基部分(RC2)がβ-グルコース環構造側に結合していることが好ましい。 Further, the bonding direction of the alkyleneoxy group to the cellulose derivative in the group C) is not particularly limited, but it is preferable that the alkylene group part (R C2 ) of the alkyleneoxy group is bonded to the β-glucose ring structure side.
 前記A)におけるR、前記B)におけるR、前記C)におけるRC1及びRC2は、さらなる置換基を有していてもよいし無置換でもよいが、無置換であることが好ましい。
 前記A)におけるR、前記B)におけるR、前記C)におけるRC1及びRC2がさらなる置換基を有する場合、さらなる置換基としては、例えば、ハロゲン原子(例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子)、ヒドロキシ基、アルコキシ基(アルキル基部分の炭素数は好ましくは1~5)、アルケニル基等が挙げられる。ただし、置換基を含む場合でもRC2の炭素数は2又は3である。なお、R、R、及びRC1がアルキル基以外である場合は、アルキル基(好ましくは炭素数1~5)を置換基として有することもできる。
R A in A), R B in B ), R C1 and R C2 in C) may have a further substituent or may be unsubstituted, but are preferably unsubstituted.
R A in the A), R B in the B), in the case where the where R C1 and R C2 in the C) has a further substituent, examples of the further substituent include a halogen atom (e.g. fluorine atom, chlorine atom, bromine Atoms, iodine atoms), hydroxy groups, alkoxy groups (the alkyl group preferably has 1 to 5 carbon atoms), alkenyl groups, and the like. However, even when a substituent is included, R C2 has 2 or 3 carbon atoms. Note that when R A , R B , and R C1 are other than an alkyl group, they may have an alkyl group (preferably having a carbon number of 1 to 5) as a substituent.
 特に、R及びRC1がさらなる置換基を有する場合、カルボキシル基、スルホン酸基、及びこれらの塩を実質的に有さないことが好ましい。セルロース誘導体がカルボキシル基、スルホン酸基、及びこれらの塩を実質的に有さないことにより、本発明の成形材料を水不溶性とすることができ、成形性を更に向上させることができる。また、セルロース誘導体がカルボキシル基、スルホン酸基、及びこれらの塩を有する場合、化合物安定性を悪化させることが知られており、特に熱分解を促進することがあるため、これらの基を含まないことが好ましい。
 なお、「カルボキシル基、スルホン酸基、及びこれらの塩を実質的に有さない」とは、本発明におけるセルロース誘導体が全くカルボキシル基、スルホン酸基、及びこれらの塩を有さない場合のみならず、本発明におけるセルロース誘導体が水に不溶な範囲で微量のカルボキシル基、スルホン酸基、及びこれらの塩を有する場合を包含するものとする。例えば、原料であるセルロースにカルボキシル基が含まれる場合があり、これを用いて前記A)~C)の置換基を導入したセルロース誘導体はカルボキシル基が含まれる場合があるが、これは「カルボキシル基、スルホン酸基、及びこれらの塩を実質的に有さないセルロース誘導体」に含まれるものとする。
 この場合、カルボキシル基、スルホン酸基、及びこれらの塩の好ましい含有量としては、セルロース誘導体に対して1質量%以下、より好ましくは0.5質量%以下である。
In particular, when R B and R C1 have a further substituent, it is preferable that they substantially have no carboxyl group, sulfonic acid group, and salts thereof. When the cellulose derivative is substantially free of carboxyl groups, sulfonic acid groups, and salts thereof, the molding material of the present invention can be made water-insoluble and the moldability can be further improved. In addition, when the cellulose derivative has a carboxyl group, a sulfonic acid group, and a salt thereof, it is known that the compound stability is deteriorated, and in particular, thermal decomposition may be promoted. It is preferable.
Note that “substantially free of carboxyl groups, sulfonic acid groups, and salts thereof” means only when the cellulose derivative in the present invention has no carboxyl groups, sulfonic acid groups, and salts thereof. In addition, the case where the cellulose derivative in the present invention has a trace amount of carboxyl groups, sulfonic acid groups, and salts thereof in a range insoluble in water is included. For example, the cellulose as a raw material may contain a carboxyl group, and the cellulose derivative using the above-described substituents A) to C) introduced therein may contain a carboxyl group. , A sulfonic acid group, and a cellulose derivative substantially free of salts thereof.
In this case, the preferred content of the carboxyl group, sulfonic acid group, and salts thereof is 1% by mass or less, more preferably 0.5% by mass or less, based on the cellulose derivative.
 また、本発明におけるセルロース誘導体は、水に不溶であることが好ましい。ここで、「水に不溶である」とは、25℃の水100質量部への溶解度が5質量部以下であることとする。 In addition, the cellulose derivative in the present invention is preferably insoluble in water. Here, “being insoluble in water” means that the solubility in 100 parts by mass of water at 25 ° C. is 5 parts by mass or less.
 本発明におけるセルロース誘導体の具体例としては、アセチルメチルセルロース、アセチルエチルセルロース、アセチルプロピルセルロース、アセチルブチルセルロース、アセチルペンチルセルロース、アセチルヘキシルセルロース、アセチルシクロヘキシルセルロース、アセチルフェニルセルロース、アセチルナフチルセルロース、プロピオニルメチルセルロース、プロピオニルエチルセルロース、プロピオニルプロピルセルロース、プロピオニルブチルセルロース、プロピオニルペンチルセルロース、プロピオニルヘキシルセルロース、プロピオニルシクロヘキシルセルロース、プロピオニルフェニルセルロース、プロピオニルナフチルセルロース、ブチリルメチルセルロース、ブチリルエチルセルロース、ブチリルプロピルセルロース、ブチリルブチルセルロース、ブチリルペンチルセルロース、ブチリルヘキシルセルロース、ブチリルシクロヘキシルセルロース、ブチリルフェニルセルロース、ブチリルナフチルセルロース、メチルセルロース-2-エチルヘキサノエート、エチルセルロース-2-エチルヘキサノエート、プロピルセルロース-2-エチルヘキサノエート、ブチルセルロース-2-エチルヘキサノエート、ペンチルセルロース-2-エチルヘキサノエート、ヘキシルセルロース-2-エチルヘキサノエート、シクロヘキシルセルロース-2-エチルヘキサノエート、フェニルセルロース-2-エチルヘキサノエート、ナフチルセルロース-2-エチルヘキサノエート、アセトキシエチルメチルアセチルセルロース、アセトキシエチルエチルアセチルセルロース、アセトキシエチルプロピルアセチルセルロース、アセトキシエチルブチルアセチルセルロース、アセトキシエチルペンチルアセチルセルロース、アセトキシエチルヘキシルアセチルセルロース、アセトキシエチルシクロヘキシルアセチルセルロース、アセトキシエチルフェニルアセチルセルロース、アセトキシエチルナフチルアセチルセルロース、アセトキシエチルメチルプロピオニルセルロース、アセトキシエチルエチルプロピオニルセルロース、アセトキシエチルプロピルプロピオニルセルロース、アセトキシエチルブチルプロピオニルセルロース、アセトキシエチルペンチルプロピオニルセルロース、アセトキシエチルヘキシルプロピオニルセルロース、アセトキシエチルシクロヘキシルプロピオニルセルロース、アセトキシエチルフェニルプロピオニルセルロース、アセトキシエチルナフチルプロピオニルセルロース、アセトキシエチルメチルセルロース-2-エチルヘキサノエート、アセトキシエチルエチルセルロース-2-エチルヘキサノエート、アセトキシエチルプロピルセルロース-2-エチルヘキサノエート、アセトキシエチルブチルセルロース-2-エチルヘキサノエート、アセトキシエチルペンチルセルロース-2-エチルヘキサノエート、アセトキシエチルヘキシルセルロース-2-エチルヘキサノエート、アセトキシエチルシクロヘキシルセルロース-2-エチルヘキサノエート、アセトキシエチルフェニルセルロース-2-エチルヘキサノエート、アセトキシエチルナフチルセルロース-2-エチルヘキサノエート、プロピオニルオキシエチルメチルアセチルセルロース、プロピオニルオキシエチルエチルアセチルセルロース、プロピオニルオキシエチルプロピルアセチルセルロース、プロピオニルオキシエチルブチルアセチルセルロース、プロピオニルオキシエチルペンチルアセチルセルロース、プロピオニルオキシエチルヘキシルアセチルセルロース、プロピオニルオキシエチルシクロヘキシルアセチルセルロース、プロピオニルオキシエチルフェニルアセチルセルロース、プロピオニルオキシエチルナフチルアセチルセルロース、プロピオニルオキシエチルメチルプロピオニルセルロース、プロピオニルオキシエチルエチルプロピオニルセルロース、プロピオニルオキシエチルプロピルプロピオニルセルロース、プロピオニルオキシエチルブチルプロピオニルセルロース、プロピオニルオキシエチルペンチルプロピオニルセルロース、プロピオニルオキシエチルヘキシルプロピオニルセルロース、プロピオニルオキシエチルシクロヘキシルプロピオニルセルロース、プロピオニルオキシエチルフェニルプロピオニルセルロース、プロピオニルオキシエチルナフチルプロピオニルセルロース、プロピオニルオキシエチルメチルセルロース-2-エチルヘキサノエート、プロピオニルオキシエチルエチルセルロース-2-エチルヘキサノエート、プロピオニルオキシエチルプロピルセルロース-2-エチルヘキサノエート、プロピオニルオキシエチルブチルセルロース-2-エチルヘキサノエート、プロピオニルオキシエチルペンチルセルロース-2-エチルヘキサノエート、プロピオニルオキシエチルヘキシルセルロース-2-エチルヘキサノエート、プロピオニルオキシエチルシクロヘキシルセルロース-2-エチルヘキサノエート、プロピオニルオキシエチルフェニルセルロース-2-エチルヘキサノエート、プロピオニルオキシエチルナフチルセルロース-2-エチルヘキサノエート、アセトキシプロピルメチルアセチルセルロース、アセトキシプロピルエチルアセチルセルロース、アセトキシプロピルプロピルアセチルセルロース、アセトキシプロピルブチルアセチルセルロース、アセトキシプロピルペンチルアセチルセルロース、アセトキシプロピルヘキシルアセチルセルロース、アセトキシプロピルシクロヘキシルアセチルセルロース、アセトキシプロピルフェニルアセチルセルロース、アセトキシプロピルナフチルアセチルセルロース、プロピオニルオキシプロピルメチルアセチルセルロース、プロピオニルオキシプロピルエチルアセチルセルロース、プロピオニルオキシプロピルプロピルアセチルセルロース、プロピオニルオキシプロピルブチルアセチルセルロース、プロピオニルオキシプロピルペンチルアセチルセルロース、プロピオニルオキシプロピルヘキシルアセチルセルロース、プロピオニルオキシプロピルシクロヘキシルアセチルセルロース、プロピオニルオキシプロピルフェニルアセチルセルロース、プロピオニルオキシプロピルナフチルアセチルセルロース、バレロキシプロピルメチルバレロイルセルロース、バレロキシブチルメチルバレロイルセルロースなどが挙げられる。 Specific examples of the cellulose derivative in the present invention include acetyl methyl cellulose, acetyl ethyl cellulose, acetyl propyl cellulose, acetyl butyl cellulose, acetyl pentyl cellulose, acetyl hexyl cellulose, acetyl cyclohexyl cellulose, acetyl phenyl cellulose, acetyl naphthyl cellulose, propionyl methyl cellulose, and propionyl ethyl cellulose. , Propionylpropylcellulose, propionylbutylcellulose, propionylpentylcellulose, propionylhexylcellulose, propionylcyclohexylcellulose, propionylphenylcellulose, propionylnaphthylcellulose, butyrylmethylcellulose, butyrylethylcellulose, butyrylpropylcellulose , Butyrylbutylcellulose, butyrylpentylcellulose, butyrylhexylcellulose, butyrylcyclohexylcellulose, butyrylphenylcellulose, butyrylnaphthylcellulose, methylcellulose-2-ethylhexanoate, ethylcellulose-2-ethylhexanoate, propylcellulose -2-ethylhexanoate, butylcellulose-2-ethylhexanoate, pentylcellulose-2-ethylhexanoate, hexylcellulose-2-ethylhexanoate, cyclohexylcellulose-2-ethylhexanoate, phenylcellulose -2-ethylhexanoate, naphthylcellulose-2-ethylhexanoate, acetoxyethylmethylacetylcellulose, acetoxyethylethylacetyl cell Acetoxyethylpropylacetylcellulose, acetoxyethylbutylacetylcellulose, acetoxyethylpentylacetylcellulose, acetoxyethylhexylacetylcellulose, acetoxyethylcyclohexylacetylcellulose, acetoxyethylphenylacetylcellulose, acetoxyethylnaphthylacetylcellulose, acetoxyethylmethylpropionylcellulose, Acetoxyethyl ethyl propionyl cellulose, Acetoxy ethyl propyl propionyl cellulose, Acetoxy ethyl butyl propionyl cellulose, Acetoxy ethyl pentyl propionyl cellulose, Acetoxy ethyl hexyl propionyl cellulose, Acetoxy ethyl cyclohexyl propionyl cellulose, Acetoxy Tylphenylpropionylcellulose, acetoxyethylnaphthylpropionylcellulose, acetoxyethylmethylcellulose-2-ethylhexanoate, acetoxyethylethylcellulose-2-ethylhexanoate, acetoxyethylpropylcellulose-2-ethylhexanoate, acetoxyethylbutylcellulose 2-ethylhexanoate, acetoxyethylpentylcellulose-2-ethylhexanoate, acetoxyethylhexylcellulose-2-ethylhexanoate, acetoxyethylcyclohexylcellulose-2-ethylhexanoate, acetoxyethylphenylcellulose-2-ethyl Hexanoate, acetoxyethyl naphthylcellulose-2-ethylhexanoate, propionyloxyethyl Acetylacetylcellulose, propionyloxyethylethylacetylcellulose, propionyloxyethylpropylacetylcellulose, propionyloxyethylbutylacetylcellulose, propionyloxyethylpentylacetylcellulose, propionyloxyethylhexylacetylcellulose, propionyloxyethylcyclohexylacetylcellulose, propionyloxyethylphenylacetyl Cellulose, propionyloxyethyl naphthylacetyl cellulose, propionyloxyethylmethylpropionylcellulose, propionyloxyethylethylpropionylcellulose, propionyloxyethylpropylpropionylcellulose, propionyloxyethylbutylpropionylcellulose, pro Onyloxyethylpentylpropionylcellulose, propionyloxyethylhexylpropionylcellulose, propionyloxyethylcyclohexylpropionylcellulose, propionyloxyethylphenylpropionylcellulose, propionyloxyethylnaphthylpropionylcellulose, propionyloxyethylmethylcellulose-2-ethylhexanoate, propionyloxyethyl Ethylcellulose-2-ethylhexanoate, propionyloxyethylpropylcellulose-2-ethylhexanoate, propionyloxyethylbutylcellulose-2-ethylhexanoate, propionyloxyethylpentylcellulose-2-ethylhexanoate, propionyloxy Ethyl hexyl cellulose -2-ethylhexanoate, propionyloxyethylcyclohexyl cellulose-2-ethylhexanoate, propionyloxyethylphenylcellulose-2-ethylhexanoate, propionyloxyethylnaphthylcellulose-2-ethylhexanoate, acetoxypropylmethyl Acetylcellulose, acetoxypropylethylacetylcellulose, acetoxypropylpropylacetylcellulose, acetoxypropylbutylacetylcellulose, acetoxypropylpentylacetylcellulose, acetoxypropylhexylacetylcellulose, acetoxypropylcyclohexylacetylcellulose, acetoxypropylphenylacetylcellulose, acetoxypropylnaphthylacetylcellulose , Propio Luoxypropylmethylacetylcellulose, propionyloxypropylethylacetylcellulose, propionyloxypropylpropylacetylcellulose, propionyloxypropylbutylacetylcellulose, propionyloxypropylpentylacetylcellulose, propionyloxypropylhexylacetylcellulose, propionyloxypropylcyclohexylacetylcellulose, propionyl Examples thereof include oxypropylphenylacetylcellulose, propionyloxypropylnaphthylacetylcellulose, valeroxypropylmethylvaleroylcellulose, valeroxybutylmethylvaleroylcellulose, and the like.
 本発明の成形材料は、前記特定のセルロース誘導体を1種のみ含んでもよいし、2種以上を含んでもよい。 The molding material of the present invention may contain only one kind of the specific cellulose derivative or two or more kinds.
 本発明におけるセルロース誘導体中のA)炭化水素基:-R、B)アシル基:-CO-R、及びC)アルキレンオキシ基:-RC2-O-とアシル基:-CO-RC1とを含む基の置換位置、並びにβ-グルコース環単位当たりの各置換基の数(置換度)は特に限定されない。 In the cellulose derivative of the present invention, A) hydrocarbon group: —R A , B) acyl group: —CO—R B , and C) alkyleneoxy group: —R C2 —O— and acyl group: —CO—R C1 And the number of substitution groups per each β-glucose ring unit (substitution degree) are not particularly limited.
 例えば、A)炭化水素基:-Rの置換度DS(繰り返し単位中、β-グルコース環の2位、3位及び6位の水酸基に対するRの数)は、1.0<DSであることが好ましく、1.0<DS<2.5がより好ましい。また、DSは1.1以上であることが好ましい。
 B)アシル基(-CO-R)の置換度DS(繰り返し単位中、β-グルコース環のセルロース構造の2位、3位及び6位の水酸基に対する-CO-Rの数)は、0.1<DSであることが好ましく、0.1<DS<2.0であることがより好ましい。
 C)アルキレンオキシ基:-RC2-O-とアシル基:-CO-RC1とを含む基の置換度DS(繰り返し単位中、β-グルコース環のセルロース構造の2位、3位及び6位の水酸基に対するC)アルキレンオキシ基:-RC2-O-とアシル基:-CO-RC1とを含む基の数)は、0<DSであることが好ましく、0<DS<1.0であることがより好ましい。0<DSであることにより、セルロース誘導体の溶融開始温度を低くできるので、熱成形をより容易に行うことができる。
 上記のような範囲の置換度とすることにより、機械強度及び成形性等を向上させることができる。
For example, A) hydrocarbon group: the degree of substitution DS A of —R A (the number of RA for the hydroxyl groups at the 2nd, 3rd and 6th positions of the β-glucose ring in the repeating unit) is 1.0 <DS A It is preferable that 1.0 <DS A <2.5. Further, DS A is preferably 1.1 or more.
B) Degree of substitution DS B of acyl group (—CO—R B ) (the number of —CO—R B with respect to hydroxyl groups at the 2nd, 3rd and 6th positions of the cellulose structure of the β-glucose ring in the repeating unit) 0.1 <DS B is preferable, and 0.1 <DS B <2.0 is more preferable.
C) Degree of substitution DS C of a group containing an alkyleneoxy group: —R C2 —O— and an acyl group: —CO—R C1 (in the repeating unit, the 2nd, 3rd and 6th positions of the cellulose structure of the β-glucose ring) position of C to the hydroxyl group) alkyleneoxy group: -R C2 -O- acyl group: the number of groups containing a -CO-R C1) is preferably 0 <DS C, 0 <DS C <1 0.0 is more preferable. 0 <By a DS C, it is possible to lower the melting initiation temperature of the cellulose derivative can be performed thermoforming easier.
By setting the degree of substitution within the above range, mechanical strength, moldability, and the like can be improved.
 また、セルロース誘導体中に存在する無置換の水酸基の数も特に限定されない。水素原子の置換度DS(繰り返し単位中、2位、3位及び6位の水酸基が無置換である割合)は0~1.5の範囲とすることができ、好ましくは0~0.6とすればよい。DSを0.6以下とすることにより、成形材料の流動性を向上させたり、熱分解の加速・成形時の成形材料の吸水による発泡等を抑制させたりできる。 Further, the number of unsubstituted hydroxyl groups present in the cellulose derivative is not particularly limited. The degree of substitution DS H of hydrogen atoms (ratio in which the hydroxyl groups at the 2nd, 3rd and 6th positions in the repeating unit are unsubstituted) can be in the range of 0 to 1.5, preferably 0 to 0.6. And it is sufficient. By the DS H and 0.6 or less, or to improve the fluidity of the molding material, the foaming and the like due to water absorption of the molding material during acceleration and molding of the pyrolysis can or is suppressed.
 また、本発明におけるセルロース誘導体は、A)炭化水素基、B)アシル基、及びC)アルキレンオキシ基とアシル基とを含む基以外の置換基を有しても良い。有してもよい置換基の例としては、例えばヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシエトキシエチル基、ヒドロキシプロポキシプロピル基、ヒドロキシエトキシエトキシエチル基、ヒドロキシプロポキシプロポキシプロピル基が挙げられる。よって、セルロース誘導体が有するすべての置換基の各置換度の総和は3であるが、(DS+DS+DS+DS)は3以下である。 In addition, the cellulose derivative in the present invention may have a substituent other than A) a hydrocarbon group, B) an acyl group, and C) a group containing an alkyleneoxy group and an acyl group. Examples of the substituent that may be included include a hydroxyethyl group, a hydroxypropyl group, a hydroxyethoxyethyl group, a hydroxypropoxypropyl group, a hydroxyethoxyethoxyethyl group, and a hydroxypropoxypropoxypropyl group. Therefore, the sum of the degree of substitution of all the substituents of the cellulose derivative is 3, but (DS A + DS B + DS C + DS H ) is 3 or less.
 また、前記C)の基におけるアルキレンオキシ基の導入量はモル置換度(MS:グルコース残基あたりの置換基の導入モル数)で表される(セルロース学会編集、セルロース辞典P142)。アルキレンオキシ基のモル置換度MSは、0<MSであることが好ましく、0<MS≦1.5であることがより好ましく、0<MS<1.0であることが更に好ましい。MSが1.5以下(MS≦1.5)であることにより、耐熱性・成形性等を向上させることができ、成形材料に好適なセルロース誘導体が得られる。 The amount of alkyleneoxy group introduced in the group C) is expressed in terms of molar substitution (MS: number of moles of substituent introduced per glucose residue) (edited by Cellulose Society, Cellulose Dictionary P142). The molar substitution degree MS of the alkyleneoxy group is preferably 0 <MS, more preferably 0 <MS ≦ 1.5, and still more preferably 0 <MS <1.0. When MS is 1.5 or less (MS ≦ 1.5), heat resistance, moldability and the like can be improved, and a cellulose derivative suitable for a molding material can be obtained.
 本発明の成形材料におけるセルロース誘導体は、セルロースに含まれる水酸基の水素原子が、前記A)で置換された基を少なくとも1つ、及び前記B)で置換された基を少なくとも1つ含むセルロース誘導体であるが、セルロースに含まれる水酸基の水素原子が置換される場合は、成形性の観点から、前記A)及び前記B)のみで置換されているか、又は前記A)、前記B)、及び前記C)のみで置換されている場合が好ましい。すなわち本発明におけるセルロース誘導体は、セルロースに含まれる水酸基の水素原子が前記A)、前記B)、及び前記C)以外の基により置換されていないことが好ましい。 The cellulose derivative in the molding material of the present invention is a cellulose derivative in which the hydrogen atom of the hydroxyl group contained in cellulose contains at least one group substituted with A) and at least one group substituted with B). However, when a hydrogen atom of a hydroxyl group contained in cellulose is substituted, from the viewpoint of moldability, it is substituted only by A) and B) or A), B), and C. ) Is preferred. That is, in the cellulose derivative in the present invention, it is preferable that the hydrogen atom of the hydroxyl group contained in the cellulose is not substituted with a group other than the above A), B), and C).
 本発明におけるセルロース誘導体の分子量は、数平均分子量(Mn)が5×10~1000×10の範囲が好ましく、10×10~500×10の範囲が更に好ましく、10×10~200×10の範囲が最も好ましい。また、重量平均分子量(Mw)は、7×10~10000×10の範囲が好ましく、15×10~5000×10の範囲が更に好ましく、100×10~3000×10の範囲が最も好ましい。この範囲の平均分子量とすることにより、成形体の成形性、力学強度等を向上させることができる。
 分子量分布(MWD)は1.1~10.0の範囲が好ましく、1.5~8.0の範囲が更に好ましい。この範囲の分子量分布とすることにより、成形性等を向上させることができる。
 本発明における、数平均分子量(Mn)、重量平均分子量(Mw)及び分子量分布(MWD)の測定は、ゲル・パーミエーション・クロマトグラフィー(GPC)を用いて行うことができる。具体的には、N-メチルピロリドンを溶媒とし、ポリスチレンゲルを使用し、標準単分散ポリスチレンの構成曲線から予め求められた換算分子量較正曲線を用いて求めることができる。
The molecular weight of the cellulose derivative in the present invention is preferably such that the number average molecular weight (Mn) is in the range of 5 × 10 3 to 1000 × 10 3 , more preferably in the range of 10 × 10 3 to 500 × 10 3 , and 10 × 10 3 to A range of 200 × 10 3 is most preferred. The weight average molecular weight (Mw) is preferably in the range of 7 × 10 3 to 10000 × 10 3 , more preferably in the range of 15 × 10 3 to 5000 × 10 3 , and in the range of 100 × 10 3 to 3000 × 10 3 . Is most preferred. By setting the average molecular weight within this range, it is possible to improve the moldability and mechanical strength of the molded body.
The molecular weight distribution (MWD) is preferably in the range of 1.1 to 10.0, and more preferably in the range of 1.5 to 8.0. By setting the molecular weight distribution within this range, moldability and the like can be improved.
In the present invention, the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (MWD) can be measured using gel permeation chromatography (GPC). Specifically, N-methylpyrrolidone is used as a solvent, a polystyrene gel is used, and the molecular weight can be determined using a conversion molecular weight calibration curve obtained in advance from a standard monodisperse polystyrene constituent curve.
2.セルロース誘導体の製造方法
 本発明におけるセルロース誘導体の製造方法は特に限定されず、セルロースを原料とし、セルロースに対しエーテル化及びエステル化することにより本発明におけるセルロース誘導体を製造することができる。セルロースの原料としては限定的でなく、例えば、綿、リンター、パルプ等が挙げられる。
2. Method for Producing Cellulose Derivative The method for producing a cellulose derivative in the present invention is not particularly limited, and the cellulose derivative in the present invention can be produced by using cellulose as a raw material and etherifying and esterifying cellulose. The raw material for cellulose is not limited, and examples thereof include cotton, linter, and pulp.
 前記A)炭化水素基:-R、及びB)アシル基:-CO-R(Rは炭化水素基を表す。)を有するセルロース誘導体の好ましい製造方法の態様は、セルロースエーテルに、塩基存在下、酸クロリド又は酸無水物等を反応させることにより、エステル化する工程を含むものである。
 前記セルロースエーテルとしては、例えば、セルロースに含まれるβ-グルコース環の2位、3位、及び6位の水酸基の水素原子の少なくとも一部が、炭化水素基に置換されたものを用いることができ、具体的には、メチルセルロース、エチルセルロース、プロピルセルロース、ブチルセルロース、アリルセルロース、ベンジルセルロース等が挙げられる。
A preferred embodiment of a method for producing a cellulose derivative having the above A) hydrocarbon group: —R A and B) acyl group: —CO—R B (R B represents a hydrocarbon group) includes cellulose ether, base It includes a step of esterification by reacting acid chloride or acid anhydride in the presence.
As the cellulose ether, for example, those in which at least a part of the hydrogen atoms of the hydroxyl groups at the 2nd, 3rd and 6th positions of the β-glucose ring contained in cellulose are substituted with hydrocarbon groups can be used. Specific examples include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, allyl cellulose, and benzyl cellulose.
 前記A)炭化水素基:-R、B)アシル基:-CO-R(Rは炭化水素基を表す。)、及びC)アルキレンオキシ基:-RC2-O-とアシル基:-CO-RC1とを含む基(RC1は炭化水素基を表し、RC2は炭素数が2~4のアルキレン基を表す。)を有するセルロース誘導体の好ましい製造方法の態様は、炭化水素基と、ヒドロキシエチル基を有するヒドロキシエチルセルロースエーテル又はヒドロキシプロピル基とを有するヒドロキシプロピルセルロースエーテルに酸クロライド又は酸無水物等を反応させることにより、エステル化(アシル化)する工程を含む方法によって行うものである。
 また、別の態様として、例えばメチルセルロース、エチルセルロース等のセルロースエーテルにプロピレンオキサイド等によりエーテル化するか、又はセルロースにメチルクロライド、エチルクロライド等のアルキルクロライド/炭素数3のアルキレンオキサイド等を作用させた後、更に酸クロライド又は酸無水物等を反応させることにより、エステル化する工程を含む方法も挙げられる。
 酸クロライドを反応させる方法としては、例えばCellulose 10;283-296,2003に記載の方法を用いることができる。
 炭化水素基とヒドロキシエチル基を有するセルロースエーテルとしては、具体的には、ヒドロキシエチルメチルセルロース、ヒドロキシエチルエチルセルロース、ヒドロキシエチルプロピルセルロース、ヒドロキシエチルアリルセルロース、ヒドロキシエチルベンジルセルロース等が挙げられる。好ましくは、ヒドロキシエチルメチルセルロース、ヒドロキシエチルエチルセルロースである。
 炭化水素基とヒドロキシプロピル基を有するセルロースエーテルとしては、具体的には、ヒドロキシプロピルメチルセルロース、ヒドロキシプロピルエチルセルロース、ヒドロキシプロピルプロピルセルロース、ヒドロキシプロピルアリルセルロース、ヒドロキシプロピルベンジルセルロース等が挙げられる。好ましくは、ヒドロキシプロピルメチルセルロース、ヒドロキシプロピルエチルセルロースである。
A) hydrocarbon group: —R A , B) acyl group: —CO—R B (R B represents a hydrocarbon group), and C) alkyleneoxy group: —R C2 —O— and an acyl group: A preferred embodiment of a method for producing a cellulose derivative having a group containing —CO—R C1 (R C1 represents a hydrocarbon group and R C2 represents an alkylene group having 2 to 4 carbon atoms) is a hydrocarbon group. And hydroxyethyl cellulose ether having a hydroxyethyl group or hydroxypropyl cellulose ether having a hydroxypropyl group are reacted by an acid chloride or an acid anhydride to react with the esterification (acylation). is there.
Further, as another embodiment, for example, after etherification with cellulose ether such as methyl cellulose or ethyl cellulose with propylene oxide or the like, alkyl chloride such as methyl chloride or ethyl chloride / alkylene oxide having 3 carbon atoms or the like is allowed to act on cellulose. Furthermore, a method including a step of esterification by reacting an acid chloride or an acid anhydride is also included.
As a method for reacting acid chloride, for example, the method described in Cellulose 10; 283-296, 2003 can be used.
Specific examples of the cellulose ether having a hydrocarbon group and a hydroxyethyl group include hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxyethyl propyl cellulose, hydroxyethyl allyl cellulose, and hydroxyethyl benzyl cellulose. Preferred are hydroxyethyl methyl cellulose and hydroxyethyl ethyl cellulose.
Specific examples of the cellulose ether having a hydrocarbon group and a hydroxypropyl group include hydroxypropylmethylcellulose, hydroxypropylethylcellulose, hydroxypropylpropylcellulose, hydroxypropylallylcellulose, hydroxypropylbenzylcellulose, and the like. Preferred are hydroxypropylmethylcellulose and hydroxypropylethylcellulose.
 酸クロリドとしては、前記B)アシル基、及びC)に含まれるアシル基に対応したカルボン酸クロライドを使用することができる。カルボン酸クロリドとしては、例えば、アセチルクロライド、プロピオニルクロライド、ブチリルクロリド、イソブチリルクロリド、ペンタノイルクロリド、2-メチルブタノイルクロリド、3-メチルブタノイルクロリド、ピバロイルクロリド、ヘキサノイルクロリド、2-メチルペンタノイルクロリド、3-メチルペンタノイルクロリド、4-メチルペンタノイルクロリド、2,2-ジメチルブタノイルクロリド、2,3-ジメチルブタノイルクロリド、3,3-ジメチルブタノイルクロリド、2-エチルブタノイルクロリド、ヘプタノイルクロリド、2-メチルヘキサノイルクロリド、3-メチルヘキサノイルクロリド、4-メチルヘキサノイルクロリド、5-メチルヘキサノイルクロリド、2,2-ジメチルペンタノイルクロリド、2,3-ジメチルペンタノイルクロリド、3,3-ジメチルペンタノイルクロリド、2-エチルペンタノイルクロリド、シクロヘキサノイルクロリド、オクタノイルクロリド、2-メチルヘプタノイルクロリド、3-メチルヘプタノイルクロリド、4-メチルヘプタノイルクロリド、5-メチルヘプタノイルクロリド、6-メチルヘプタノイルクロリド、2,2-ジメチルヘキサノイルクロリド、2,3-ジメチルヘキサノイルクロリド、3,3-ジメチルヘキサノイルクロリド、2-エチルヘキサノイルクロリド、2-プロピルペンタノイルクロリド、ノナノイルクロリド、2-メチルオクタノイルクロリド、3-メチルオクタノイルクロリド、4-メチルオクタノイルクロリド、5-メチルオクタノイルクロリド、6-メチルオクタノイルクロリド、2,2-ジメチルヘプタノイルクロリド、2,3-ジメチルヘプタノイルクロリド、3,3-ジメチルヘプタノイルクロリド、2-エチルヘプタノイルクロリド、2-プロピルヘキサノイルクロリド、2-ブチルペンタノイルクロリド、デカノイルクロリド、2-メチルノナノイルクロリド、3-メチルノナノイルクロリド、4-メチルノナノイルクロリド、5-メチルノナノイルクロリド、6-メチルノナノイルクロリド、7-メチルノナノイルクロリド、2,2-ジメチルオクタノイルクロリド、2,3-ジメチルオクタノイルクロリド、3,3-ジメチルオクタノイルクロリド、2-エチルオクタノイルクロリド、2-プロピルヘプタノイルクロリド、2-ブチルヘキサノイルクロリド等が挙げられる。 As the acid chloride, B) acyl group and carboxylic acid chloride corresponding to the acyl group contained in C) can be used. Examples of the carboxylic acid chloride include acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, pentanoyl chloride, 2-methylbutanoyl chloride, 3-methylbutanoyl chloride, pivaloyl chloride, hexanoyl chloride, 2-methylpentanoyl chloride, 3-methylpentanoyl chloride, 4-methylpentanoyl chloride, 2,2-dimethylbutanoyl chloride, 2,3-dimethylbutanoyl chloride, 3,3-dimethylbutanoyl chloride, 2- Ethylbutanoyl chloride, heptanoyl chloride, 2-methylhexanoyl chloride, 3-methylhexanoyl chloride, 4-methylhexanoyl chloride, 5-methylhexanoyl chloride, 2,2-dimethylpentanoyl chloride, , 3-dimethylpentanoyl chloride, 3,3-dimethylpentanoyl chloride, 2-ethylpentanoyl chloride, cyclohexanoyl chloride, octanoyl chloride, 2-methylheptanoyl chloride, 3-methylheptanoyl chloride, 4-methyl Heptanoyl chloride, 5-methylheptanoyl chloride, 6-methylheptanoyl chloride, 2,2-dimethylhexanoyl chloride, 2,3-dimethylhexanoyl chloride, 3,3-dimethylhexanoyl chloride, 2-ethylhexanoyl Chloride, 2-propylpentanoyl chloride, nonanoyl chloride, 2-methyloctanoyl chloride, 3-methyloctanoyl chloride, 4-methyloctanoyl chloride, 5-methyloctanoyl chloride, 6-methyloctanoy Chloride, 2,2-dimethylheptanoyl chloride, 2,3-dimethylheptanoyl chloride, 3,3-dimethylheptanoyl chloride, 2-ethylheptanoyl chloride, 2-propylhexanoyl chloride, 2-butylpentanoyl chloride, Decanoyl chloride, 2-methylnonanoyl chloride, 3-methylnonanoyl chloride, 4-methylnonanoyl chloride, 5-methylnonanoyl chloride, 6-methylnonanoyl chloride, 7-methylnonanoyl chloride, 2,2- Examples thereof include dimethyloctanoyl chloride, 2,3-dimethyloctanoyl chloride, 3,3-dimethyloctanoyl chloride, 2-ethyloctanoyl chloride, 2-propylheptanoyl chloride, 2-butylhexanoyl chloride and the like.
 酸無水物としては、例えば前記B)アシル基、及びC)に含まれるアシル基に対応したカルボン酸無水物を使用することができる。このようなカルボン酸無水物としては、例えば、酢酸無水物、プロピオン酸無水物、酪酸無水物、吉草酸無水物、ヘキサン酸無水物、ヘプタン酸無水物、オクタン酸無水物、2-エチルヘキサン酸無水物、ノナン酸無水物等が挙げられる。
 なお、前述したとおり、本発明におけるセルロース誘導体は置換基としてカルボン酸を有さないことが好ましいため、例えば無水フタル酸、無水マレイン酸等のジカルボン酸等、セルロースと反応させてカルボキシル基が生じる化合物を用いないことが好ましい。
As the acid anhydride, for example, carboxylic acid anhydrides corresponding to the acyl group contained in the above B) acyl group and C) can be used. Examples of such carboxylic anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride, octanoic anhydride, 2-ethylhexanoic acid. An anhydride, nonanoic acid anhydride, etc. are mentioned.
As described above, since the cellulose derivative in the present invention preferably has no carboxylic acid as a substituent, for example, a dicarboxylic acid such as phthalic anhydride, maleic anhydride, or the like, and a compound that generates a carboxyl group by reacting with cellulose. It is preferable not to use.
 そのほかの具体的な製造条件等は、常法に従うことができる。例えば、「セルロースの事典」131頁~164頁(朝倉書店、2000年)等に記載の方法を参考にすることができる。 Other specific manufacturing conditions can follow the usual method. For example, the method described in “Encyclopedia of Cellulose” pages 131 to 164 (Asakura Shoten, 2000) can be referred to.
3.芳香族ポリエステル
 本発明の成形材料は芳香族ポリエステルを含有する。
 芳香族ポリエステルは、結晶性を有し、硬い構造を有するため、本発明における特定のセルロース誘導体と混ぜて成形材料とすることで、特定のセルロース誘導体を単独で用いた場合よりも、摺動性を向上させることができる。更に、本発明における特定のセルロース誘導体は、エーテル構造とエステル構造を含むため、従来のセルロースエステルなどよりも、主鎖周りにより自由度の高いエーテル結合を有するため芳香族ポリエステルとの親和性に優れる。そのため、芳香族ポリエステルは、本発明における特定のセルロース誘導体に対する分散性に優れ、両者は良好に混ざり合うため、特定のセルロース誘導体を単独で用いた場合に対して耐衝撃性、及び成形性が更に向上する。また、剛性、曲げ強度、及び耐熱性といった性能にも優れる。
3. Aromatic polyester The molding material of the present invention contains an aromatic polyester.
Aromatic polyester has crystallinity and has a hard structure, so by mixing with a specific cellulose derivative in the present invention to form a molding material, it is more slidable than when a specific cellulose derivative is used alone. Can be improved. Furthermore, since the specific cellulose derivative in the present invention includes an ether structure and an ester structure, it has an ether bond having a higher degree of freedom around the main chain than a conventional cellulose ester and the like, and thus has an excellent affinity with an aromatic polyester. . Therefore, the aromatic polyester is excellent in dispersibility with respect to the specific cellulose derivative in the present invention, and both are mixed well. Therefore, the impact resistance and moldability are further improved when the specific cellulose derivative is used alone. improves. Moreover, it is excellent also in performance, such as rigidity, bending strength, and heat resistance.
 本発明でいう芳香族ポリエステルとは、芳香族ジカルボン酸とジオール、又はそのエステル誘導体とを主成分とする縮合反応により得られる重合体ないしは共重合体である。
 本発明における芳香族ポリエステルは、セルロース誘導体の剛性を損なわず摺動性を付与するという理由から、曲げ弾性率が1.5GPa(JIS K-7203での測定値)より大きいことが好ましく、2.0GPa~3.5GPaであることがより好ましい。
The aromatic polyester referred to in the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising an aromatic dicarboxylic acid and a diol or an ester derivative thereof.
The aromatic polyester in the present invention preferably has a flexural modulus larger than 1.5 GPa (measured value according to JIS K-7203) because it imparts slidability without impairing the rigidity of the cellulose derivative. More preferably, it is 0 GPa to 3.5 GPa.
 本発明における芳香族ポリエステルの原料である芳香族ジカルボン酸としてはテレフタル酸、イソフタル酸、オルトフタル酸、1,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸、4,4’-ビフェニルジカルボン酸、4,4’-ビフェニルエーテルジカルボン酸、4,4’-ビフェニルメタンジカルボン酸、4,4’-ビフェニルスルホンジカルボン酸、4,4’-ビフェニルイソプロピリデンジカルボン酸、1,2-ビス(フェノキシ)エタン-4,4’-ジカルボン酸、2,5-アントラセンジカルボン酸、2,6-アントラセンジカルボン酸、4,4’-p-ターフェニレンジカルボン酸、2,5-ピリジンジカルボン酸等の芳香族系ジカルボン酸が好適に用いられ、特にテレフタル酸、2,6-ナフタレンジカルボン酸が好ましく使用できる。 Examples of the aromatic dicarboxylic acid that is a raw material of the aromatic polyester in the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 4,4′-biphenylmethane dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane Aromatic dicarboxylic acids such as -4,4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4'-p-terphenylene dicarboxylic acid, 2,5-pyridinedicarboxylic acid Acids are preferably used, particularly terephthalic acid and 2,6-naphthalenedica. Bonn acid can be preferably used.
 芳香族ジカルボン酸は二種以上を混合して使用してもよい。なお少量であれば、該ジカルボン酸と共にアジピン酸、アゼライン酸、セバシン酸、ドデカンジ酸等の脂肪族ジカルボン酸、シクロヘキサンジカルボン酸等の脂環族ジカルボン酸等を一種以上混合使用することも可能である。 Aromatic dicarboxylic acids may be used as a mixture of two or more. In addition, if it is a small amount, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanediic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid together with the dicarboxylic acid. .
 また本発明の芳香族ポリエステルを構成する原料であるジオールとしては、エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキシレングリコール、ネオペンチルグリコール、2-メチル-1,3-プロパンジオール、ジエチレングリコール、トリエチレングリコール、等の脂肪族ジオール、1,4-シクロヘキサンジメタノール等の脂環族ジオール等、及びそれらの混合物等が挙げられる。 Examples of the diol that is a raw material constituting the aromatic polyester of the present invention include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, and triethylene glycol. , Alicyclic diols such as 1,4-cyclohexanedimethanol, and mixtures thereof.
 具体的な芳香族ポリエステルとしては、ポリエチレンテレフタレート(PET)、ポリプロピレンテレフタレート、ポリブチレンテレフタレート(PBT)、ポリへキシレンテレフタレート、ポリエチレンナフタレート(PEN)、ポリブチレンナフタレート(PBN)、ポリエチレン-1,2-ビス(フェノキシ)エタン-4,4’-ジカルボキシレート、等の他、ポリエチレンイソフタレート/テレフタレート、ポリブチレンテレフタレート/イソフタレート、等のような共重合ポリエステルが挙げられる。これらのうち、機械的性質等のバランスがとれたポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレートが好ましく使用でき、ポリエチレンテレフタレート、ポリブチレンテレフタレートがより好ましく使用できる。本発明においては、これらを単独でも用いても、2種以上を組み合わせて用いても良い。 Specific aromatic polyesters include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2 In addition to bis (phenoxy) ethane-4,4′-dicarboxylate, etc., there may be mentioned copolyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, etc. Among these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate having a good balance of mechanical properties and the like can be preferably used, and polyethylene terephthalate and polybutylene terephthalate can be more preferably used. In the present invention, these may be used alone or in combination of two or more.
 本発明における芳香族ポリエステルの分子量は、数平均分子量(Mn)が5×10~1000×10の範囲が好ましく、10×10~500×10の範囲が更に好ましく、10×10~200×10の範囲が最も好ましい。また、重量平均分子量(Mw)は、7×10~10000×10の範囲が好ましく、15×10~5000×10の範囲が更に好ましく、100×10~3000×10の範囲が最も好ましい。この範囲の平均分子量とすることにより、マトリックス樹脂との分散性、成形体の成形性、力学強度等を向上させることができる。
 分子量分布(MWD)は1.1~10.0の範囲が好ましく、1.5~8.0の範囲が更に好ましい。この範囲の分子量分布とすることにより、マトリックス樹脂との分散性、成形性等を向上させることができる。
 本発明における、数平均分子量(Mn)、重量平均分子量(Mw)及び分子量分布(MWD)の測定は、ゲル・パーミエーション・クロマトグラフィー(GPC)を用いて行うことができる。具体的には、ペンタフルオロフェノールを溶媒とし、ポリスチレンゲルを使用し、標準単分散ポリスチレンの構成曲線から予め求められた換算分子量較正曲線を用いて求めることができる。
The molecular weight of the aromatic polyester in the present invention is preferably a number average molecular weight (Mn) in the range of 5 × 10 3 to 1000 × 10 3 , more preferably in the range of 10 × 10 3 to 500 × 10 3 , and 10 × 10 3. A range of ˜200 × 10 3 is most preferred. The weight average molecular weight (Mw) is preferably in the range of 7 × 10 3 to 10000 × 10 3 , more preferably in the range of 15 × 10 3 to 5000 × 10 3 , and in the range of 100 × 10 3 to 3000 × 10 3 . Is most preferred. By setting the average molecular weight within this range, the dispersibility with the matrix resin, the moldability of the molded body, the mechanical strength, and the like can be improved.
The molecular weight distribution (MWD) is preferably in the range of 1.1 to 10.0, and more preferably in the range of 1.5 to 8.0. By setting the molecular weight distribution within this range, dispersibility with the matrix resin, moldability, and the like can be improved.
In the present invention, the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (MWD) can be measured using gel permeation chromatography (GPC). Specifically, it can be determined using a converted molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene using pentafluorophenol as a solvent and using polystyrene gel.
 芳香族ポリエステルは市販品を用いてもよく、ポリエチレンテレフタレート樹脂(三井PET J005、三井ペット樹脂(株)製)、ポリブチレンテレフタレート樹脂(ジュラネックス2002、日本ポリプラスチック(株)製)などが挙げられる。 As the aromatic polyester, commercially available products may be used, and examples thereof include polyethylene terephthalate resin (Mitsui PET J005, manufactured by Mitsui Pet Resin Co., Ltd.), polybutylene terephthalate resin (Juranex 2002, manufactured by Nippon Polyplastics Co., Ltd.), and the like. .
 かかる芳香族ポリエステルの製造方法については、常法に従い、チタン、ゲルマニウム、アンチモン等を含有する重縮合触媒の存在下に、加熱しながらジカルボン酸成分と前記ジオール成分とを重合させ、副生する水又は低級アルコールを系外に排出することにより行われる。 With respect to the method for producing such an aromatic polyester, in accordance with a conventional method, in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., the dicarboxylic acid component and the diol component are polymerized while heating, and water produced as a by-product. Alternatively, it is carried out by discharging lower alcohol out of the system.
4.相溶化剤
 本発明の成形材料は、更に相溶化剤を含有することが好ましい。これによって、前記芳香族ポリエステルは、本発明におけるセルロース誘導体に対する分散性が更に向上するので、特定のセルロース誘導体を単独で用いた場合と比較しても、剛性、曲げ強度、耐熱性といった性能に優れる。
4). Compatibilizer The molding material of the present invention preferably further contains a compatibilizer. As a result, the aromatic polyester further improves dispersibility with respect to the cellulose derivative in the present invention. Therefore, the aromatic polyester is superior in performance such as rigidity, bending strength, and heat resistance as compared with the case where a specific cellulose derivative is used alone. .
 本発明における相溶化剤は、低分子化合物であっても、高分子化合物であってもよいが、エポキシ基、カルボジイミド基、イソシアネート基、オキサゾリン基、酸無水物基などの鎖延長を伴う反応性を持つポリマーが好ましく、特に、カルボン酸無水物基、エポキシ基、イソシアネート基、オキサゾリン基を有するものが好ましい。
 好ましい相溶化剤としては、カルボン酸無水物、エポキシ基、イソシアネート基、及びオキサゾリン基で変性された重合体、ブロック共重合体、グラフト重合体、並びにランダム共重合体、更に種々のノニオン系界面活性剤、カップリング剤、架橋剤を挙げることができる。
 相溶化剤は、上記の条件を満たす材料であれば特に限定されないが、具体的には、日本油脂(株)製モディパーシリーズ、住友化学(株)製、ボンドファースト、ボンダインシリーズ、日本石油(株)社製レクスパールシリーズ、東亞合成(株)社製レゼダシリーズ、アルフォンシリーズ、日本触媒(株)製エポクロスシリーズ、旭化成ケミカルズ(株)社製デュラネートシリーズ(いずれも商品名)などの市販品が好適に用いられる。また相溶化剤はこれらに限定されることはなく、「プラスチック相溶化剤 開発・評価・リサイクル」(シーエムシー出版)に記載の相溶化剤なども好適に用いることができる。
The compatibilizing agent in the present invention may be a low molecular compound or a high molecular compound, but has reactivity with chain extension such as an epoxy group, a carbodiimide group, an isocyanate group, an oxazoline group, and an acid anhydride group. A polymer having a carboxylic acid anhydride group, an epoxy group, an isocyanate group, or an oxazoline group is particularly preferable.
Preferred compatibilizers include polymers modified with carboxylic acid anhydrides, epoxy groups, isocyanate groups, and oxazoline groups, block copolymers, graft polymers, random copolymers, and various nonionic surfactants. Agents, coupling agents, and crosslinking agents.
The compatibilizing agent is not particularly limited as long as it satisfies the above conditions, and specifically, Nippon Oil & Fats Modiper Series, Sumitomo Chemical Co., Ltd., Bond First, Bondine Series, Nippon Oil Commercially available such as Lexpearl series manufactured by Co., Ltd., Reseda series manufactured by Toagosei Co., Ltd., Alfon series, Epocross series manufactured by Nippon Shokubai Co., Ltd., Duranate series manufactured by Asahi Kasei Chemicals Co., Ltd. The product is preferably used. In addition, the compatibilizer is not limited to these, and the compatibilizer described in “Plastic compatibilizer development / evaluation / recycling” (CMC Publishing Co., Ltd.) can also be suitably used.
5.成形材料、及び成形体
 本発明の成形材料は、上記で説明したセルロース誘導体と芳香族ポリエステルとを含有しており、任意に相溶化剤を含有する。また必要に応じてその他の添加剤を含有することができる。
 本発明の成形材料に含まれる成分の含有割合は、特に限定されない。
 本発明の成形材料に含まれるセルロース誘導体の含有割合は、特に限定されない。好ましくはセルロース誘導体を全固形分に対して、35質量%以上、より好ましくは45質量%以上99質量%以下、更に好ましくは60質量%以上95質量%以下含有する。
 本発明の成形材料に含まれる芳香族ポリエステルの含有割合は、特に限定されない。好ましくは芳香族ポリエステルを全固形分に対して1質量%以上70質量%以下、より好ましくは5質量%以上50質量%以下含有する。
 また、耐衝撃性、成形加工性、摺動性の鼎立の観点から、セルロース誘導体と芳香族ポリエステルとの質量組成比(セルロース誘導体/芳香族ポリエステル)が、20/80~95/5であることが好ましく、より好ましくは40/60~90/10、更に好ましくは、60/40~90/10である。
5. Molding material and molded body The molding material of the present invention contains the cellulose derivative described above and an aromatic polyester, and optionally contains a compatibilizing agent. Moreover, another additive can be contained as needed.
The content rate of the component contained in the molding material of this invention is not specifically limited.
The content ratio of the cellulose derivative contained in the molding material of the present invention is not particularly limited. Preferably, the cellulose derivative is contained in an amount of 35% by mass or more, more preferably 45% by mass or more and 99% by mass or less, still more preferably 60% by mass or more and 95% by mass or less based on the total solid content.
The content ratio of the aromatic polyester contained in the molding material of the present invention is not particularly limited. Preferably, the aromatic polyester is contained in an amount of 1 to 70% by mass, more preferably 5 to 50% by mass, based on the total solid content.
In addition, from the standpoint of impact resistance, molding processability, and slidability, the mass composition ratio of the cellulose derivative to the aromatic polyester (cellulose derivative / aromatic polyester) is 20/80 to 95/5. Is more preferable, more preferably 40/60 to 90/10, still more preferably 60/40 to 90/10.
 本発明の成形材料が相溶化剤を含有する場合、その含有量は限定的でないが、セルロース誘導体と芳香族ポリエステルの合計100質量部に対して0.1~30質量部が好ましく、更に好ましくは0.5~20質量部である。この範囲とすることにより、十分な相溶性向上効果を得ることができ、また、成形材料の粘度増加などの不具合が生じ難い。 When the molding material of the present invention contains a compatibilizing agent, the content is not limited, but is preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight in total of the cellulose derivative and the aromatic polyester. 0.5 to 20 parts by mass. By setting it within this range, a sufficient compatibility improvement effect can be obtained, and problems such as an increase in the viscosity of the molding material are unlikely to occur.
 本発明の成形材料は、セルロース誘導体、及び芳香族ポリエステルのほか、必要に応じて、酸化防止剤、フィラー(強化材)、難燃剤等の種々の添加剤を含有していてもよい。 The molding material of the present invention may contain various additives such as an antioxidant, a filler (reinforcing material), a flame retardant, etc., as necessary, in addition to the cellulose derivative and the aromatic polyester.
 本発明の成形材料が酸化防止剤を含有する場合、その含有量は限定的でないが、成形材料中、通常30質量%以下、好ましくは0.01~10質量%とすればよい。この範囲とすることにより、混練や成型プロセスでの加熱に対して樹脂が十分な安定性の向上効果を得ることができ好ましい。
 酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、イオウ系酸化防止剤、リン系酸化防止剤等が挙げられ、好ましくは、フェノール系酸化防止剤である。フェノール系酸化防止剤としては、チバ・スペシャルティ・ケミカルズ(株)製のイルガノックス1010、イルガノックス1076、イルガノックス3114等を好適に使用できる
When the molding material of the present invention contains an antioxidant, its content is not limited, but it is usually 30% by mass or less, preferably 0.01 to 10% by mass in the molding material. By setting it within this range, the resin can obtain a sufficient stability improving effect against heating in the kneading or molding process, which is preferable.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like, and phenol-based antioxidants are preferable. As the phenolic antioxidant, Irganox 1010, Irganox 1076, Irganox 3114, etc. manufactured by Ciba Specialty Chemicals Co., Ltd. can be suitably used.
 本発明の成形材料は、フィラーを含有することにより、成形材料によって形成される成形体の機械的特性を強化することができる。
 フィラーとしては、公知のものを使用できる。フィラーの形状は、繊維状、板状、粒状、粉末状等いずれでもよい。また、無機物でも有機物でもよい。
 具体的には、無機フィラーとしては、ガラス繊維、炭素繊維、グラファイト繊維、金属繊維、チタン酸カリウムウイスカー、ホウ酸アルミニウムウイスカー、マグネシウム系ウイスカー、珪素系ウイスカー、ワラステナイト、セピオライト、スラグ繊維、ゾノライト、エレスタダイト、石膏繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア繊維、窒化硼素繊維、窒化硅素繊維及び硼素繊維等の繊維状の無機フィラーや;ガラスフレーク、非膨潤性雲母、カーボンブラック、グラファイト、金属箔、セラミックビーズ、タルク、クレー、マイカ、セリサイト、ゼオライト、ベントナイト、ドロマイト、カオリン、微粉ケイ酸、長石粉、チタン酸カリウム、シラスバルーン、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、酸化カルシウム、酸化アルミニウム、酸化チタン、酸化マグネシウム、ケイ酸アルミニウム、酸化ケイ素、水酸化アルミニウム、水酸化マグネシウム、石膏、ノバキュライト、ドーソナイト、白土等の板状や粒状の無機フィラーが挙げられる。
By containing the filler, the molding material of the present invention can reinforce the mechanical properties of the molded body formed of the molding material.
A well-known thing can be used as a filler. The shape of the filler may be any of fibrous, plate-like, granular, powdery and the like. Further, it may be inorganic or organic.
Specifically, as the inorganic filler, glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, slag fiber, zonolite, Elastadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, and other inorganic fillers; glass flakes, non-swellable mica, carbon black, graphite, metal foil , Ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silicate, feldspar, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide Beam, aluminum oxide, titanium oxide, magnesium oxide, aluminum silicate, silicon oxide, aluminum hydroxide, magnesium hydroxide, gypsum, novaculite, dawsonite, and a plate-like or granular inorganic fillers of clay or the like.
 有機フィラーとしては、ポリエステル繊維、ナイロン繊維、アクリル繊維、再生セルロース繊維、アセテート繊維等の合成繊維、ケナフ、ラミー、木綿、ジュート、麻、サイザル、マニラ麻、亜麻、リネン、絹、ウール等の天然繊維、微結晶セルロース、さとうきび、木材パルプ、紙屑、古紙等から得られる繊維状の有機フィラーや、有機顔料等の粒状の有機フィラーが挙げられる。 Organic fillers include synthetic fibers such as polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, and acetate fiber, and natural fibers such as kenaf, ramie, cotton, jute, hemp, sisal, Manila hemp, flax, linen, silk, and wool. Examples thereof include fibrous organic fillers obtained from microcrystalline cellulose, sugar cane, wood pulp, paper waste, waste paper and the like, and granular organic fillers such as organic pigments.
 成形材料がフィラーを含有する場合、その含有量は限定的でないが、セルロース誘導体と芳香族ポリエステルの合計100質量部に対して、通常30質量部以下、好ましくは5~10質量部とすればよい。 When the molding material contains a filler, the content is not limited, but is usually 30 parts by mass or less, preferably 5 to 10 parts by mass with respect to 100 parts by mass in total of the cellulose derivative and the aromatic polyester. .
 本発明の成形材料は、難燃剤を含有してもよい。これによって、その燃焼速度の低下又は抑制といった難燃効果を向上させることができる。
 難燃剤は、特に限定されず、常用のものを用いることができる。例えば、臭素系難燃剤、塩素系難燃剤、リン含有難燃剤、ケイ素含有難燃剤、窒素化合物系難燃剤、無機系難燃剤等が挙げられる。これらの中でも、樹脂との複合時や成形加工時に熱分解してハロゲン化水素が発生して加工機械や金型を腐食させたり、作業環境を悪化させたりすることがなく、また、焼却廃棄時にハロゲンが気散したり、分解してダイオキシン類等の有害物質の発生等によって環境に悪影響を与える可能性が少ないことから、リン含有難燃剤及びケイ素含有難燃剤が好ましい。
The molding material of the present invention may contain a flame retardant. Thereby, the flame retarding effect such as reduction or suppression of the burning rate can be improved.
The flame retardant is not particularly limited, and a conventional flame retardant can be used. For example, brominated flame retardants, chlorine-based flame retardants, phosphorus-containing flame retardants, silicon-containing flame retardants, nitrogen compound-based flame retardants, inorganic flame retardants and the like can be mentioned. Among these, hydrogen halides are not generated by thermal decomposition during resin compounding or molding, and do not corrode processing machines or molds or deteriorate the working environment. Phosphorus-containing flame retardants and silicon-containing flame retardants are preferred because they are less likely to adversely affect the environment through the generation of harmful substances such as dioxins when they are diffused or decomposed.
 リン含有難燃剤としては、特に限定されることはなく、常用のものを用いることができる。例えば、リン酸エステル、リン酸縮合エステル、ポリリン酸塩などの有機リン系化合物が挙げられる。 The phosphorus-containing flame retardant is not particularly limited, and a commonly used one can be used. Examples thereof include organic phosphorus compounds such as phosphate esters, phosphate condensation esters, and polyphosphates.
 リン酸エステルの具体例としては、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリ(2-エチルヘキシル)ホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリス(イソプロピルフェニル)ホスフェート、トリス(フェニルフェニル)ホスフェート、トリナフチルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート、ジフェニル(2-エチルヘキシル)ホスフェート、ジ(イソプロピルフェニル)フェニルホスフェート、モノイソデシルホスフェート、2-アクリロイルオキシエチルアシッドホスフェート、2-メタクリロイルオキシエチルアシッドホスフェート、ジフェニル-2-アクリロイルオキシエチルホスフェート、ジフェニル-2-メタクリロイルオキシエチルホスフェート、メラミンホスフェート、ジメラミンホスフェート、メラミンピロホスフェート、トリフェニルホスフィンオキサイド、トリクレジルホスフィンオキサイド、メタンホスホン酸ジフェニル、フェニルホスホン酸ジエチルなどを挙げることができる。 Specific examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) Phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl Acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl -2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate Can be mentioned.
 リン酸縮合エステルとしては、例えば、レゾルシノールポリフェニルホスフェート、レゾルシノールポリ(ジ-2,6-キシリル)ホスフェート、ビスフェノールAポリクレジルホスフェート、ハイドロキノンポリ(2,6-キシリル)ホスフェート並びにこれらの縮合物などの芳香族リン酸縮合エステル等を挙げることができる。 Examples of the phosphoric acid condensed ester include resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and condensates thereof. Aromatic phosphoric acid condensed ester and the like.
 また、リン酸、ポリリン酸と周期律表1族~14族の金属、アンモニア、脂肪族アミン、芳香族アミンとの塩からなるポリリン酸塩を挙げることもできる。ポリリン酸塩の代表的な塩として、金属塩としてリチウム塩、ナトリウム塩、カルシウム塩、バリウム塩、鉄(II)塩、鉄(III)塩、アルミニウム塩など、脂肪族アミン塩としてメチルアミン塩、エチルアミン塩、ジエチルアミン塩、トリエチルアミン塩、エチレンジアミン塩、ピペラジン塩などがあり、芳香族アミン塩としてはピリジン塩、トリアジン等が挙げられる。 In addition, polyphosphates composed of salts of phosphoric acid, polyphosphoric acid and metals of Groups 1 to 14 of the periodic table, ammonia, aliphatic amines, and aromatic amines can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts and the like as metal salts, methylamine salts as aliphatic amine salts, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts and triazines.
 また、前記以外にも、トリスクロロエチルホスフェート、トリスジクロロプロピルホスフェート、トリス(β-クロロプロピル)ホスフェート)などの含ハロゲンリン酸エステル、また、リン原子と窒素原子が二重結合で結ばれた構造を有するホスファゼン化合物、リン酸エステルアミドを挙げることができる。
 これらのリン含有難燃剤は、1種単独でも2種以上を組み合わせて用いてもよい。
In addition to the above, halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris (β-chloropropyl) phosphate), and structures in which a phosphorus atom and a nitrogen atom are connected by a double bond Phosphazene compounds having phosphoric acid and phosphoric ester amides.
These phosphorus-containing flame retardants may be used singly or in combination of two or more.
 ケイ素含有難燃剤としては、二次元又は三次元構造の有機ケイ素化合物、ポリジメチルシロキサン、又はポリジメチルシロキサンの側鎖又は末端のメチル基が、水素原子、置換又は非置換の脂肪族炭化水素基、芳香族炭化水素基で置換又は修飾されたもの、いわゆるシリコーンオイル、又は変性シリコーンオイルが挙げられる。 Examples of the silicon-containing flame retardant include an organic silicon compound having a two-dimensional or three-dimensional structure, polydimethylsiloxane, or a methyl group at a side chain or a terminal of polydimethylsiloxane, a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, Examples thereof include those substituted or modified with an aromatic hydrocarbon group, so-called silicone oils, or modified silicone oils.
 置換又は非置換の脂肪族炭化水素基、芳香族炭化水素基としては、例えば、アルキル基、シクロアルキル基、フェニル基、ベンジル基、アミノ基、エポキシ基、ポリエーテル基、カルボキシル基、メルカプト基、クロロアルキル基、アルキル高級アルコールエステル基、アルコール基、アラルキル基、ビニル基、又はトリフロロメチル基等が挙げられる。
 これらのケイ素含有難燃剤は1種単独でも2種以上を組み合わせて用いてもよい。
Examples of the substituted or unsubstituted aliphatic hydrocarbon group and aromatic hydrocarbon group include an alkyl group, a cycloalkyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, a polyether group, a carboxyl group, a mercapto group, Examples include a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group.
These silicon-containing flame retardants may be used alone or in combination of two or more.
 また、前記リン含有難燃剤又はケイ素含有難燃剤以外の難燃剤としては、例えば、水酸化マグネシウム、水酸化アルミニウム、三酸化アンチモン、五酸化アンチモン、アンチモン酸ソーダ、ヒドロキシスズ酸亜鉛、スズ酸亜鉛、メタスズ酸、酸化スズ、酸化スズ塩、硫酸亜鉛、酸化亜鉛、酸化第一鉄、酸化第二鉄、酸化第一錫、酸化第二スズ、ホウ酸亜鉛、ホウ酸アンモニウム、オクタモリブデン酸アンモニウム、タングステン酸の金属塩、タングステンとメタロイドとの複合酸化物、スルファミン酸アンモニウム、臭化アンモニウム、ジルコニウム系化合物、グアニジン系化合物、フッ素系化合物、黒鉛、膨潤性黒鉛等の無機系難燃剤を用いることができる。これらの他の難燃剤は、1種単独で用いても、2種以上を併用して用いてもよい。 Examples of the flame retardant other than the phosphorus-containing flame retardant or the silicon-containing flame retardant include, for example, magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, Metastannic acid, tin oxide, tin oxide salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, ammonium borate, ammonium octamolybdate, tungsten Inorganic flame retardants such as acid metal salts, complex oxides of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, fluorine compounds, graphite, and swellable graphite can be used. . These other flame retardants may be used alone or in combination of two or more.
 本発明の成形材料が難燃剤を含有する場合、その含有量は限定的でないが、セルロース誘導体と芳香族ポリエステルの合計100質量部に対して、通常30質量部以下、好ましくは2~10質量部とすればよい。この範囲とすることにより、十分な難燃性向上効果を得ることができ、ペレットブロッキングの発生の抑制ができる。 When the molding material of the present invention contains a flame retardant, the content is not limited, but is usually 30 parts by mass or less, preferably 2 to 10 parts by mass with respect to a total of 100 parts by mass of the cellulose derivative and the aromatic polyester. And it is sufficient. By setting it as this range, a sufficient flame retardancy improving effect can be obtained, and the occurrence of pellet blocking can be suppressed.
 本発明の成形材料は、前記したもの以外にも、本発明の目的を阻害しない範囲で、成形性・難燃性等の各種特性をより一層改善する目的で他の成分を含んでいてもよい。
 他の成分としては、例えば、前記セルロース誘導体及び前記芳香族ポリエステル以外のポリマー、可塑剤、安定剤(紫外線吸収剤など)、離型剤(脂肪酸、脂肪酸金属塩、オキシ脂肪酸、脂肪酸エステル、脂肪族部分鹸化エステル、パラフィン、低分子量ポリオレフィン、脂肪酸アミド、アルキレンビス脂肪酸アミド、脂肪族ケトン、脂肪酸低級アルコールエステル、脂肪酸多価アルコールエステル、脂肪酸ポリグリコールエステル、変成シリコーン)、帯電防止剤、難燃助剤、加工助剤、ドリップ防止剤、抗菌剤、防カビ剤等が挙げられる。更に、染料や顔料を含む着色剤などを添加することもできる。
The molding material of the present invention may contain other components other than those described above for the purpose of further improving various properties such as moldability and flame retardancy within the range not impairing the object of the present invention. .
Examples of other components include polymers other than the cellulose derivative and the aromatic polyester, plasticizers, stabilizers (ultraviolet absorbers, etc.), mold release agents (fatty acids, fatty acid metal salts, oxyfatty acids, fatty acid esters, aliphatics. Partially saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, modified silicone), antistatic agent, flame retardant aid , Processing aids, anti-drip agents, antibacterial agents, antifungal agents and the like. Further, a coloring agent containing a dye or a pigment can be added.
 前記セルロース誘導体及び前記芳香族ポリエステル以外のポリマーとしては、芳香族ポリエステル以外の熱可塑性ポリマー、熱硬化性ポリマーのいずれも用い得るが、成形性の点から熱可塑性ポリマーが好ましい。セルロース誘導体及び芳香族ポリエステル以外のポリマーの具体例としては、低密度ポリエチレン、直鎖状低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、エチレン-プロピレン-非共役ジエン共重合体、エチレン-ブテン-1共重合体、ポリプロピレンホモポリマー、ポリプロピレンコポリマー(エチレン-プロピレンブロックコポリマーなど)、ポリブテン-1及びポリ-4-メチルペンテン-1等のポリオレフィン、ナイロン6、ナイロン46、ナイロン66、ナイロン610、ナイロン612、ナイロン6T、ナイロン12等のポリアミド、ポリスチレン、ハイインパクトポリスチレン、ポリアセタール(ホモポリマー及び共重合体を含む)、ポリウレタン、芳香族及び脂肪族ポリケトン、ポリフェニレンサルファイド、ポリエーテルエーテルケトン、熱可塑性澱粉樹脂、ポリメタクリル酸メチルやメタクリル酸エステル-アクリル酸エステル共重合体などのアクリル樹脂、AS樹脂(アクリロニトリル-スチレン共重合体)、ポリ塩化ビニル、ポリ塩化ビニリデン、ビニルエステル系樹脂、無水マレイン酸-スチレン共重合体、MS樹脂(メタクリル酸メチル-スチレン共重合体)、ポリカーボネート、ポリアリレート、ポリスルホン、ポリエーテルスルホン、フェノキシ樹脂、ポリフェニレンエーテル、変性ポリフェニレンエーテル、ポリエーテルイミド等の熱可塑性ポリイミド、ポリテトラフルオロエチレン、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン-エチレン共重合体、テトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体、ポリクロロトリフルオロエチレン、ポリフッ化ビニリデン、テトラフルオロエチレン-ヘキサフルオロプロピレン-パーフルオロアルキルビニルエーテル共重合体などのフッ素系ポリマー、酢酸セルロース、ポリビニルアルコール、不飽和ポリエステル、メラミン樹脂、フェノール樹脂、尿素樹脂、ポリイミドなどを挙げることができる。
 また、各種アクリルゴム、エチレン-酢酸ビニル共重合体、エチレン-アクリル酸共重合体及びそのアルカリ金属塩(いわゆるアイオノマー)、エチレン-アクリル酸アルキルエステル共重合体(例えば、エチレン-アクリル酸エチル共重合体、エチレン-アクリル酸ブチル共重合体)、ジエン系ゴム(例えば、1,4-ポリブタジエン、1,2-ポリブタジエン、ポリイソプレン、ポリクロロプレン)、ジエンとビニル単量体との共重合体(例えば、スチレン-ブタジエンランダム共重合体、スチレン-ブタジエンブロック共重合体、スチレン-ブタジエン-スチレンブロック共重合体、スチレン-イソプレンランダム共重合体、スチレン-イソプレンブロック共重合体、スチレン-イソプレン-スチレンブロック共重合体、ポリブタジエンにスチレンをグラフト共重合させたもの、ブタジエン-アクリロニトリル共重合体)、ポリイソブチレン、イソブチレンとブタジエン又はイソプレンとの共重合体、ブチルゴム、天然ゴム、チオコールゴム、多硫化ゴム、アクリルゴム、ニトリルゴム、ポリエーテルゴム、エピクロロヒドリンゴム、フッ素ゴム、シリコーンゴム、その他ポリウレタン系やポリエステル系、ポリアミド系などの熱可塑性エラストマー等が挙げられる。
As the polymer other than the cellulose derivative and the aromatic polyester, any of a thermoplastic polymer and a thermosetting polymer other than the aromatic polyester can be used, but a thermoplastic polymer is preferable from the viewpoint of moldability. Specific examples of polymers other than cellulose derivatives and aromatic polyesters include low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, Ethylene-butene-1 copolymer, polypropylene homopolymer, polypropylene copolymer (such as ethylene-propylene block copolymer), polyolefins such as polybutene-1 and poly-4-methylpentene-1, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 6T, nylon 12 and other polyamides, polystyrene, high impact polystyrene, polyacetal (including homopolymers and copolymers), polyurethane, aromatic and aliphatic polyketo , Polyphenylene sulfide, polyether ether ketone, thermoplastic starch resin, acrylic resin such as polymethyl methacrylate and methacrylic ester-acrylic ester copolymer, AS resin (acrylonitrile-styrene copolymer), polyvinyl chloride, poly Vinylidene chloride, vinyl ester resin, maleic anhydride-styrene copolymer, MS resin (methyl methacrylate-styrene copolymer), polycarbonate, polyarylate, polysulfone, polyethersulfone, phenoxy resin, polyphenylene ether, modified polyphenylene ether , Thermoplastic polyimide such as polyetherimide, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer Fluoropolymers such as tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, cellulose acetate, polyvinyl alcohol, Saturated polyester, melamine resin, phenol resin, urea resin, polyimide and the like can be mentioned.
Various acrylic rubbers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers and alkali metal salts thereof (so-called ionomers), ethylene-acrylic acid alkyl ester copolymers (for example, ethylene-ethyl acrylate copolymer) Copolymer, ethylene-butyl acrylate copolymer), diene rubber (for example, 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (for example, Styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer Polymer, polybutadiene Styrene-grafted styrene, butadiene-acrylonitrile copolymer), polyisobutylene, copolymer of isobutylene and butadiene or isoprene, butyl rubber, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, nitrile rubber, poly Examples include ether rubber, epichlorohydrin rubber, fluoro rubber, silicone rubber, and other thermoplastic elastomers such as polyurethane, polyester, and polyamide.
 更に、各種の架橋度を有するものや、各種のミクロ構造、例えばシス構造、トランス構造等を有するもの、ビニル基などを有するもの、あるいは各種の平均粒径を有するものや、コア層とそれを覆う1以上のシェル層から構成され、また隣接し合った層が異種の重合体から構成されるいわゆるコアシェルゴムと呼ばれる多層構造重合体なども使用することができ、更にシリコーン化合物を含有したコアシェルゴムも使用することができる。
 これらのポリマーは、1種単独で用いても、2種以上を併用してもよい。
Furthermore, those having various degrees of crosslinking, those having various microstructures such as cis structure and trans structure, those having vinyl groups, those having various average particle diameters, core layers and the like A multi-layer structure polymer called a so-called core-shell rubber, which is composed of one or more shell layers to be covered and whose adjacent layers are composed of different types of polymers, can also be used, and further a core-shell rubber containing a silicone compound Can also be used.
These polymers may be used alone or in combination of two or more.
 本発明の成形材料がセルロース誘導体及び前記芳香族ポリエステル以外のポリマーを含有する場合、その含有量は、セルロース誘導体と芳香族ポリエステルの合計100質量部に対して30質量部以下が好ましく、2~10質量部がより好ましい。 When the molding material of the present invention contains a polymer other than the cellulose derivative and the aromatic polyester, the content thereof is preferably 30 parts by mass or less with respect to 100 parts by mass in total of the cellulose derivative and the aromatic polyester. Part by mass is more preferable.
 本発明の成形材料は、可塑剤を含有してもよい。これにより、難燃性及び成形性をより一層向上させることができる。可塑剤としては、ポリマーの成形に常用されるものを用いることができる。例えば、ポリエステル系可塑剤、グリセリン系可塑剤、多価カルボン酸エステル系可塑剤、ポリアルキレングリコール系可塑剤及びエポキシ系可塑剤等が挙げられる。 The molding material of the present invention may contain a plasticizer. Thereby, a flame retardance and a moldability can be improved further. As the plasticizer, those commonly used for polymer molding can be used. Examples thereof include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.
 ポリエステル系可塑剤の具体例としては、アジピン酸、セバチン酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、ジフェニルジカルボン酸、ロジンなどの酸成分と、プロピレングリコール、1,3-ブタンジオール、1,4-ブタンジオール、1,6-ヘキサンジオール、エチレングリコール、ジエチレングリコールなどのジオール成分からなるポリエステルや、ポリカプロラクトンなどのヒドロキシカルボン酸からなるポリエステル等が挙げられる。これらのポリエステルは単官能カルボン酸若しくは単官能アルコールで末端封鎖されていてもよく、またエポキシ化合物などで末端封鎖されていてもよい。 Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, propylene glycol, 1,3-butanediol, 1,4 -Polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.
 グリセリン系可塑剤の具体例としては、グリセリンモノアセトモノラウレート、グリセリンジアセトモノラウレート、グリセリンモノアセトモノステアレート、グリセリンジアセトモノオレート及びグリセリンモノアセトモノモンタネート等が挙げられる。 Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.
 多価カルボン酸系可塑剤の具体例としては、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジブチル、フタル酸ジオクチル、フタル酸ジヘプチル、フタル酸ジベンジル、フタル酸ブチルベンジルなどのフタル酸エステル、トリメリット酸トリブチル、トリメリット酸トリオクチル、トリメリット酸トリヘキシルなどのトリメリット酸エステル、アジピン酸ジイソデシル、アジピン酸n-オクチル-n-デシル、アジピン酸メチルジグリコールブチルジグリコール、アジピン酸ベンジルメチルジグリコール、アジピン酸ベンジルブチルジグリコールなどのアジピン酸エステル、アセチルクエン酸トリエチル、アセチルクエン酸トリブチルなどのクエン酸エステル、アゼライン酸ジ-2-エチルヘキシルなどのアゼライン酸エステル、セバシン酸ジブチル、及びセバシン酸ジ-2-エチルヘキシル等が挙げられる。 Specific examples of polycarboxylic acid plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, and trimellitic acid. Trimellitic acid esters such as tributyl, trioctyl trimellitic acid, trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, adipic acid Adipic acid esters such as benzylbutyl diglycol, citrate esters such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebashi Dibutyl, and include di-2-ethylhexyl sebacate and the like.
 ポリアルキレングリコール系可塑剤の具体例としては、ポリエチレングリコール、ポリプロピレングリコール、ポリ(エチレンオキサイド・プロピレンオキサイド)ブロック及び/又はランダム共重合体、ポリテトラメチレングリコール、ビスフェノール類のエチレンオキシド付加重合体、ビスフェノール類のプロピレンオキシド付加重合体、ビスフェノール類のテトラヒドロフラン付加重合体などのポリアルキレングリコールあるいはその末端エポキシ変性化合物、末端エステル変性化合物、及び末端エーテル変性化合物等が挙げられる。 Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, and bisphenols. And a polyalkylene glycol such as a propylene oxide addition polymer, a tetrahydrofuran addition polymer of bisphenol, or a terminal epoxy-modified compound thereof, a terminal ester-modified compound, a terminal ether-modified compound, and the like.
 エポキシ系可塑剤とは、一般にはエポキシステアリン酸アルキルと大豆油とからなるエポキシトリグリセリドなどを指すが、その他にも、主にビスフェノールAとエピクロロヒドリンを原料とするような、いわゆるエポキシ樹脂も使用することができる。 The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.
 その他の可塑剤の具体例としては、ネオペンチルグリコールジベンゾエート、ジエチレングリコールジベンゾエート、トリエチレングリコールジ-2-エチルブチレートなどの脂肪族ポリオールの安息香酸エステル、ステアリン酸アミドなどの脂肪酸アミド、オレイン酸ブチルなどの脂肪族カルボン酸エステル、アセチルリシノール酸メチル、アセチルリシノール酸ブチルなどのオキシ酸エステル、ペンタエリスリトール、各種ソルビトール等が挙げられる。 Specific examples of other plasticizers include benzoate esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxy acid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, and various sorbitols.
 本発明の成形材料が可塑剤を含有する場合、その含有量は、セルロース誘導体と芳香族ポリエステルの合計100質量部に対して通常30質量部以下であり、0.005~20質量部が好ましく、より好ましくは0.01~10質量部である。 When the molding material of the present invention contains a plasticizer, the content thereof is usually 30 parts by mass or less, preferably 0.005 to 20 parts by mass with respect to 100 parts by mass in total of the cellulose derivative and the aromatic polyester, More preferably, it is 0.01 to 10 parts by mass.
 本発明の成形体は、前記セルロース誘導体と前記芳香族ポリエステルを含む成形材料を成形することにより得られる。より具体的には、前記セルロース誘導体と前記芳香族ポリエステル、又は、前記セルロース誘導体と前記芳香族ポリエステル及び必要に応じて各種添加剤等を含む成形材料を加熱し、各種の成形方法により成形する工程を含む製造方法によって得られる。
 本発明の成形体の製造方法は、前記成形材料を加熱し、成形する工程を含む。
 成形方法としては、例えば、射出成形、押し出し成形、ブロー成形等が挙げられる。
 加熱温度は、通常160~300℃であり、好ましくは180~260℃である。
The molded body of the present invention can be obtained by molding a molding material containing the cellulose derivative and the aromatic polyester. More specifically, the step of heating the cellulose derivative and the aromatic polyester, or the molding material containing the cellulose derivative and the aromatic polyester and various additives as necessary, and molding them by various molding methods. It is obtained by the manufacturing method containing.
The method for producing a molded body of the present invention includes a step of heating and molding the molding material.
Examples of the molding method include injection molding, extrusion molding, blow molding and the like.
The heating temperature is usually 160 to 300 ° C, preferably 180 to 260 ° C.
 本発明の成形体の用途は、とくに限定されるものではないが、例えば、電気電子機器(家電、OA・メディア関連機器、光学用機器及び通信機器等)の内装又は外装部品、自動車、機械部品、住宅・建築用材料等が挙げられる。これらの中でも、優れた耐熱性及び耐衝撃性を有しており、環境への負荷が小さい観点から、例えば、コピー機、プリンター、パソコン、テレビ等といった電気電子機器用の外装部品(特に筐体)として好適に使用することができる。 The use of the molded product of the present invention is not particularly limited. For example, interior or exterior parts of electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.), automobiles, mechanical parts, etc. And materials for housing and construction. Among these, from the viewpoint of having excellent heat resistance and impact resistance and low environmental load, for example, exterior parts for electric and electronic devices such as copiers, printers, personal computers, televisions (especially casings) ) Can be suitably used.
 以下、本発明に係る実施例及び比較例及びこれらを用いた評価試験の結果を示し、本発明を更に詳細に説明する。なお、本発明はこれら実施例に限定されるものではない。 Hereinafter, examples and comparative examples according to the present invention and results of evaluation tests using these will be described, and the present invention will be described in more detail. The present invention is not limited to these examples.
<合成例1:アセトキシプロピルメチルアセチルセルロース(C-1)の合成>
 メカニカルスターラー、温度計、冷却管、滴下ロートをつけた5Lの三ツ口フラスコにヒドロキシプロピルメチルセルロース(商品名メトローズ90SH-100:信越化学製)60g、N,N-ジメチルアセトアミド2100mLを量り取り、室温で攪拌した。反応系が透明になり完溶したことを確認した後、アセチルクロライド101mLをゆっくりと滴下し、系の温度を80℃~90℃に昇温した。このまま3時間攪拌した後、反応系の温度を室温まで冷却した。反応溶液を水10Lへ激しく攪拌しながら投入すると、白色固体が析出した。白色固体を吸引ろ過によりろ別し、大量の水で3回洗浄を行った。得られた白色固体を100℃で6時間真空乾燥することにより目的のセルロース誘導体(C-1)(アセトキシプロピルメチルアセチルセルロース)を白色粉体として得た。このセルロース誘導体(C-1)の25℃での水への溶解度は0.1質量%未満であった(不溶)。
<Synthesis Example 1: Synthesis of acetoxypropylmethylacetylcellulose (C-1)>
In a 5 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, weigh 60 g of hydroxypropylmethylcellulose (trade name Metroze 90SH-100: Shin-Etsu Chemical Co., Ltd.) and 2100 mL of N, N-dimethylacetamide and stir at room temperature. did. After confirming that the reaction system became transparent and completely dissolved, 101 mL of acetyl chloride was slowly added dropwise to raise the temperature of the system to 80 ° C. to 90 ° C. After stirring for 3 hours, the temperature of the reaction system was cooled to room temperature. When the reaction solution was added to 10 L of water with vigorous stirring, a white solid was precipitated. The white solid was filtered off by suction filtration and washed with a large amount of water three times. The obtained white solid was vacuum-dried at 100 ° C. for 6 hours to obtain the objective cellulose derivative (C-1) (acetoxypropylmethylacetylcellulose) as a white powder. The solubility of this cellulose derivative (C-1) in water at 25 ° C. was less than 0.1% by mass (insoluble).
<合成例2、3、4:アセトキシエチルメチルアセチルセルロース(C-2)、メチルアセチルセルロース(C-3)、エチルアセチルセルロース(C-4)の合成>
 合成例1におけるヒドロキシプロピルメチルセルロース(商品名メトローズ90SH-100:信越化学製)をヒドロキシエチルメチルセルロース(商品名マーポローズME-250T:松本油脂製)、メチルセルロース(商品名マーポローズM-4000:松本油脂製株式会社製)、エチルセルロース(商品名エトセル300CP:ダウケミカル製)に変更した以外は合成例1と同様にしてアセトキシエチルメチルアセチルセルロース(C-2)、メチルアセチルセルロース(C-3)、エチルアセチルセルロース(C-4)を得た。これらのセルロース誘導体(C-2)、(C-3)、(C-4)の25℃での水への溶解度はいずれも0.1質量%未満であった(不溶)。
<Synthesis Examples 2, 3, and 4: Synthesis of acetoxyethyl methyl acetyl cellulose (C-2), methyl acetyl cellulose (C-3), and ethyl acetyl cellulose (C-4)>
Hydroxypropyl methylcellulose (trade name Metrolose 90SH-100: manufactured by Shin-Etsu Chemical Co., Ltd.) in Synthesis Example 1 was replaced by hydroxyethyl methylcellulose (trade name Marporose ME-250T: manufactured by Matsumoto Yushi), methylcellulose (trade name Marporose M-4000: manufactured by Matsumoto Yushi Co., Ltd.) And acetoxyethyl methyl acetyl cellulose (C-2), methyl acetyl cellulose (C-3), ethyl acetyl cellulose (C-3) in the same manner as in Synthesis Example 1 except that it was changed to ethyl cellulose (trade name Etcel 300CP: manufactured by Dow Chemical). C-4) was obtained. The solubility of these cellulose derivatives (C-2), (C-3), and (C-4) in water at 25 ° C. was less than 0.1% by mass (insoluble).
<合成例5:メチルセルロース-2-エチルヘキサノエート(C-5)の合成>
 メカニカルスターラー、温度計、冷却管、滴下ロートをつけた3Lの三ツ口フラスコにメチルセルロース(和光純薬製:メチル置換度1.8)80g、ピリジン1500mLを量り取り、室温で攪拌した。ここに水冷下、2-エチルヘキサノイルクロリド173mLをゆっくりと滴下し、更に60℃で6時間攪拌した。反応後、室温に戻し、氷冷下、メタノール200mLを加えてクエンチした。反応溶液を水12Lへ激しく攪拌しながら投入すると、白色固体が析出した。白色固体を吸引ろ過によりろ別し、大量のメタノール溶媒で3回洗浄を行った。得られた白色固体を100℃で6時間真空乾燥することによりメチルセルロース-2-エチルヘキサノエート(C-5)を得た。このセルロース誘導体(C-5)の25℃での水への溶解度は0.1質量%未満であった(不溶)。
<Synthesis Example 5: Synthesis of methylcellulose-2-ethylhexanoate (C-5)>
In a 3 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, 80 g of methylcellulose (manufactured by Wako Pure Chemical Industries, Ltd .: methyl substitution degree 1.8) and 1500 mL of pyridine were weighed and stirred at room temperature. Under water cooling, 173 mL of 2-ethylhexanoyl chloride was slowly added dropwise thereto, and the mixture was further stirred at 60 ° C. for 6 hours. After the reaction, the reaction solution was returned to room temperature and quenched by adding 200 mL of methanol under ice cooling. When the reaction solution was added to 12 L of water with vigorous stirring, a white solid was precipitated. The white solid was filtered off by suction filtration and washed 3 times with a large amount of methanol solvent. The resulting white solid was vacuum-dried at 100 ° C. for 6 hours to obtain methylcellulose-2-ethylhexanoate (C-5). The solubility of this cellulose derivative (C-5) in water at 25 ° C. was less than 0.1% by mass (insoluble).
<合成例6:バレロキシプロピルメチルバレロイルセルロース(C-6)の合成>
 合成例5におけるメチルセルロース(和光純薬製:メチル置換度1.8)に変えて、ヒドロキシプロピルメチルセルロース(商品名メトローズ90SH-100:信越化学製)、及び2-エチルヘキサノイルクロリドに変えてバレロイルクロライドを用いた以外、合成例5と同様にして、バレロキシプロピルメチルバレロイルセルロース(C-6)を得た。このセルロース誘導体(C-6)の25℃での水への溶解度は0.1質量%未満であった(不溶)。
<Synthesis Example 6: Synthesis of valeroxypropyl methyl valeroyl cellulose (C-6)>
Instead of methyl cellulose in Synthesis Example 5 (manufactured by Wako Pure Chemical Industries, Ltd .: methyl substitution degree 1.8), hydroxypropylmethyl cellulose (trade name Metroze 90SH-100: manufactured by Shin-Etsu Chemical Co., Ltd.) and valeroyl in place of 2-ethylhexanoyl chloride Valeroxypropylmethylvaleroylcellulose (C-6) was obtained in the same manner as in Synthesis Example 5 except that chloride was used. The solubility of this cellulose derivative (C-6) in water at 25 ° C. was less than 0.1% by mass (insoluble).
<合成例7:バレロキシブチルメチルバレロイルセルロース(C-7)の合成>
 合成例6におけるヒドロキシプロピルメチルセルロース(商品名メトローズ90SH-100:信越化学製)に変えてヒドロキシブチルメチルセルロースを用いた以外、合成例6と同様にしてバレロキシブチルメチルバレロイルセルロース(C-7)を得た。このセルロース誘導体(C-7)の25℃での水への溶解度は0.1質量%未満であった(不溶)。
<Synthesis Example 7: Synthesis of valeroxybutyl methyl valeroyl cellulose (C-7)>
Valeroxybutylmethyl valeroyl cellulose (C-7) was synthesized in the same manner as in Synthesis Example 6 except that hydroxybutylmethylcellulose was used instead of hydroxypropylmethylcellulose (trade name Metroze 90SH-100: manufactured by Shin-Etsu Chemical) in Synthesis Example 6. Obtained. The solubility of this cellulose derivative (C-7) in water at 25 ° C. was less than 0.1% by mass (insoluble).
 なお、以上で得られたセルロース誘導体が有する炭化水素基の種類及び置換度、アルキレンオキシ基の種類及びモル置換度、アシル基の種類及びアシル化度は、Cellulose Communication 6,73-79(1999)に記載の方法を利用して、H-NMRにより、観測及び決定した。なお、炭化水素基の置換度とはグルコース環ユニットに置換した炭化水素基のモル数であり、0以上3未満の値をとる。アルキレンオキシ基のモル置換度とは、グルコース環ユニットに置換したアルキレンオキシ基のモル数であり、0以上の値をとる。また、アシル化度とは、セルロースのグルコース環又はエーテル置換基に存在する水酸基をエステル化することによりアシル基で置換した程度を示し、0以上100以下で示す。
 また、コロイド滴定法を行い、上記セルロース誘導体(C-1)~(C-7)におけるカルボキシル基又はスルホン酸基の置換度が0.02未満(すなわち、カルボキシル基又はスルホン酸基の含有量がセルロース誘導体に対して0.5質量%未満)であることを確認した。
Note that the types and substitution degrees of hydrocarbon groups, the types and molar substitutions of alkyleneoxy groups, the types of acyl groups, and the degrees of acylation of the cellulose derivatives obtained above are described in Cellulose Communication 6, 73-79 (1999). Was observed and determined by 1 H-NMR using the method described in 1 ). The degree of substitution of the hydrocarbon group is the number of moles of the hydrocarbon group substituted on the glucose ring unit, and takes a value of 0 or more and less than 3. The molar substitution degree of the alkyleneoxy group is the number of moles of the alkyleneoxy group substituted on the glucose ring unit, and takes a value of 0 or more. The degree of acylation indicates the degree of substitution with an acyl group by esterifying a hydroxyl group present in the glucose ring or ether substituent of cellulose, and is represented by 0 or more and 100 or less.
Further, a colloid titration method is performed, and the degree of substitution of carboxyl groups or sulfonic acid groups in the cellulose derivatives (C-1) to (C-7) is less than 0.02 (that is, the content of carboxyl groups or sulfonic acid groups is It was confirmed that it was less than 0.5% by mass with respect to the cellulose derivative.
<セルロース誘導体の分子量測定>
 得られたセルロース誘導体について、数平均分子量(Mn)、重量平均分子量(Mw)、を測定した。これらの測定方法は以下の通りである。
[分子量及び分子量分布]
 数平均分子量(Mn)、重量平均分子量(Mw)の測定は、ゲル・パーミエーション・クロマトグラフィー(GPC)を用いた。具体的には、N-メチルピロリドンを溶媒とし、ポリスチレンゲルを使用し、標準単分散ポリスチレンの構成曲線から予め求められた換算分子量較正曲線を用いて求めた。GPC装置は、HLC-8220GPC(東ソー社製)を使用した。
<Measurement of molecular weight of cellulose derivative>
About the obtained cellulose derivative, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured. These measuring methods are as follows.
[Molecular weight and molecular weight distribution]
For the measurement of the number average molecular weight (Mn) and the weight average molecular weight (Mw), gel permeation chromatography (GPC) was used. Specifically, N-methylpyrrolidone was used as a solvent, a polystyrene gel was used, and a molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene was used. As the GPC apparatus, HLC-8220 GPC (manufactured by Tosoh Corporation) was used.
 得られたセルロース誘導体が有する炭化水素基の種類及び置換度、アルキレンオキシ基の種類及びモル置換度、アシル基の種類及びアシル化度、数平均分子量(Mn)、並びに質量平均分子量(Mw)をまとめて表1に示す。なお、表1には比較例で使用したセルロース誘導体(H-1)についても記載した。 The type and degree of substitution of hydrocarbon groups, the type and molar substitution of alkyleneoxy groups, the type and degree of acylation of acyl groups, the number average molecular weight (Mn), and the mass average molecular weight (Mw) of the obtained cellulose derivative These are summarized in Table 1. Table 1 also shows the cellulose derivative (H-1) used in the comparative example.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
[成形体の作製]
 セルロース誘導体(C-1~C-7、H-1)、芳香族ポリエステル、相溶化剤、酸化防止剤を表2に示す配合割合(質量%)で混合し、セルロース樹脂組成物を作製した。この樹脂組成物を二軸混練押出機(テクノベル(株)製、Ultranano)に供給しペレットを作製し、ついで得られたペレットを、射出成形機(ファナック(株)Roboshot S-2000i、自動射出成形機)に供給して、4×10×80mmの多目的試験片を成形した。
[Production of molded body]
Cellulose derivatives (C-1 to C-7, H-1), aromatic polyester, compatibilizer, and antioxidant were mixed in the blending proportions (mass%) shown in Table 2 to prepare a cellulose resin composition. This resin composition was supplied to a twin-screw kneading extruder (manufactured by Technobel Co., Ltd., Ultranano) to produce pellets, and then the obtained pellets were injected into an injection molding machine (FANUC Corporation Robot S-2000i, automatic injection molding). Machine), 4 × 10 × 80 mm multi-purpose test pieces were molded.
 なお、表2において、芳香族ポリエステル、相溶化剤、酸化防止剤は以下のものを示す。
 ・PET:ポリエチレンテレフタレート樹脂(三井PET J005、三井ペット樹脂(株)製)
 ・PBT:ポリブチレンテレフタレート樹脂(ジュラネックス2002、日本ポリプラスチック(株)製)
 ・相溶化剤:モディパーA4400、日本油脂(株)社製(エチレン-グリシジルメタクリレート-graft-アクリロニトリル-スチレン樹脂)
 ・酸化防止剤:フェノール系酸化防止剤イルガノックス1010(チバ・スペシャルティ・ケミカルズ(株)製)
In Table 2, aromatic polyesters, compatibilizers and antioxidants are as follows.
PET: Polyethylene terephthalate resin (Mitsui PET J005, manufactured by Mitsui Pet Resin Co., Ltd.)
・ PBT: Polybutylene terephthalate resin (Duranex 2002, manufactured by Nippon Polyplastics Co., Ltd.)
・ Compatibilizer: Modiper A4400, manufactured by NOF Corporation (ethylene-glycidyl methacrylate-graft-acrylonitrile-styrene resin)
・ Antioxidant: Phenolic antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals)
[評価]
 得られた多目的試験片を用いて、以下の項目について評価した。評価結果等を表2に示す。
[Evaluation]
The following items were evaluated using the obtained multipurpose test piece. The evaluation results are shown in Table 2.
(曲げ弾性率)
 ISO178に準拠して、射出成形にて成形した試験片を23℃±2℃、50%±5%RHで48時間以上調整した後、インストロン(東洋精機製、ストログラフV50)によって支点間距離64mm、試験速度2mm/minで曲げ弾性率を測定した。測定は3回測定の平均値である。
(Flexural modulus)
In accordance with ISO178, after adjusting the test piece molded by injection molding for 48 hours or more at 23 ° C ± 2 ° C, 50% ± 5% RH, the distance between fulcrums by Instron (Toyo Seiki, Strograph V50) The flexural modulus was measured at 64 mm and a test speed of 2 mm / min. The measurement is an average of three measurements.
(曲げ強度)
 ISO178に準拠して、射出成形にて成形した試験片を23℃±2℃、50%±5%RHで48時間以上調整した後、インストロン(東洋精機製、ストログラフV50)によって支点間距離64mm、試験速度2mm/minで曲げ試験をおこない、試験中の最大応力を曲げ強度とした。測定は3回測定の平均値である。
(Bending strength)
In accordance with ISO178, after adjusting the test piece molded by injection molding for 48 hours or more at 23 ° C ± 2 ° C, 50% ± 5% RH, the distance between fulcrums by Instron (Toyo Seiki, Strograph V50) A bending test was performed at 64 mm and a test speed of 2 mm / min, and the maximum stress during the test was defined as the bending strength. The measurement is an average of three measurements.
(熱変形温度(HDT))
 ISO75に準拠して、試験片の中央に一定の曲げ荷重(1.8MPa)を加え(フラットワイズ方向)、等速度で昇温させ、中央部のひずみが0.34mmに達したときの温度(℃)を測定した。熱変形温度測定装置は、(株)東洋精機製作所製 HDTテスタ6M-2を用いた。測定は3回測定の平均値である。
(Heat deformation temperature (HDT))
In accordance with ISO75, a constant bending load (1.8 MPa) is applied to the center of the test piece (in the flatwise direction), the temperature is increased at a constant speed, and the temperature when the strain at the center reaches 0.34 mm ( ° C). As a thermal deformation temperature measuring device, HDT tester 6M-2 manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. The measurement is an average of three measurements.
(シャルピー衝撃強度)
 ISO179に準拠して、射出成形にて成形した試験片に入射角45±0.5°、先端0.25±0.05mmのノッチを形成し、23℃±2℃、50%±5%RHで48時間以上静置した後、シャルピー衝撃試験機((株)東洋精機製作所製)によってエッジワイズにて衝撃強度を測定した。測定は3回測定の平均値である。
(Charpy impact strength)
In accordance with ISO 179, a notch having an incident angle of 45 ± 0.5 ° and a tip of 0.25 ± 0.05 mm is formed on a test piece molded by injection molding, 23 ° C. ± 2 ° C., 50% ± 5% RH Then, the impact strength was measured edgewise with a Charpy impact tester (manufactured by Toyo Seiki Seisakusho). The measurement is an average of three measurements.
(成形性評価)
 成形性評価は、射出成形機での成形適性を示しており、成形搬送性及び射出性ともに優れている樹脂組成物を○、いずれか一方に課題がある樹脂組成物を△、両方に課題がある樹脂組成物を×とした。
 なお、成形搬送性は、樹脂計量時に異音などの計量不良が起こる場合は課題があるとし、問題なく計量できれば優れているとした。射出性は、成型品にバリ、ヒケ、シルバースキン、気泡などの成型不良が発生すれば課題があるとし、問題なく成型できれば優れているとした。
(Formability evaluation)
The moldability evaluation shows the moldability in an injection molding machine. A resin composition that is excellent in both mold transportability and injection property is indicated by ○, a resin composition that has a problem in either one, and a problem in both. A certain resin composition was set as x.
In addition, the moldability is considered to be a problem when a measurement failure such as abnormal noise occurs at the time of resin measurement, and is excellent if measurement can be performed without any problem. Injectability is considered to be a problem if molding defects such as burrs, sink marks, silver skin, and bubbles occur in the molded product, and excellent if it can be molded without problems.
(分散性評価)
 分散性の指標として、光学顕微鏡(ニコンLV100)を用いて評価をした。ミクロトームで2μmに薄切し1000倍で観察し、下記基準で評価した。
 ○:凝集物が観察されない場合
 △:凝集物がわずかに観察される場合
 ×:凝集物が多数観察される場合
(Dispersibility evaluation)
As an index of dispersibility, an optical microscope (Nikon LV100) was used for evaluation. A microtome was sliced to 2 μm, observed at 1000 times, and evaluated according to the following criteria.
○: When aggregates are not observed Δ: When aggregates are slightly observed ×: When many aggregates are observed
(摺動性)
 射出成形機を用いて、外径25.6mm、内径20.0mmの中空円筒形の試験片を成形し、JIS K7218A法に基づきスラスト式摩擦摩耗試験を使用して表面傷付き性を評価した。相手材としては試験片と同じものを用いた。判定は次の基準に従った。
 全く傷がつかない:◎
 わずかに傷がつく:○
 細かい傷が目立つ:△
 傷が著しい   :×
(Sliding property)
Using an injection molding machine, a hollow cylindrical test piece having an outer diameter of 25.6 mm and an inner diameter of 20.0 mm was molded, and surface scratch resistance was evaluated using a thrust type frictional wear test based on the JIS K7218A method. The same material as the test piece was used as the counterpart material. The determination was in accordance with the following criteria.
Not scratched at all: ◎
Slightly scratched: ○
Fine scratches stand out: △
Scratch is remarkable: ×
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
 表2より、本発明におけるセルロース誘導体と芳香族ポリエステルとを含有する成形材料からなる実施例1、8~13の試験片について、該セルロース誘導体単独の成形材料からなる試験片(比較例1)と比較して、摺動性が向上している。また、剛性、曲げ強度、耐衝撃性、及び耐熱性にも優れる。本発明におけるセルロース誘導体を含有しない成形材料からなる比較例2及び3の試験片は耐衝撃性に劣っていた。セルロースエステルと芳香族ポリエステルを含有する成形材料からなる試験片(比較例4)は、実施例の試験片よりも耐衝撃性に劣っていた。 From Table 2, with respect to the test pieces of Examples 1 and 8 to 13 made of the molding material containing the cellulose derivative and the aromatic polyester in the present invention, the test piece made of the molding material of the cellulose derivative alone (Comparative Example 1) and In comparison, the slidability is improved. Moreover, it is excellent also in rigidity, bending strength, impact resistance, and heat resistance. The test pieces of Comparative Examples 2 and 3 made of a molding material containing no cellulose derivative in the present invention were inferior in impact resistance. The test piece (Comparative Example 4) made of a molding material containing cellulose ester and aromatic polyester was inferior in impact resistance to the test piece of the example.
 本発明の成形材料は、優れた熱可塑性を有するため、加熱成形などにより成形することができる。また、本発明の成形材料、及び成形体は、剛性、曲げ強度、耐熱性といった性能に優れ、かつ良好な耐衝撃性、成形加工性、及び摺動性を有しており、例えば自動車、家電、電気電子機器等の構成部品、機械部品、住宅・建築用材料等として好適に使用することができる。また、本発明の成形材料は、植物由来の樹脂であるセルロースから得られるセルロース誘導体を使用しているため、温暖化防止に貢献できる素材として、従来の石油由来の樹脂に代替できる。 Since the molding material of the present invention has excellent thermoplasticity, it can be molded by heat molding or the like. Further, the molding material and the molded body of the present invention are excellent in performance such as rigidity, bending strength, and heat resistance, and have good impact resistance, molding processability, and sliding property. It can be suitably used as a component part such as an electric / electronic device, a machine part, a house / building material, and the like. Moreover, since the molding material of this invention uses the cellulose derivative obtained from the cellulose which is plant-derived resin, it can substitute for the conventional petroleum-derived resin as a raw material which can contribute to global warming prevention.
 本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
 本出願は、2009年12月25日出願の日本特許出願(特願2009-295096)、に基づくものであり、その内容はここに参照として取り込まれる。
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2009-295096) filed on Dec. 25, 2009, the contents of which are incorporated herein by reference.

Claims (17)

  1.  セルロースに含まれる水酸基の水素原子が、
     下記A)で置換された基を少なくとも1つ、及び
     下記B)で置換された基を少なくとも1つ含むセルロース誘導体と、
     芳香族ポリエステルとを含有する成形材料。
     A)炭化水素基:-R
     B)アシル基:-CO-R(Rは炭化水素基を表す。)
    The hydrogen atom of the hydroxyl group contained in cellulose
    A cellulose derivative comprising at least one group substituted in A) below and at least one group substituted in B) below;
    A molding material containing an aromatic polyester.
    A) Hydrocarbon group: —R A
    B) Acyl group: —CO—R B (R B represents a hydrocarbon group.)
  2.  前記セルロース誘導体が、更に、セルロースに含まれる水酸基の水素原子が下記C)で置換された基を少なくとも1つ含む、請求項1に記載の成形材料。
     C)アルキレンオキシ基:-RC2-O-とアシル基:-CO-RC1とを含む基(RC1は炭化水素基を表し、RC2は炭素数が2~4のアルキレン基を表す。)
    The molding material according to claim 1, wherein the cellulose derivative further comprises at least one group in which a hydrogen atom of a hydroxyl group contained in cellulose is substituted by the following C).
    C) a group containing an alkyleneoxy group: —R C2 —O— and an acyl group: —CO—R C1 (R C1 represents a hydrocarbon group, and R C2 represents an alkylene group having 2 to 4 carbon atoms. )
  3.  前記C)アルキレンオキシ基とアシル基とを含む基が、下記一般式(3)で表される構造を含む基である、請求項2に記載の成形材料。
    Figure JPOXMLDOC01-appb-C000001
    (式中、RC1は炭化水素基を表し、RC2は炭素数が2~4のアルキレン基を表す。
    nは1以上の整数を表す。)
    The molding material according to claim 2, wherein the C) group containing an alkyleneoxy group and an acyl group is a group containing a structure represented by the following general formula (3).
    Figure JPOXMLDOC01-appb-C000001
    (Wherein R C1 represents a hydrocarbon group, and R C2 represents an alkylene group having 2 to 4 carbon atoms.
    n represents an integer of 1 or more. )
  4.  前記Rが炭素数1~4のアルキル基である、請求項1~3のいずれか一項に記載の成形材料。 The molding material according to any one of claims 1 to 3, wherein R A is an alkyl group having 1 to 4 carbon atoms.
  5.  前記Rがメチル基又はエチル基である、請求項1~4のいずれか一項に記載の成形材料。 The molding material according to any one of claims 1 to 4, wherein R A is a methyl group or an ethyl group.
  6.  前記R及びRC1が、それぞれ独立に、アルキル基又はアリール基である、請求項2~5のいずれか一項に記載の成形材料。 The molding material according to any one of claims 2 to 5, wherein R B and R C1 are each independently an alkyl group or an aryl group.
  7.  前記R及びRC1が、それぞれ独立に、メチル基、エチル基又はプロピル基である、請求項2~6のいずれか一項に記載の成形材料。 The molding material according to any one of claims 2 to 6, wherein R B and R C1 are each independently a methyl group, an ethyl group, or a propyl group.
  8.  前記Rが、炭素数3~10の分岐構造を有する炭化水素基である、請求項1~6のいずれか一項に記載の成形材料。 The molding material according to any one of claims 1 to 6, wherein R B is a hydrocarbon group having a branched structure having 3 to 10 carbon atoms.
  9.  前記アルキレンオキシ基が下記式(1)又は(2)で表される基である、請求項2~8のいずれか一項に記載の成形材料。
    Figure JPOXMLDOC01-appb-C000002
    The molding material according to any one of claims 2 to 8, wherein the alkyleneoxy group is a group represented by the following formula (1) or (2).
    Figure JPOXMLDOC01-appb-C000002
  10.  前記セルロース誘導体が、カルボキシル基、スルホン酸基、及びこれらの塩を実質的に有さない、請求項1~9のいずれか一項に記載の成形材料。 The molding material according to any one of claims 1 to 9, wherein the cellulose derivative has substantially no carboxyl group, sulfonic acid group, or salt thereof.
  11.  前記セルロース誘導体が水に不溶である、請求項1~10のいずれか一項に記載の成形材料。 The molding material according to any one of claims 1 to 10, wherein the cellulose derivative is insoluble in water.
  12.  前記芳香族ポリエステルが、ポリエチレンテレフタレート(PET)又はポリブチレンテレフタレート(PBT)である請求項1~11のいずれか一項に記載の成形材料。 The molding material according to any one of claims 1 to 11, wherein the aromatic polyester is polyethylene terephthalate (PET) or polybutylene terephthalate (PBT).
  13.  更に、相溶化剤を含有する請求項1~12のいずれか一項に記載の成形材料。 The molding material according to any one of claims 1 to 12, further comprising a compatibilizing agent.
  14.  前記相溶化剤が、カルボン酸無水物、又は、エポキシ基、イソシアネート基及びオキサゾリン基からなる群より選ばれる少なくとも1種を有する化合物である、請求項13に記載の成形材料。 The molding material according to claim 13, wherein the compatibilizer is a carboxylic acid anhydride or a compound having at least one selected from the group consisting of an epoxy group, an isocyanate group and an oxazoline group.
  15.  請求項1~14のいずれか一項に記載の成形材料を加熱成形して得られる成形体。 A molded body obtained by thermoforming the molding material according to any one of claims 1 to 14.
  16.  請求項1~14のいずれか一項に記載の成形材料を加熱し、成形する工程を含む、成形体の製造方法。 A method for producing a molded body, comprising a step of heating and molding the molding material according to any one of claims 1 to 14.
  17.  請求項15に記載の成形体から構成される電気電子機器用筐体。 A housing for electrical and electronic equipment comprising the molded body according to claim 15.
PCT/JP2010/073244 2009-12-25 2010-12-22 Molding material, molded article and process for production thereof, and housing for electric/electronic device WO2011078289A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013069417A1 (en) * 2011-11-08 2013-05-16 富士フイルム株式会社 Electrophotographic photoconductor, copying machine using same, and dope for forming photosensitive layer thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003119296A (en) * 2001-10-11 2003-04-23 Fuji Photo Film Co Ltd Cellulose ester film
JP2004051897A (en) * 2002-07-23 2004-02-19 Daicel Chem Ind Ltd Anisotropic light-scattering sheet
JP2005154550A (en) * 2003-11-25 2005-06-16 Fuji Photo Film Co Ltd Cellulose film, optical film using the film, image display device and silver halide photographic sensitized material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4399305B2 (en) * 2004-03-30 2010-01-13 ダイセル化学工業株式会社 Cellulose ether acetate optical film
JP5233063B2 (en) * 2004-09-17 2013-07-10 東レ株式会社 Resin composition and molded article comprising the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003119296A (en) * 2001-10-11 2003-04-23 Fuji Photo Film Co Ltd Cellulose ester film
JP2004051897A (en) * 2002-07-23 2004-02-19 Daicel Chem Ind Ltd Anisotropic light-scattering sheet
JP2005154550A (en) * 2003-11-25 2005-06-16 Fuji Photo Film Co Ltd Cellulose film, optical film using the film, image display device and silver halide photographic sensitized material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013069417A1 (en) * 2011-11-08 2013-05-16 富士フイルム株式会社 Electrophotographic photoconductor, copying machine using same, and dope for forming photosensitive layer thereof
JP2013101221A (en) * 2011-11-08 2013-05-23 Fujifilm Corp Electrophotographic photoreceptor, copying machine using the same, and dope for forming photosensitive layer of the same

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