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WO2010047351A1 - Dérivé cellulosique, composition de résine, corps moulé obtenu à partir du dérivé cellulosique, et boîtier fait de ce corps moulé et destiné à un dispositif électrique ou électronique - Google Patents

Dérivé cellulosique, composition de résine, corps moulé obtenu à partir du dérivé cellulosique, et boîtier fait de ce corps moulé et destiné à un dispositif électrique ou électronique Download PDF

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Publication number
WO2010047351A1
WO2010047351A1 PCT/JP2009/068139 JP2009068139W WO2010047351A1 WO 2010047351 A1 WO2010047351 A1 WO 2010047351A1 JP 2009068139 W JP2009068139 W JP 2009068139W WO 2010047351 A1 WO2010047351 A1 WO 2010047351A1
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Prior art keywords
cellulose derivative
group
chain acyl
acyl group
cellulose
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PCT/JP2009/068139
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English (en)
Japanese (ja)
Inventor
俊英 芳谷
寛 野副
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富士フイルム株式会社
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Publication of WO2010047351A1 publication Critical patent/WO2010047351A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate

Definitions

  • the present invention relates to a cellulose derivative, a resin composition, a molded body, and a casing for an electric / electronic device.
  • 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 the amount of carbon dioxide in the atmosphere is greatly increased, which is considered to be one of the causes of global warming.
  • polymers such as ABS and PC made from petroleum, which is a fossil resource, have excellent characteristics as materials for components for electric and electronic equipment, but are made from petroleum, which is a fossil resource, From the viewpoint of preventing global warming, it is desirable to reduce the amount used.
  • 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.
  • an object of the present invention is to provide a cellulose derivative and a resin composition that have a low water absorption rate, have good thermoplasticity, strength, and elongation at break, and are suitable for molding.
  • the present inventors have focused on the molecular structure of cellulose and found that by making the cellulose into a cellulose derivative having a specific structure, the water absorption is low and good thermoplasticity, impact resistance and elongation at break are expressed.
  • the present invention has been completed. That is, the said subject can be achieved by the following means.
  • 3. The cellulose derivative according to 2 above, wherein the aliphatic chain acyl group having 5 to 20 carbon atoms has a branched structure. 4). 4. The cellulose derivative according to any one of 1 to 3 above, wherein the short chain acyl group is a propionyl group. 5).
  • the cellulose derivative or resin composition of the present invention Since the cellulose derivative or resin composition of the present invention has excellent thermoplasticity, it can be formed into a molded body.
  • the molded body formed of the cellulose derivative or the resin composition of the present invention has a low water absorption rate and has good impact resistance, breaking elongation, etc., and therefore a member requiring impact resistance and breaking elongation, For example, it can be suitably used as a housing for electrical and electronic equipment.
  • it since it is a plant-derived resin, it can be replaced with a conventional petroleum-derived resin as a material that can contribute to the prevention of global warming.
  • the cellulose derivative of the present invention is a cellulose derivative in which at least a part of hydrogen atoms of a hydroxyl group contained in cellulose is substituted with a short chain acyl group and a long chain acyl group.
  • the present invention will be described in detail.
  • Cellulose Derivative In the cellulose derivative of the present invention, at least part of the hydrogen atoms of the hydroxyl group contained in cellulose ((C 6 H 10 O 5 ) n ) is substituted with a short-chain acyl group and a long-chain acyl group. That is, the cellulose derivative of the present invention has a repeating unit represented by the following general formula (1).
  • R 2 , R 3 and R 6 each independently represent a hydrogen atom or a substituent. However, at least a part of R 2 , R 3 , and R 6 is substituted with a short-chain acyl long-chain acyl group. Substitution with a short-chain acyl group and a long-chain acyl group may be part of a plurality of R 2 , R 3 and R 6 , so that R 2 , R 3 and R 6 which are not short-chain acyl groups or long-chain acyl groups are It may be a hydrogen atom or another substituent.
  • the short chain acyl group means an acyl group having a relatively small number of carbon atoms and may contain heteroatoms such as oxygen and sulfur in the chain.
  • an aliphatic acyl group having 2 to 4 carbon atoms is preferable, specifically, an acetyl group, a propionyl group, and a butyryl group are preferable, and an acetyl group and a propionyl group are more preferable.
  • the long chain acyl group means an acyl group having more carbon atoms than the short chain acyl group and may contain heteroatoms such as oxygen and sulfur in the chain.
  • the long chain acyl group is preferably an aliphatic chain acyl group having 5 to 20 carbon atoms (aliphatic acyl group having a straight chain or branched structure) from the viewpoint of impact resistance and elongation at break.
  • An aliphatic chain acyl group having a branched structure of ⁇ 20 is more preferred.
  • the number of carbon atoms of the long-chain acyl group is particularly preferably 8 or more from the viewpoint of impact resistance and moisture absorption suppression.
  • long chain acyl groups include 2-methylbutyryl, 3-methylbutyryl, n-hexanoyl, 2-methylvaleryl, 2-ethylbutyryl, 2-methylhexanoyl, n-octanoyl, 2-ethylhexyl.
  • the short chain acyl group is preferably an aliphatic acyl group having 2 to 4 carbon atoms
  • the long chain acyl group is preferably an aliphatic chain acyl group having 5 to 20 carbon atoms.
  • the cellulose derivative of the present invention exhibits thermoplasticity by replacing at least part of the hydrogen atoms contained in the hydroxyl group of the ⁇ -glucose ring with a short-chain acyl group and a long-chain acyl group. It is suitable for molding.
  • the cellulose derivative of the present invention has a low water absorption, and can exhibit excellent strength and elongation at break as a molded body.
  • 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 polymerized 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 of the present invention only needs to contain a short-chain acyl group and a long-chain acyl group in any part of the whole, and may be composed of the same repeating unit or a plurality of types of repeating units. It may consist of units. Moreover, the cellulose derivative of the present invention does not need to contain both a short-chain acyl group and a long-chain acyl group in one repeating unit.
  • a monomer in which a part of R 2 , R 3 and R 6 is substituted with a short-chain acyl group, and a part of R 2 , R 3 and R 6 are substituted with a long-chain acyl group (2) one repeating unit R 2 , R 3 and R 6 are both substituted with a short-chain acyl group and a long-chain acyl group. It may be a polymer composed of a single monomer. Further, (3) a polymer in which different types of repeating units represented by the general formula (1) are randomly polymerized may be used.
  • a part of the polymer 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 (1)).
  • R 2 , R 3 and R 6 may be partially substituted with a hydrocarbon group or the like.
  • the chain part of the long-chain acyl group having 5 to 20 carbon atoms may be either a straight chain structure or a branched structure, but is preferably composed of an aliphatic group having a branched structure and branched to the ⁇ -position of the carbonyl group. More preferably, it consists of an aliphatic having a structure.
  • glass transition temperature (Tg) can be made high and strength, such as impact resistance, can be improved. Conventionally, it was thought that when a long-chain acyl group was substituted for cellulose, Tg was remarkably lowered.
  • Tg has a rigid glucopyranose ring as a main chain skeleton
  • Tg as conventionally considered
  • a 2-ethylbutyryl group, 2-ethylhexyl group, 2-propylpentanoyl group and the like are particularly preferable.
  • the short chain acyl group and the long chain acyl group may have a further substituent.
  • Further substituents include, for example, a hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, A hydrazino group, an imino group, etc. are mentioned.
  • substitution positions of the short-chain acyl group and the long-chain acyl group in the cellulose derivative there are no particular limitations on the substitution positions of the short-chain acyl group and the long-chain acyl group in the cellulose derivative, and the numbers (degree of substitution) of the short-chain acyl group and the long-chain acyl group per ⁇ -glucose ring unit.
  • the substitution degree DS A of the short chain acyl group (the number of short chain acyl groups with respect to the hydroxyl groups at the 2nd, 3rd and 6th positions of the ⁇ -glucose ring in the repeating unit) is usually about 1.0 or more, preferably It may be about 1.5 to 2.5.
  • Substitution degree DS B of the long chain acyl group (the number of long chain acyl groups with respect to the hydroxyl groups at the 2nd, 3rd and 6th positions of the cellulose structure of the ⁇ -glucose ring in the repeating unit) is usually about 0.1 or more, preferably It may be about 0.3 to 1.5. By setting it as a substituent of such a range, breaking elongation, brittleness, etc. can be improved.
  • the number of unsubstituted hydroxyl groups present in the cellulose derivative is not particularly limited.
  • Hydrogen atom substitution degree DS C (ratio in which the hydroxyl groups at the 2-position, 3-position and 6-position in the repeating unit are unsubstituted) is usually about 0.01 to 1.5, preferably about 0.05 to 1.2. And it is sufficient.
  • the DS C by 0.01 or more, it is possible to improve the fluidity of the resin composition. Further, by setting the DS C and 1.5 or less, or to improve the fluidity of the resin composition, foaming or the like due to water absorption of the resin composition during acceleration and molding of the pyrolysis can or is suppressed. Note that the sum of the degrees of substitution (DS A + DS B + DS C ) is 3.
  • the molecular weight of the cellulose derivative of the present invention is such that the number average molecular weight (Mn) is in the range of 5,000 to 500,000, more preferably in the range of 10,000 to 300,000, and most preferably in the range of 25,000 to 200,000.
  • the weight average molecular weight (Mw) is preferably in the range of 10,000 to 100,000, more preferably in the range of 20,000 to 600,000, and most preferably in the range of 50,000 to 500,000.
  • the molecular weight distribution (Mw / Mn) is preferably in the range of 1.1 to 5.0, more preferably in the range of 1.5 to 3.5.
  • the number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) can be measured using gel permeation chromatography (GPC). Specifically, tetrahydrofuran can be used as a solvent, polystyrene gel can be used, and the molecular weight can be obtained using a conversion molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene.
  • GPC gel permeation chromatography
  • the method for producing the cellulose derivative of the present invention is not particularly limited, and can be produced by using cellulose as a raw material and substituting the hydrogen atom of the hydroxyl group of cellulose with a short-chain acyl group and a long-chain acyl group. .
  • a raw material of a cellulose For example, cotton, a linter, a pulp, etc. can be used.
  • a preferred production method requires acyl chloride in cellulose ether (a cellulose derivative in which at least a part of the hydrogen atoms of hydroxyl groups at positions 2, 3 and 6 of the ⁇ -glucose ring is substituted with a hydrocarbon group). And a step of reacting in the presence of a base.
  • Examples of the acyl chloride used when the hydrogen atom of the hydroxyl group of cellulose is substituted with a short-chain acyl group include acetyl chloride, propionyl chloride, butyryl chloride and the like. Acetyl chloride and propionyl chloride are preferable, and acetyl chloride is more preferable.
  • Examples of the acyl chloride used for substitution with a long-chain acyl group include 2-methylbutyryl chloride, 3-methylbutyryl chloride, n-hexanoyl chloride, 2-methylvaleryl chloride, 2-ethylbutyryl.
  • Chloride 2-methylhexanoyl chloride, n-octanoyl chloride, 2-ethylhexyl chloride, 2-propylpentanoyl chloride, n-lauroyl chloride, 2-butyloctanoyl chloride, n-myristoyl chloride, n-palmitoyl chloride, 2 -Hexyl decanoyl chloride, n-stearoyl chloride, isostearoyl chloride, n-araquinoyl chloride, etc., preferably 2-ethylbutyryl chloride, 3-methylbutyryl chloride, 2-ethyl Rubutyryl chloride, 2-ethylhexyl chloride, 2-propylpentanoyl chloride, 2-hexyldecanoyl chloride, isostearoyl chloride, more preferably 2-ethylbutyryl chloride, 2-ethylhexyl chloride, 2-propylpent
  • pyridine for example, pyridine, lutidine, dimethylaminopyridine, triethylamine, diethylbutylamine, diazabicycloundecene, potassium carbonate and the like can be used. Of these, pyridine, dimethylaminopyridine and the like are preferable.
  • Resin composition containing cellulose derivative and molded article contains the cellulose derivative of the present invention, and may contain other additives as necessary.
  • the content ratio of the components contained in the resin composition is not particularly limited.
  • the cellulose derivative is preferably contained in an amount of 75% by mass or more, more preferably 80% by mass or more, and still more preferably 80 to 100% by mass.
  • the resin composition of the present invention may contain various additives such as a filler and a flame retardant as necessary.
  • the resin composition of the present invention may contain a filler (reinforcing material). By containing the filler, the mechanical properties of the molded body formed from the resin composition can be enhanced.
  • 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,
  • 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 particularly limited, but is usually 30 parts by mass or less, preferably 5 to 10 parts by mass with respect to 100 parts by mass of the cellulose derivative.
  • the resin composition 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
  • phosphoric acid condensed esters examples 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 examples include resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and condensates thereof.
  • 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 particularly limited, but is usually 30 parts by mass or less, preferably 2 to 10 parts by mass with respect to 100 parts by mass of the cellulose derivative. By setting it as this range, improvement in impact resistance, brittleness, etc. and occurrence of pellet blocking can be suppressed.
  • the resin composition of the present invention is not limited to the purpose of the present invention, and other properties are intended to further improve various properties such as moldability and flame retardancy.
  • Ingredients may be included.
  • other components include polymers other than the cellulose derivatives, plasticizers, stabilizers (antioxidants, UV absorbers, etc.), mold release agents (fatty acids, fatty acid metal salts, oxyfatty acids, fatty acid esters, aliphatic moieties.
  • 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) and the like. Further, a coloring agent containing a dye or a pigment can be added.
  • thermoplastic polymer As the polymer other than the cellulose derivative, either a thermoplastic polymer or a thermosetting polymer can be used, but a thermoplastic polymer is preferable from the viewpoint of moldability.
  • polymers other than cellulose derivatives 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, polybutylene terephthalate, polyethylene terephthalate and other aromatic polyesters, etc.
  • Polyamide such as polyester, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 6T, nylon 12, etc., polystyrene, high impact polystyrene, polyacetate (Including homopolymers and copolymers), polyurethanes, aromatic and aliphatic polyketones, polyphenylene sulfide, polyether ether ketone, thermoplastic starch resins, polymethyl methacrylate and methacrylate-acrylate copolymers Acrylic resin, AS resin (acrylonitrile-styrene copolymer), ABS resin, AES resin (ethylene rubber reinforced AS resin), ACS resin (chlorinated polyethylene reinforced AS resin), ASA resin (acrylic rubber reinforced AS resin) ), Polyvinyl chloride, polyvinylidene chloride, vinyl ester resin, maleic anhydride-styrene copolymer, MS resin (methyl methacrylate-styrene copolymer), polycarbonate, polyarylate, polysulfone,
  • those having various degrees of crosslinking those having various microstructures, for example, those having a cis structure, a trans structure, etc., those having a vinyl group, or those having various average particle diameters (in the resin composition)
  • a multilayer structure polymer called a so-called core shell rubber, which is composed of a core layer and one or more shell layers covering the core layer and whose adjacent layers are composed of different types of polymers, can also be used.
  • a core-shell rubber containing a silicone compound can also be used.
  • the content thereof is preferably 30 parts by mass or less, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the cellulose derivative.
  • the resin composition 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.
  • Tributyl ester 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, 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.
  • 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 resin composition of the present invention contains a plasticizer
  • its content is usually 5 parts by mass or less, preferably 0.005 to 5 parts by mass, more preferably 0.005 parts by mass with respect to 100 parts by mass of the cellulose derivative. 01 to 1 part by mass.
  • the molded article of the present invention is obtained by molding a resin composition containing the cellulose derivative of the present invention or the cellulose derivative of the present invention and an additive (preferably a filler). More specifically, the resin composition containing the cellulose derivative of the present invention or the cellulose derivative of the present invention and a filler is melted by heating or the like and molded by various molding methods. Examples of the molding method include injection molding, extrusion molding, blow molding and the like. The heating temperature is usually 160 to 260 ° C., preferably 180 to 240 ° 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 impact, for example, exterior parts for electrical and electronic equipment such as copiers, printers, personal computers, and televisions (especially casings). Can be suitably used.
  • ⁇ Synthesis Example 1 Synthesis of propionyl cellulose> 50 g of cellulose (manufactured by Nippon Paper Industries Co., Ltd .: KC Flock W400) and 1800 mL of dimethylacetamide were weighed in a 3 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel and stirred at 120 ° C. for 2 hours. Next, 150 g of lithium chloride was added, and the mixture was further stirred for 1 hour. After returning the reaction solution to room temperature, 73 g of propionyl chloride was added dropwise at room temperature, and the mixture was further stirred at 90 ° C. for 2 hours.
  • ⁇ Synthesis Example 2 Synthesis of butyrylcellulose> 50 g of cellulose (manufactured by Nippon Paper Industries Co., Ltd .: KC Flock W400) and 1800 mL of dimethylacetamide were weighed in a 3 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel and stirred at 120 ° C. for 2 hours. Next, 150 g of lithium chloride was added, and the mixture was further stirred for 1 hour. After returning the reaction solution to room temperature, 84 g of butyryl chloride was added dropwise at room temperature, and the mixture was further stirred at 90 ° C. for 2 hours.
  • the white solid was filtered off by suction filtration and washed 3 times with a large amount of methanol solvent.
  • the obtained white solid was vacuum-dried at 100 ° C. for 6 hours to obtain the objective cellulose derivative (P-2) as a white powder (107.0 g).
  • the 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 obtained white solid was vacuum-dried at 100 ° C. for 6 hours to obtain the desired cellulose derivative (P-3) as a white powder (98.4 g).
  • Table 1 shows the number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) of the obtained cellulose derivative.
  • Table 1 also describes cellulose derivatives of comparative examples described later. Further, the obtained cellulose derivative, the degree of substitution DS A short chain acyl group substitution degree DS B of long-chain acyl group, and the substitution degree DS C hydrogen atoms, in Cellulose Communication 6,73-79 (1999) Determined by 1 H-NMR using the method described. The results are shown in Table 2.
  • the cellulose derivative (P-1) obtained above is supplied to an injection molding machine (semi-automatic injection molding machine, manufactured by Imoto Seisakusho Co., Ltd.), cylinder temperature 190 ° C., mold temperature 30 ° C., injection pressure 1.5 kgf / Multi-purpose test piece (impact test piece) of 4 ⁇ 10 ⁇ 80 mm at cm 2 and full length 80 mm, end width 20 mm, distance between grips 50 mm, width between grips 10 mm, thickness 2 mm (tensile test piece ) Was molded.
  • cellulose derivatives (P-2) to (P-5), H-1 (cellulose acetate having an adamantylcarbonyl group described in Example 1 of JP-A-2002-293802) as a comparative example
  • H-2 Daicel diacetyl cellulose A: acetyl substitution degree 2.15
  • H-3 Daicel diacetyl cellulose B: acetyl substitution degree 2.45
  • H-4 Eastman Chemical Co .: cellulose acetate propionate 480) -20
  • H-5 were molded according to the molding conditions shown in Table 2 to prepare multipurpose test pieces (impact test pieces) and dumbbell-shaped test pieces (tensile test pieces).
  • the cylinder temperature in each polymer molding was set to a temperature at which the melt flow rate was in the range of 6 to 9 g / 10 min, and the mold temperature was 30 ° C.
  • Each test piece was evaluated by the following method. The results are shown in Table 2.
  • Charpy impact strength According to ISO 179, a notch having an incident angle of 45 ⁇ 0.5 ° and a tip of 0.25 ⁇ 0.05 mm is formed on the multipurpose test piece (impact test piece) molded by injection molding at 23 ° C. After storing at ⁇ 2 ° C. and 50% ⁇ 5% RH for 48 hours or more, the impact strength was measured edgewise by a Charpy impact tester (manufactured by Toyo Seiki).
  • Equilibrium moisture content water absorption
  • Wd dry mass of multipurpose test piece
  • the test piece obtained from the cellulose derivative of the present invention has high Charpy impact strength, low water absorption, and high elongation at break. From this, it can be seen that by modifying both the short-chain acyl group and the long-chain acyl group on cellulose, the water absorption is decreased and the impact resistance, hygroscopicity, and flexibility are improved. That is, it can be understood that an unexpected effect of improving impact resistance, hygroscopicity, and flexibility was obtained by substituting the hydroxyl group in cellulose with both a short-chain acyl group and a long-chain acyl group. In addition, H-5 of Comparative Example 5 was too soft to be evaluated as indicated by “-” in the table.
  • the cellulose derivative or resin composition of the present invention Since the cellulose derivative or resin composition of the present invention has excellent thermoplasticity, it can be formed into a molded body.
  • the molded body formed of the cellulose derivative or the resin composition of the present invention has a low water absorption rate and has good impact resistance, breaking elongation, etc., and therefore a member requiring impact resistance and breaking elongation, For example, it can be suitably used as a housing for electrical and electronic equipment.
  • it since it is a plant-derived resin, it can be replaced with a conventional petroleum-derived resin as a material that can contribute to the prevention of global warming.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

La présente invention concerne un dérivé cellulosique faiblement hydrophile qui, présentant de bonnes caractéristiques de thermoplasticité, de résistance, et d'allongement à la rupture, se prête particulièrement au moulage. L'invention concerne une composition de résine contenant le dérivé cellulosique, un corps moulé obtenu à partir de ce composé cellulosique, et un boîtier fait de ce corps moulé et destiné à un dispositif électronique. Ce dérivé cellulosique est caractérisé en ce que certains au moins des atomes d'hydrogène des groupes hydroxy contenus dans la cellulose sont substitués par des groupes acyle à chaîne courte et des groupes acyle à chaîne longue.
PCT/JP2009/068139 2008-10-22 2009-10-21 Dérivé cellulosique, composition de résine, corps moulé obtenu à partir du dérivé cellulosique, et boîtier fait de ce corps moulé et destiné à un dispositif électrique ou électronique WO2010047351A1 (fr)

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WO2017217504A1 (fr) * 2016-06-17 2017-12-21 日本電気株式会社 Composition de résine à base de cellulose, article moulé, et produit l'utilisant
WO2017217503A1 (fr) * 2016-06-17 2017-12-21 日本電気株式会社 Composition de résine à base de cellulose, article moulé, et son produit
WO2019049196A1 (fr) * 2017-09-05 2019-03-14 株式会社ダイセル Ester de cellulose d'acide gras mixte et procédé de fabrication d'ester de cellulose d'acide gras mixte
US20210198435A1 (en) * 2018-08-28 2021-07-01 National University Corporation Kanazawa University Composite material derived from lignocellulosic biomass and method for producing the same
US11161917B2 (en) 2013-08-23 2021-11-02 Nec Corporation Method for producing cellulose derivative, and cellulose derivative
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US10941282B2 (en) 2016-06-17 2021-03-09 Nec Corporation Cellulose resin composition, molded body and product using same
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US11149133B2 (en) 2016-06-17 2021-10-19 Nec Corporation Cellulose resin composition, molded body and product using same
WO2017217504A1 (fr) * 2016-06-17 2017-12-21 日本電気株式会社 Composition de résine à base de cellulose, article moulé, et produit l'utilisant
WO2019049196A1 (fr) * 2017-09-05 2019-03-14 株式会社ダイセル Ester de cellulose d'acide gras mixte et procédé de fabrication d'ester de cellulose d'acide gras mixte
US20210198435A1 (en) * 2018-08-28 2021-07-01 National University Corporation Kanazawa University Composite material derived from lignocellulosic biomass and method for producing the same
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