WO2010038711A1 - セルロース誘導体及びその製造方法、樹脂組成物、成形体及びその製造方法、電子機器用筐体 - Google Patents
セルロース誘導体及びその製造方法、樹脂組成物、成形体及びその製造方法、電子機器用筐体 Download PDFInfo
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- WO2010038711A1 WO2010038711A1 PCT/JP2009/066821 JP2009066821W WO2010038711A1 WO 2010038711 A1 WO2010038711 A1 WO 2010038711A1 JP 2009066821 W JP2009066821 W JP 2009066821W WO 2010038711 A1 WO2010038711 A1 WO 2010038711A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B13/00—Preparation of cellulose ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08L1/32—Cellulose ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/32—Cellulose ether-esters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
Definitions
- the present invention relates to a novel cellulose derivative, a method for producing a cellulose derivative, a resin composition, a molded article, a method for producing the same, and a casing for 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 the amount of carbon dioxide in the atmosphere greatly increases, 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 electronic devices, 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.
- Patent Document 2 a method for reducing petroleum-derived resources by using plant-derived resources such as starch as part of petroleum-derived raw materials has been proposed.
- Patent Document 2 further improvements are required from the perspective of aiming for a more complete carbon neutral material.
- an object of the present invention is to provide a cellulose derivative and a resin composition that have good thermoplasticity, strength, and elongation at break and are suitable for molding.
- the inventors of the present invention have focused on the molecular structure of cellulose and found that by making the cellulose into a cellulose derivative having a specific structure, the present inventors have achieved good thermoplasticity, impact resistance and elongation at break, and completed the present invention. It came to do. That is, the said subject can be achieved by the following means.
- the cellulose derivative according to 1 above, wherein the a) hydrocarbon group is a methyl group or an ethyl group. 6). 2. The cellulose derivative according to 1 above, wherein the a) hydrocarbon group is a methyl group. 7).
- a method for producing a cellulose derivative according to the above 1, comprising a step of reacting a chloroformate with cellulose ether in the presence of a base. 8). 2. A resin composition containing the cellulose derivative as described in 1 above. 9. A molded product obtained by molding the cellulose derivative according to 1 or the resin composition according to 8 above. 10.
- a method for producing a molded body, comprising a step of heating and molding the cellulose derivative according to 1 or the resin composition according to 8 above. 11. 10.
- a casing for electronic equipment comprising the molded article according to 9 above.
- 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 good impact resistance, breaking elongation, etc., members that require impact resistance and breaking elongation, for example, for electronic devices It can be suitably used as a housing.
- 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 has at least one of a) a hydrocarbon group, and b) an aliphatic oxycarbonyl group and an aromatic oxycarbonyl group. That is, 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 a hydrocarbon group, an aliphatic oxycarbonyl group, or an aromatic oxycarbonyl group.
- R represents an aliphatic group or an aromatic group.
- a cellulose derivative having an aliphatic oxycarbonyl group or an aromatic oxycarbonyl group is referred to as “cellulose (aliphatic group name or aromatic group name) carbonate”.
- the cellulose derivative of the present invention has at least one of a) a hydrocarbon group, and b) an aliphatic oxycarbonyl group and an aromatic oxycarbonyl 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, a hydrocarbon group, an aliphatic oxycarbonyl group or an aromatic oxycarbonyl group. However, at least one of R 2 , R 3 , and R 6 represents a hydrocarbon group, and at least one represents an aliphatic oxycarbonyl group or an aromatic oxycarbonyl group.
- the cellulose derivative of the present invention as described above, at least part of the hydrogen atoms contained in the hydroxyl group of the ⁇ -glucose ring is substituted with at least one of a hydrocarbon group, an aliphatic oxycarbonyl group, and an aromatic oxycarbonyl group. Therefore, thermoplasticity can be expressed and it is suitable for molding processing. Moreover, the cellulose derivative of the present invention can exhibit excellent strength and elongation at break as a molded body. Furthermore, since cellulose is a complete 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 of the present invention only needs to contain a hydrocarbon group and an aliphatic oxycarbonyl group or an aromatic oxycarbonyl group in any part of the whole, and may be composed of the same repeating unit. It may be composed of a plurality of types of repeating units. Moreover, the cellulose derivative of the present invention does not need to contain both the hydrocarbon group and the aliphatic oxycarbonyl group or aromatic oxycarbonyl group in one repeating unit.
- R 2, R 3 and a repeating unit part of R 6 is substituted with a hydrocarbon group
- R 2, R 3 and part of R 6 is an aliphatic oxycarbonyl group or an aromatic oxy
- It may be a cellulose derivative composed of a repeating unit substituted with a carbonyl group, and (2) a hydrocarbon group and an aliphatic oxycarbonyl group or aromatic group in R 2 , R 3 and R 6 of one repeating unit. It may be a cellulose derivative composed of a single repeating unit in which both of the group oxycarbonyl groups are substituted.
- (3) a cellulose derivative in which different types of repeating units represented by the general formula (1) are bonded at random may be used.
- a part of 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 (1)).
- the a) hydrocarbon group may be either an aliphatic group or an aromatic group. In the case of an aliphatic group, it may be linear, branched or cyclic, and may have an unsaturated bond.
- the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group. Specific examples include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, cyclohexyl group and the like. A methyl group or an ethyl group is preferable, and a methyl group is more preferable. These may be used alone or in a combination of two or more.
- the a) hydrocarbon group is an aromatic group
- those having 6 to 18 carbon atoms are preferred, and those having 6 to 10 carbon atoms are more preferred.
- Specific examples include a phenyl group, a naphthyl group, a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a 1-methyl-2-phenylethyl group, a cinnamyl group, and a trityl group.
- Particularly preferred is a benzyl group.
- the number of carbon atoms of the hydrocarbon group is preferably 1 to 9, and more preferably 1 to 4.
- the hydrocarbon group is preferably an aliphatic group.
- the hydrocarbon group may further have a substituent, and examples of the further substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a cyano group, and the like.
- a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom
- the number of carbon atoms in the aliphatic group of the aliphatic oxycarbonyl group in b) is preferably 1 to 18, more preferably 3 to 10, further preferably 6 to 10, and particularly preferably 7 to 9. .
- the aliphatic moiety of the aliphatic oxycarbonyl group may have any of a linear structure, a branched structure, and a cyclic structure.
- Aliphatic groups include methyl, ethyl, propyl, isopropyl, allyl, isopropentyl, butyl, isobutyl, 3-butenyl, pentyl, hexyl, phenyl, heptyl, octyl Benzyl group, tolyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like. These may be used alone or in a combination of two or more.
- the carbon number of the aromatic group of the aromatic oxycarbonyl group in b) is preferably 6-30, more preferably 6-20, and even more preferably 6-10.
- they are a phenyl group, an alkylmethylphenyl group, and a benzyl group.
- the aliphatic oxycarbonyl group or aromatic oxycarbonyl 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.
- the cellulose derivative of the present invention may have at least one of b) an aliphatic oxycarbonyl group and an aromatic oxycarbonyl group, but preferably has at least an aliphatic oxycarbonyl group.
- Substitution position of the hydrocarbon group and aliphatic oxycarbonyl group or aromatic oxycarbonyl group in the cellulose derivative, and the hydrocarbon group and aliphatic oxycarbonyl group or aromatic oxycarbonyl group per ⁇ -glucose ring unit The number (substitution degree) of is not particularly limited.
- the degree of substitution DS B of the hydrocarbon group (the number of hydrocarbon groups relative to the hydroxyl groups at the 2nd, 3rd and 6th positions of the ⁇ -glucose ring in the repeating unit) is preferably 1.0 or more. The range of 5 to 2.5 is more preferable.
- Degree of substitution DS C of aliphatic oxycarbonyl group or aromatic oxycarbonyl group (aliphatic oxycarbonyl group or aromatic oxycarbonyl with respect to hydroxyl groups at positions 2, 3 and 6 of the cellulose structure of the ⁇ -glucose ring in the repeating unit)
- the number of groups is preferably 0.1 or more, more preferably in the range of 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.
- the substitution degree DS A of hydrogen atoms (ratio in which the hydroxyl groups at the 2-position, 3-position and 6-position in the repeating unit are unsubstituted) is preferably in the range of 0.01 to 1.5, preferably 0.2 to 1 A range of .2 is more preferred.
- the DS A by 0.01 or more, it is possible to improve the fluidity of the resin composition. Further, by setting the DS A 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 preferably in the range of 5,000 to 1,000,000, more preferably in the range of 10,000 to 500,000, and most preferably in the range of 50,000 to 200,000.
- the weight average molecular weight (Mw) is preferably in the range of 7000 to 5000000, more preferably in the range of 15000 to 2500,000, and most preferably in the range of 200000 to 150,000.
- the molecular weight distribution (MWD) is preferably in the range of 1.1 to 10, and more preferably in the range of 1.5 to 7.
- the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (MWD) can be measured using gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- tetrahydrofuran can be used as a solvent
- polystyrene gel can be used
- the molecular weight can be obtained using a conversion molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene.
- the cellulose derivative of the present invention may have other substituents not mentioned above.
- the method for producing the cellulose derivative of the present invention is not particularly limited.
- the hydrogen atom of the hydroxyl group of cellulose is a hydrocarbon group, an aliphatic oxycarbonyl group, or an aromatic oxycarbonyl group. It can manufacture by substituting.
- a raw material of a cellulose For example, cotton, a linter, a pulp, etc. can be used.
- cellulose ether (a cellulose derivative in which at least part of the hydrogen atoms of the hydroxyl groups at the 2-position, 3-position and 6-position of the ⁇ -glucose ring is substituted with a hydrocarbon group) in the presence of a base, It includes a step of reacting chloroformate or the like.
- the cellulose ether by which the hydrogen atom of the hydroxyl group contained in a cellulose was substituted by the hydrocarbon group can be used, for example.
- Specific examples include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, allyl cellulose, and benzyl cellulose.
- chloroformate esters examples include methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, butyl chloroformate, isobutyl chloroformate, hexyl chloroformate, tolyl chloroformate, octyl chloroformate, 2-ethylhexyl chloroformate, Examples include phenyl chloroformate and benzyl chloroformate.
- 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 further 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 silica, feldspar powder, potassium titanate, shira
- 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 preferably 30 parts by mass or less, more 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.
- a flame retardant is not particularly limited, and 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 compounding with resin or during molding, causing corrosion of processing machines and molds, and worsening the work 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, etc. 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 thereof is not particularly limited, but is preferably 30 parts by mass or less with respect to 100 parts by mass of the cellulose derivative, and is 2 to 10 parts by mass. Is more preferable. 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. Furthermore, a coloring agent containing a dye or a pigment can be added.
- any of a thermoplastic polymer and a thermosetting polymer can be used, but a thermoplastic polymer is preferable from the viewpoint of moldability.
- polymers other than cellulose derivatives include polyolefins such as low density polyethylene, high density polyethylene and polypropylene, polyesters, polyamides, polystyrenes, polyacetals, polyurethanes, aromatic and aliphatic polyketones, polyphenylene sulfide, polyetheretherketone, polyimide , Thermoplastic starch resin, polystyrene, acrylic resin, AS resin, ABS resin, AES resin, ACS resin, AAS resin, polyvinyl chloride resin, polyvinylidene chloride, vinyl ester resin, polyurethane, MS resin, polycarbonate, polyarylate , Polysulfone, polyethersulfone, phenoxy resin, polyphenylene oxide, poly-4-methylpentene-1, polyetherimide, cellulose
- ethylene-propylene copolymers ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers and alkali metal salts thereof (so-called ionomers), Ethylene-glycidyl (meth) acrylate copolymer, ethylene-alkyl acrylate copolymer (for example, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer), acid-modified ethylene-propylene copolymer , Diene rubber (eg, polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (eg, styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-
- 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 multi-layered 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 in which adjacent layers are composed of different polymers, and the like
- 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 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 content thereof is preferably 5 parts by mass or less, more preferably 0.005 to 5 parts by mass with respect to 100 parts by mass of the cellulose derivative. More preferably, the content is 01 to 1 part by mass.
- the molded article of the present invention can be produced by heating and molding a resin composition containing the cellulose derivative of the present invention or the cellulose derivative of the present invention and an additive (preferably 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 heated and melted and molded by various molding methods. Examples of the molding method include injection molding, extrusion molding, blow molding and the like.
- the heating temperature can be in the range of 160 to 260 ° C, and preferably in the range of 180 to 240 ° C.
- the use of the molded product of the present invention is not particularly limited.
- interior or exterior parts of electric 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 (especially casings) for electrical and electronic equipment such as copiers, printers, personal computers, and televisions. ) Can be suitably used.
- the reaction solution was diluted with 1.4 L of acetone, and poured into water / methanol 10 L / 10 L with vigorous stirring, whereby a white solid was precipitated.
- the white solid was filtered off by suction filtration and washed three times with a large amount of isopropanol.
- the obtained white solid was vacuum-dried at 100 ° C. for 6 hours to obtain the desired cellulose derivative (H-5) (ethyl carbonate acetyl cellulose, acetyl substitution degree 2.2, ethyl carbonate substitution degree 0.3) as white powder. (75.0 g).
- Table 1 shows the number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (MWD), and glass transition temperature (Tg) of the obtained cellulose derivative. These measuring methods are as follows.
- the number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (MWD) were measured using gel permeation chromatography (GPC). Specifically, tetrahydrofuran was used as a solvent, polystyrene gel was used, and the molecular weight was determined using a conversion molecular weight calibration curve obtained in advance from the constituent curve of standard monodisperse polystyrene. As the GPC apparatus, HLC-8220 GPC (manufactured by Tosoh Corporation) was used.
- Example 1 Production of molded body made of cellulose derivative> [Test specimen preparation]
- 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 250 ° C., mold temperature 30 ° C., injection pressure 1.8 kgf / Multipurpose test pieces (impact test pieces and thermal deformation test pieces) of 4 ⁇ 10 ⁇ 80 mm were formed at cm 2 .
- the cylinder temperature in the polymer molding was set to a temperature at which the melt flow rate was in the range of 5 to 15 g / 10 min.
- the mold temperature was 30 ° C.
- the molded body formed of the cellulose derivative or cellulose resin composition of the present invention has good impact resistance, heat resistance, etc., and is a component of automobiles, home appliances, electrical and electronic equipment, mechanical parts, It can be suitably used as a building material or the like.
- the cellulose derivative of the present invention is a plant-derived resin, it can be replaced with a conventional petroleum-derived resin as a material that can contribute to prevention of global warming.
Abstract
Description
そこで、本発明の目的は、良好な熱可塑性、強度及び破断伸度を有し、成形加工に適したセルロース誘導体及び樹脂組成物を提供することである。
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。
2.前記b)脂肪族オキシカルボニル基又は芳香族オキシカルボニル基が、脂肪族カルボニルオキシ基である、上記1に記載のセルロース誘導体。
3.前記脂肪族カルボニルオキシ基の脂肪族基の炭素数が6~10である、上記2に記載のセルロース誘導体。
4.前記a)炭化水素基の炭素数が1~9である、上記1に記載のセルロース誘導体。
5.前記a)炭化水素基がメチル基又はエチル基である、上記1に記載のセルロース誘導体。
6.前記a)炭化水素基がメチル基である、上記1に記載のセルロース誘導体。
7.上記1に記載のセルロース誘導体の製造方法であって、セルロースエーテルに、塩基存在下、クロロギ酸エステルを反応させる工程を含む、セルロース誘導体の製造方法。
8.上記1に記載のセルロース誘導体を含有する樹脂組成物。
9.上記1に記載のセルロース誘導体又は上記8に記載の樹脂組成物を成形して得られる成形体。
10.上記1に記載のセルロース誘導体又は上記8に記載の樹脂組成物を加熱及び成形する工程を含む、成形体の製造方法。
11.上記9に記載の成形体から構成される電子機器用筐体。
すなわち、本発明のセルロース誘導体は、セルロース((C6H10O5)n)に含まれる水酸基の水素原子の少なくとも一部が、炭化水素基及び、脂肪族オキシカルボニル基及び芳香族オキシカルボニル基の少なくともいずれかで置換されており、炭化水素基で置換されていることによりエーテル構造が形成され、脂肪族オキシカルボニル基又は芳香族オキシカルボニル基で置換されていることにより、カーボネート構造(-O-C(O)-O-R:Rは脂肪族基又は芳香族基を表す。)が形成される。なお、後述の実施例では、脂肪族オキシカルボニル基又は芳香族オキシカルボニル基を有するセルロース誘導体を「セルロース(脂肪族基名又は芳香族基名)カーボネート」と称する。
以下、本発明について詳細に説明する。
本発明のセルロース誘導体は、a)炭化水素基、及び、b)脂肪族オキシカルボニル基及び芳香族オキシカルボニル基の少なくともいずれかを有する。
すなわち、本発明のセルロース誘導体は、下記一般式(1)で表される繰り返し単位を有する。
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。
例えば、(1)R2、R3及びR6の一部が炭化水素基で置換されている繰り返し単位と、R2、R3及びR6の一部が脂肪族オキシカルボニル基又は芳香族オキシカルボニ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であってよいし、(2)ひとつの繰り返し単位のR2、R3及びR6に炭化水素基及び脂肪族オキシカルボニル基又は芳香族オキシカルボニル基の両方が置換されている単一の繰り返し単位から構成されるセルロース誘導体であってもよい。さらには、(3)一般式(1)で表される繰り返し単位であって異なる種類の繰り返し単位が、ランダムに結合しているセルロース誘導体であってもよい。
なお、セルロース誘導体の一部には、無置換の繰り返し単位(すなわち、前記一般式(1)において、R2、R3及びR6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。
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。
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、オクチル基、2-エチルヘキシル基、ノニル基、シクロヘキシル基等が挙げられる。好ましくはメチル基又はエチル基であり、より好ましくはメチル基である。これらは1種単独のものでもよいし、2種以上が組み合わされたものでもよい。
炭化水素基の炭素数は、好ましくは1~9であり、さらに好ましくは1~4である。
炭化水素基は脂肪族基であることが好ましい。
脂肪族オキシカルボニル基の脂肪族部位は、直鎖構造、分岐構造及び環状構造のいずれであってもよい。
脂肪族基としては、メチル基、エチル基、プロピル基、イソプロピル基、アリル基、イソプロペンチル基、ブチル基、イソブチル基、3-ブテニル基、ペンチル基、ヘキシル基、フェニル基、ヘプチル基、オクチル基、ベンジル基、トリル基、オクチル基、2-エチルヘキシル基、ノニル基、デシル基、ウンデシル基、ドデシル基等が挙げられる。これらは1種単独のものでもよいし、2種以上が組み合わされたものでもよい。
具体的には、フェニル基、アルキルフェニル基、ナフチル基、フェナントリル基、アントリル基、ベンジル基、2-フェニルエチル基、3-フェニルプロピル基、1-メチル-2-フェニルエチル基、シンナミル基、トリチル基等が挙げられる。好ましくは、フェニル基、アルキルメチルフェニル基、ベンジル基である。
例えば、炭化水素基の置換度DSB(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炭化水素基の数)は、1.0以上であることが好ましく、1.5~2.5の範囲がより好ましい。
脂肪族オキシカルボニル基又は芳香族オキシカルボニル基の置換度DSC(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脂肪族オキシカルボニル基又は芳香族オキシカルボニル基の数)は0.1以上であることが好ましく、0.3~1.5の範囲がより好ましい。このような範囲の置換基とすることにより、破断伸度、脆性等を向上させることができる。
水素原子の置換度DSA(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0.01~1.5の範囲であることが好ましく、0.2~1.2の範囲がより好ましい。DSAを0.01以上とすることにより、樹脂組成物の流動性を向上させることができる。また、DSAを1.5以下とすることにより、樹脂組成物の流動性を向上させたり、熱分解の加速・成形時の樹脂組成物の吸水による発泡等を抑制させたりできる。
なお、各置換度の総和(DSA+DSB+DSC)は3である。
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、テトラヒドロフランを溶媒とし、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。
本発明の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、セルロースの水酸基の水素原子を炭化水素基及び、脂肪族オキシカルボニル基及び芳香族オキシカルボニル基の少なくともいずれかによって置換することにより製造することができる。セルロースの原料としては特に制限はなく、例えば、綿、リンター、パルプ等を用いることができる。
好ましい製造方法の態様は、セルロースエーテル(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セルロース誘導体)に、塩基存在下、クロロギ酸エステル等を反応させる工程を含むものである。
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。
本発明の樹脂組成物は、本発明のセルロース誘導体を含有しており、必要に応じてその他の添加剤を含有することができる。
樹脂組成物に含まれる成分の含有割合は、特に限定されない。好ましくはセルロース誘導体を75質量%以上、より好ましくは80質量%以上、さらに好ましくは80~100質量%含有する。
本発明の樹脂組成物は、本発明のセルロース誘導体のほか、必要に応じて、フィラー、難燃剤等の種々の添加剤を含有していてもよい。
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、窒化硅素繊維およ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。
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、リン含有難燃剤およびケイ素含有難燃剤が好ましい。
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。
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。
他の成分としては、例えば、前記セルロース誘導体以外のポリマー、可塑剤、安定剤(酸化防止剤、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)等が挙げられる。さらに、染料や顔料を含む着色剤などを添加することもできる。
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。
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、160~260℃の範囲とすることができ、好ましくは180~240℃の範囲である。
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メチルセルロース(和光純薬製:メチル置換度1.8)50g、ピリジン2Lを量り取り、室温で攪拌した。溶解を確認後、氷冷下、クロロギ酸プロピル295gをゆっくりと滴下し、5℃から15℃の間で3時間攪拌した。反応後、メタノール200mLを加えてクエンチした。反応溶液をメタノール/水(5L/5L)へ激しく攪拌しながら投入すると、黄白色固体が析出した。黄白色固体を吸引ろ過によりろ別し、大量のメタノールで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(P-1)(メチルセルロースプロピルカーボネート、置換度は表2に記載)を白色粉体として得た(56.0g)。
合成例1においてクロロギ酸プロピルをクロロギ酸ヘキシルに変更した以外は同様にして目的のセルロース誘導体(P-2)(メチルセルロースヘキシルカーボネート、置換度は表2に記載)を白色粉体として得た(62.0g)。
合成例1においてクロロギ酸プロピルをクロロギ酸オクチルに変更した以外は同様にして目的のセルロース誘導体(P-3)(メチルセルロースオクチルカーボネート、置換度は表2に記載)を白色粉体として得た(60.2g)。
合成例1においてメチルセルロース(和光純薬製:メチル置換度1.8)を後述の比較化合物H-2に変更し、クロロギ酸プロピルをクロロギ酸-2-エチルヘキシルに変更した以外は同様にして目的のセルロース誘導体(P-4)(メチルセルロース-2-エチルヘキシルカーボネート、置換度は表2に記載)を白色粉体として得た(60.0g)。
合成例1においてクロロギ酸プロピルをクロロギ酸-2-エチルヘキシルに変更した以外は同様にして目的のセルロース誘導体(P-5)(メチルセルロース-2-エチルヘキシルカーボネート、置換度は表2に記載)を白色粉体として得た(71.1g)。
合成例1においてメチルセルロース(和光純薬製:メチル置換度1.8)を後述の比較化合物H-2に変更し、クロロギ酸プロピルをクロロギ酸イソプロピルに変更した以外は同様にして目的のセルロース誘導体(P-6)(メチルセルロースイソプロピルカーボネート、置換度は表2に記載)を白色粉体として得た(37.2g)。
合成例1においてメチルセルロース(和光純薬製:メチル置換度1.8)をエチルセルロース(アルドリッチ製:エチル置換度2.4)に変更し、クロロギ酸プロピルをクロロギ酸オクチルに変更した以外は同様にして目的のセルロース誘導体(P-7)(エチルセルロースオクチルカーボネート、置換度は表2に記載)を白色粉体として得た(44.4g)。
合成例1においてメチルセルロース(和光純薬製:メチル置換度1.8)をエチルセルロース(アルドリッチ製:エチル置換度2.4)に変更し、クロロギ酸プロピルをクロロギ酸-2-エチルヘキシルに変更した以外は同様にして目的のセルロース誘導体(P-8)(エチルセルロース-2-エチルヘキシルカーボネート、置換度は表2に記載)を白色粉体として得た(47.0g)。
合成例1においてクロロギ酸プロピルをクロロギ酸フェニルに変更した以外は同様にして目的のセルロース誘導体(P-9)(メチルセルロースフェニルカーボネート、置換度は表2に記載)を黄白色粉体として得た(85.7g)。
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セルロース(日本製紙製:KCフロックW400)50g、ジメチルアセトアミド1.8L量り取り120℃で2時間攪拌した。次いでリチウムクロライド150gを添加しさらに1時間撹拌した。反応液を室温まで戻した後、ピリジン370mLを添加し、さらに氷冷下でクロロギ酸エチル502gを滴下し、さらに室温で5時間撹拌した。反応溶液をメタノール10Lへ激しく攪拌しながら投入すると、黄白色固体が析出した。黄白色固体を吸引ろ過によりろ別し、大量のメタノールで3回洗浄を行った。得られた黄白色個体を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(H-1)(セルロースエチルカーボネート、置換度は表2に記載)を黄白色粉体として得た(81.6g)。
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)100g、ジメチルアセトアミド2Lを量り取り室温で攪拌した。ここに、粉末水酸化ナトリウム100gを加えて60℃で1時間撹拌後、反応液を冷却し水冷下でヨウ化メチル80mLを滴下し、50℃で3時間撹拌した。反応溶液をメタノール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、大量のイソプロパノールで3回洗浄を行った。得られた白色個体を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(H-2)(メチルセルロース、メチル置換度2.1)を白色粉体として得た(85.3g)。
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アセチルセルロース(ダイセル社製:アセチル置換度2.2)70g、ピリジン1.4Lを量り取り室温で攪拌した。ここに、氷冷下、クロロギ酸エチル42gを加えて10℃で1時間撹拌した。反応溶液をアセトン1.4Lで希釈し、水/メタノール10L/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、大量のイソプロパノールで3回洗浄を行った。得られた白色個体を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(H-5)(エチルカーボネートアセチルセルロース、アセチル置換度2.2、エチルカーボネート置換度0.3)を白色粉体として得た(75.0g)。
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)、分子量分布(MWD)、ガラス転移温度(Tg)を表1に示す。なお、これらの測定方法は以下の通りである。
数平均分子量(Mn)、重量平均分子量(Mw)、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)を用いた。具体的には、テトラヒドロフランを溶媒とし、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。
示差走査熱量計(品番:DSC6200、セイコー電子社製)を用いて10℃/分で昇温して測定した。なお、表中、“-”と表示されているものは、Tgが観測される前に熱分解が観測されたことを意味する。また、表中、“不明瞭”と表示されているものは、後述の溶融成形が可能であったことからTgを有するが、DSC測定において明瞭なピークが観測されなかったことを意味する。
[試験片作製]
上記で得られたセルロース誘導体(P-1)を射出成形機((株)井元製作所製、半自動射出成形機)に供給してシリンダー温度250℃、金型温度30℃、射出圧力1.8kgf/cm2にて4×10×80mmの多目的試験片(衝撃試験片および熱変形試験片)を成形した。
ポリマー成形におけるシリンダー温度はメルトフローレートが5~15g/10minの範囲となる温度に設定した。金型温度は30℃とした。
[フィルム作製]
上記で得られたセルロース誘導体(P-1)をミニプレス機(東洋精機(株)製)を用いて、プレス温度240℃にて100μmの溶融成形フィルムを作製した。
実施例1と同様にして、セルロース誘導体(P-2)~(P-9)、比較化合物としてセルロース誘導体(H-1)、(H-2)、(H-3)(和光純薬製:メチルセルロース、メチル置換度1.8)、(H-4)(アルドリッチ製:エチルセルロース、エチル置換度2.4)、(H-5)を用いて、表2の成形条件に従って成形し試験片を作製した。
得られた試験片について、(株)東洋精機製作所製シャルピー衝撃試験機を用いて、下記の方法にしたがってシャルピー衝撃強度を測定した。結果を表2に示す。
[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、30℃±2℃、50%±5%RHで48時間以上調整した後、シャルピー衝撃試験機によってエッジワイズにて衝撃強度を測定した。
得られたフィルムについて、JIS K7127の方法にしたがって破断伸度を測定した。結果を表2に示す。
即ち、本発明のセルロース誘導体によれば、熱可塑性の発現と優れた耐衝撃性および破断伸度が得られるという予期せぬ効果が発現することがわかる。
本出願は、2008年9月30日出願の日本特許出願(特願2008-255042)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。
Claims (11)
- a)炭化水素基、及び、b)脂肪族オキシカルボニル基及び芳香族オキシカルボニル基の少なくともいずれかを有するセルロース誘導体。
- 前記b)脂肪族オキシカルボニル基又は芳香族オキシカルボニル基が、脂肪族カルボニルオキシ基である、請求項1に記載のセルロース誘導体。
- 前記脂肪族カルボニルオキシ基の脂肪族基の炭素数が6~10である、請求項2に記載のセルロース誘導体。
- 前記a)炭化水素基の炭素数が1~9である、請求項1に記載のセルロース誘導体。
- 前記a)炭化水素基がメチル基又はエチル基である、請求項1に記載のセルロース誘導体。
- 前記a)炭化水素基がメチル基である、請求項1に記載のセルロース誘導体。
- 請求項1に記載のセルロース誘導体の製造方法であって、セルロースエーテルに、塩基存在下、クロロギ酸エステルを反応させる工程を含む、セルロース誘導体の製造方法。
- 請求項1に記載のセルロース誘導体を含有する樹脂組成物。
- 請求項1に記載のセルロース誘導体又は請求項8に記載の樹脂組成物を成形して得られる成形体。
- 請求項1に記載のセルロース誘導体又は請求項8に記載の樹脂組成物を加熱及び成形する工程を含む、成形体の製造方法。
- 請求項9に記載の成形体から構成される電子機器用筐体。
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JP2020019854A (ja) * | 2018-07-31 | 2020-02-06 | 株式会社ダイセル | セルロース誘導体とその成形体 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5273988A (en) * | 1975-12-17 | 1977-06-21 | Hoechst Ag | Process for modifying waterrsoluble hydroxyalkyllcellulose ether and process for preparing aqueous solution of such modified product |
US5068321A (en) * | 1988-10-27 | 1991-11-26 | Wolff Walsrode Aktiengesellschaft | Carbonic acid esters of polysaccharides and a process for their production |
JPH0565301A (ja) * | 1991-09-09 | 1993-03-19 | Asahi Chem Ind Co Ltd | カーボネート化セルロース誘導体 |
JPH0594006A (ja) * | 1991-10-01 | 1993-04-16 | Asahi Chem Ind Co Ltd | 耐光性ペリクル |
JPH05194601A (ja) * | 1991-09-17 | 1993-08-03 | Wolff Walsrode Ag | 炭酸多糖類の製造方法 |
JPH06279502A (ja) * | 1993-03-29 | 1994-10-04 | Asahi Chem Ind Co Ltd | カーボネート化セルロース誘導体の製法 |
JPH06279501A (ja) * | 1993-03-29 | 1994-10-04 | Asahi Chem Ind Co Ltd | カーボネート化セルロース誘導体及びその製造方法 |
US5463034A (en) * | 1988-10-27 | 1995-10-31 | Wolff Walsrode Aktiengesellschaft | Polysaccharides, process for their preparation and their use |
JP2004359737A (ja) * | 2003-06-03 | 2004-12-24 | Teijin Ltd | カーボネート化澱粉誘導体およびその製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2938464A1 (de) | 1979-09-22 | 1981-04-09 | Bayer Ag, 5090 Leverkusen | Thermoplastische polycarbonate, ihre herstellung und ihre verwendung als formkoerper und folien |
JP4610187B2 (ja) | 2003-12-26 | 2011-01-12 | ダイセル化学工業株式会社 | セルロースエステル系樹脂組成物 |
JP5532531B2 (ja) | 2006-06-19 | 2014-06-25 | 三菱化学株式会社 | ポリカーボネート共重合体及びその製造方法 |
-
2008
- 2008-09-30 JP JP2008255042A patent/JP2010084028A/ja active Pending
-
2009
- 2009-09-28 CN CN200980138556.4A patent/CN102164966B/zh not_active Expired - Fee Related
- 2009-09-28 US US13/121,858 patent/US8598336B2/en not_active Expired - Fee Related
- 2009-09-28 WO PCT/JP2009/066821 patent/WO2010038711A1/ja active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5273988A (en) * | 1975-12-17 | 1977-06-21 | Hoechst Ag | Process for modifying waterrsoluble hydroxyalkyllcellulose ether and process for preparing aqueous solution of such modified product |
US5068321A (en) * | 1988-10-27 | 1991-11-26 | Wolff Walsrode Aktiengesellschaft | Carbonic acid esters of polysaccharides and a process for their production |
US5463034A (en) * | 1988-10-27 | 1995-10-31 | Wolff Walsrode Aktiengesellschaft | Polysaccharides, process for their preparation and their use |
JPH0565301A (ja) * | 1991-09-09 | 1993-03-19 | Asahi Chem Ind Co Ltd | カーボネート化セルロース誘導体 |
JPH05194601A (ja) * | 1991-09-17 | 1993-08-03 | Wolff Walsrode Ag | 炭酸多糖類の製造方法 |
JPH0594006A (ja) * | 1991-10-01 | 1993-04-16 | Asahi Chem Ind Co Ltd | 耐光性ペリクル |
JPH06279502A (ja) * | 1993-03-29 | 1994-10-04 | Asahi Chem Ind Co Ltd | カーボネート化セルロース誘導体の製法 |
JPH06279501A (ja) * | 1993-03-29 | 1994-10-04 | Asahi Chem Ind Co Ltd | カーボネート化セルロース誘導体及びその製造方法 |
JP2004359737A (ja) * | 2003-06-03 | 2004-12-24 | Teijin Ltd | カーボネート化澱粉誘導体およびその製造方法 |
Non-Patent Citations (2)
Title |
---|
"Cellulose no Jiten", ASAKURA PUBLISHING CO., LTD, 10 November 2000 (2000-11-10), pages 140 - 144, 479 TO 486 * |
"Cellulose no Kagaku", ASAKURA PUBLISHING CO., LTD., 20 April 2005 (2005-04-20), pages 114 - 116 * |
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CN102164966A (zh) | 2011-08-24 |
US20110183090A1 (en) | 2011-07-28 |
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