[go: up one dir, main page]

WO2020049947A1 - Additive for cellulose ester resin, and cellulose ester composition - Google Patents

Additive for cellulose ester resin, and cellulose ester composition Download PDF

Info

Publication number
WO2020049947A1
WO2020049947A1 PCT/JP2019/031356 JP2019031356W WO2020049947A1 WO 2020049947 A1 WO2020049947 A1 WO 2020049947A1 JP 2019031356 W JP2019031356 W JP 2019031356W WO 2020049947 A1 WO2020049947 A1 WO 2020049947A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
cellulose ester
ester resin
additive
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/031356
Other languages
French (fr)
Japanese (ja)
Inventor
知代 尾崎
裕輔 田尻
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to CN201980057461.3A priority Critical patent/CN112673062A/en
Priority to JP2020541082A priority patent/JP6897880B2/en
Priority to KR1020217004000A priority patent/KR102454821B1/en
Publication of WO2020049947A1 publication Critical patent/WO2020049947A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • C08J2301/10—Esters of organic acids

Definitions

  • the present invention relates to an additive for a cellulose ester resin and a cellulose ester composition.
  • cellulose ester is transparent, optically isotropic and tough, it is widely used as an optical film such as a film for protecting a polarizing film used in a liquid crystal display or a polarized sunglass lens. Further, cellulose ester films are widely used because they exhibit appropriate moisture permeability and are easily bonded to a polarizing film (polyvinyl alcohol (PVA) / iodine) using water paste. Phosphate esters such as triphenyl phosphate (TPP) and ester compounds are used in cellulose ester films for the purpose of controlling a plasticizer and moisture permeability (Patent Documents 1 and 2).
  • An object of the present invention is to provide an additive for a cellulose ester resin that improves storage stability and a cellulose ester composition that has improved storage stability.
  • the present inventor has studied various means and found that, when a specific metal compound is added to a cellulose ester resin together with a polyester-based additive, hydrolysis of the cellulose ester resin under wet heat conditions is suppressed. As a result, the present invention has been completed.
  • the present invention relates to the following.
  • a cellulose ester resin composition comprising the cellulose ester resin additive according to any one of [6] to [9] and a cellulose ester resin.
  • the additive for a cellulose ester resin of the present invention contains one or more metal compounds selected from fatty acid metal salts, metal hydroxides and metal carbonates.
  • the additive for a cellulose ester resin of the present invention contains a metal compound selected from fatty acid salts of metals, hydroxides of metals, and carbonates of metals.
  • metal in one embodiment of the present invention, one or more metals selected from alkali metals, alkaline earth metals, zinc, aluminum, cobalt, nickel, manganese, zirconium, lead, and bismuth are used. be able to.
  • alkali metal include lithium, sodium, and potassium.
  • alkaline earth metal include calcium and barium.
  • lithium, sodium, aluminum, calcium, zinc and barium are preferably used, and calcium and barium are particularly preferably used.
  • the fatty acid metal salt in one embodiment of the present invention is preferably a salt of a fatty acid having 2 to 30 carbon atoms and a metal, more preferably a salt of a fatty acid having 4 to 28 carbon atoms and a metal. Further, a salt of a fatty acid having 6 to 22 carbon atoms with a metal is more preferable. Further, as the fatty acid, a saturated fatty acid, an unsaturated fatty acid, and a derivative thereof can be used, but a saturated fatty acid is preferably used.
  • fatty acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, adipic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, sebacic acid, neodecanoic acid, undecylic acid, lauric acid Acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, 12-hydroxystearic acid, nonadecylic acid, henicosylic acid, tricosylic acid, oleic acid, vaccenic acid, linoleic acid, linoleic acid, Examples include, but are not limited to, eleostearic acid, arachidic acid, mead acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, monta
  • Metal hydroxide In one embodiment of the present invention, a metal hydroxide such as sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, aluminum hydroxide, barium hydroxide, or the like can be used as the metal compound.
  • a metal hydroxide such as sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, aluminum hydroxide, barium hydroxide, or the like can be used as the metal compound.
  • Metal carbonate In one embodiment of the present invention, a metal carbonate such as lithium carbonate, sodium carbonate, magnesium carbonate, potassium carbonate, calcium carbonate, and barium carbonate can be used as the metal compound.
  • the additive for cellulose ester resin is used in combination with a polyester-based additive containing polybasic acid and polyhydric alcohol as essential raw materials.
  • the polyester-based additive is an additive containing a polyester as a main component, and at least 50 parts by mass of the polyester, preferably at least 60 parts by mass, more preferably at least 100 parts by mass of the polyester-based additive. It is an additive containing 65 parts by mass.
  • polyester in the present embodiment uses a polybasic acid and a polyhydric alcohol as essential raw materials.
  • polybasic acid examples include aromatic polycarboxylic acids, aliphatic polycarboxylic acids, oxypolycarboxylic acids, and derivatives thereof.
  • aromatic polycarboxylic acid examples include phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6- Examples thereof include naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, trimellitic acid, trimesic acid, and pyromellitic acid.
  • phthalic acid isophthalic acid, and terephthalic acid are preferred from the viewpoint of obtaining a composition having excellent strength.
  • the aliphatic polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, oxalic acid, decanedicarboxylic acid, fumaric acid, maleic acid, tetrahydrophthalic acid, Examples thereof include hexahydrophthalic acid, 1,2-dicarboxycyclohexane, and 1,2-dicarboxycyclohexene, and these may be used alone or in combination of two or more.
  • succinic acid, adipic acid, sebacic acid, and 1,2-dicarboxycyclohexane are preferable from the viewpoint of excellent compatibility with the cellulose resin.
  • the oxypolycarboxylic acid include oxypolycarboxylic acids such as tartaric acid, tartronic acid, malic acid, and citric acid, and may be used alone or in combination of two or more.
  • the number of carbon atoms excluding carbon contained in the carboxyl group of the polybasic acid is not particularly limited, but is preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 6.
  • polyhydric alcohol examples include a chain aliphatic polyhydric alcohol, a cycloaliphatic polyhydric alcohol, and an aromatic polyhydric alcohol.
  • linear aliphatic polyhydric alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 2- Methyl-1,3-propanediol, 2-butyl-2-ethylpropanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5 -Pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethyl
  • ethylene glycol 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2-methyl-, from the viewpoint of excellent compatibility with the cellulose resin.
  • Preferred are 1,3-propanediol, 1,5-pentanediol, diethylene glycol and dipropylene glycol.
  • cycloaliphatic polyhydric alcohol examples include 1,2-cyclopentanediol, 1,3-cyclopentanediol, cyclopentanedimethanol, cyclohexanediol, cyclohexanedimethanol, cycloheptanediol, cycloheptanedimethanol, hydrogen Bisphenol A and the like may be used alone or in combination of two or more.
  • the aromatic polyhydric alcohol include hydroquinone, resorcinol, bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct, bisphenol F, ethylene oxide adduct of bisphenol F, propylene oxide adduct, biphenol, and biphenol. Examples thereof include an ethylene oxide adduct, 1,2-benzenedimethanol, 1,3-benzenedimethanol, and 1,4-benzenedimethanol. These may be used alone or in combination of two or more.
  • the number of carbon atoms in the polyhydric alcohol is not particularly limited, but is preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 4.
  • the number average molecular weight (Mn) of the polyester additive in one embodiment of the present invention is preferably in the range of 200 to 2,000, more preferably in the range of 250 to 1500, and still more preferably in the range of 300 to 1200.
  • the number average molecular weight (Mn) is a value converted into polystyrene based on a gel permeation chromatography (GPC) measurement.
  • GPC gel permeation chromatography
  • the terminal of the polyester of the present embodiment may be blocked with a residue of a monocarboxylic acid or a residue of a monoalcohol.
  • an aliphatic monocarboxylic acid As the monocarboxylic acid used in the present embodiment, an aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, an aromatic monocarboxylic acid, or the like can be used.
  • the aliphatic monocarboxylic acid include acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexylic acid, nonanoic acid, and derivatives thereof. May be used together.
  • acetic acid is preferred from the viewpoint of excellent compatibility with the cellulose resin.
  • Examples of the alicyclic monocarboxylic acid include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof, and may be used alone or in combination of two or more.
  • aromatic monocarboxylic acids examples include benzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, tetramethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, cumic acid, para-tert-butylbenzoic acid, orthotoluic acid, Benzoic acid such as metatoluic acid, paratoluic acid, ethoxybenzoic acid, propoxybenzoic acid, naphthoic acid, nicotinic acid, furoic acid, and anisic acid having an alkyl group introduced into the benzene ring, 2-hydroxybenzoic acid (salicylic acid), 3 Monohydroxybenzoic acids such as -hydroxybenzoic acid, 4-hydroxybenzoic acid (parahydroxybenzoic acid), and 3,5-di-tert-butyl-4-hydroxybenzoic acid; 2,3-dihydroxybenzoic acid (2-pyrocatec) Acid), 2,4-dihydroxybenzo
  • benzoic acid and paratoluic acid are preferred from the viewpoint of excellent compatibility with the cellulose resin.
  • the number of carbon atoms excluding the carbon of the carboxyl group of the monocarboxylic acid is not particularly limited, but is preferably 1 to 12, and more preferably 1 to 8.
  • Examples of the monoalcohol used in the present embodiment include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert -Pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, decyl alcohol, lauryl alcohol, lactic acid Examples thereof include methyl and ethyl lactate, and they may be used alone or in combination of two or more.
  • the number of carbon atoms of the monoalcohol is not particularly limited, but is preferably 1 to 18, more preferably 2 to 12, and still more preferably 4 to 10.
  • the polyester-based additive further includes an ester compound containing polybasic acid and monoalcohol or polyhydric alcohol and monocarboxylic acid as essential raw materials.
  • the ester compound of the present embodiment may be a diester containing dibasic acid and monoalcohol as essential raw materials, or a diester containing monocarboxylic acid and glycol as essential raw materials.
  • the polybasic acid, polyhydric alcohol, monocarboxylic acid, and monoalcohol are the same as the polybasic acid, polyhydric alcohol, monocarboxylic acid, and monoalcohol in the polyester, and thus description thereof is omitted.
  • dibasic acid As the dibasic acid used in one embodiment of the present invention, an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid can be used.
  • the aliphatic dicarboxylic acid for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid, or a mixture thereof Derivatives and the like.
  • aromatic dicarboxylic acid examples include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, Examples thereof include 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and derivatives thereof.
  • the number of carbon atoms excluding the carboxyl group of the dibasic acid is not particularly limited, but is preferably 1 to 12, and more preferably 2 to 8.
  • the glycol used in one embodiment of the present invention includes ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methylpropanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,2-cyclopentanediol, 1,3-cyclopentane Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, hydrogenated bisphenol A, dimer diol, bisphenol A, bisphenol A Ethylene oxide adducts and propylene oxide adducts It is
  • the content of the ester compound in the polyester-based additive is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less in the polyester-based additive.
  • the polyester-based additive and the ester compound are prepared by subjecting the raw material to the esterification reaction in the presence of an esterification catalyst, if necessary, for example, in a temperature range of 180 to 250 ° C. for 10 to 25 hours. It can be manufactured by doing.
  • the conditions such as the temperature and time of the esterification reaction are not particularly limited, and may be appropriately set.
  • the monocarboxylic acid or dicarboxylic acid the acid itself may be used as a raw material, or its ester compound, acid chloride, anhydride of dicarboxylic acid, or the like may be used as a raw material.
  • esterification catalyst examples include a titanium catalyst such as tetraisopropyl titanate and tetrabutyl titanate; a tin catalyst such as dibutyltin oxide; and an organic sulfonic acid catalyst such as p-toluenesulfonic acid.
  • the amount of the esterification catalyst to be used may be appropriately set, but it is usually preferable to use the esterification catalyst in the range of 0.001 to 0.1 part by mass with respect to 100 parts by mass of the raw material.
  • the cellulose ester resin composition of the present invention contains a cellulose ester resin additive and a cellulose ester resin.
  • cellulose ester resin examples include those obtained by esterifying a part or all of the hydroxyl groups of cellulose obtained from cotton linter, wood pulp, kenaf and the like.
  • the cellulose ester resin include, for example, cellulose acetate such as triacetyl cellulose and diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate, and the like. No. These cellulose ester resins can be used alone or in combination of two or more. When a film comprising the cellulose ester resin composition of the present invention is used as an optical film, particularly as a polarizing plate protective film, the use of cellulose acetate can provide a film having excellent mechanical properties and transparency. Therefore, it is preferable.
  • the obtained optical film comprising the cellulose ester resin composition has mechanical properties and transparency. This is preferable because the film has excellent properties.
  • the average acetylation degree of the cellulose acetate is preferably in the range of 54 to 62.5% by mass.
  • the average acetylation degree of cellulose acetate is preferably in the range of 50.0 to 58% by mass.
  • the average degree of acetylation is a mass ratio of acetic acid produced by saponifying the cellulose acetate with reference to the mass of the cellulose acetate.
  • the cellulose ester resin preferably has a number average molecular weight in the range of 70,000 to 300,000 because the mechanical properties of the film can be improved. When higher mechanical properties are required, it is more preferable to use those having a range of 80,000 to 200,000.
  • the content of the metal compound in the cellulose ester resin composition of the present invention is preferably 10 to 3000 ppm, more preferably 50 to 2000 ppm, and more preferably 200 to 1000 ppm based on 100 parts by mass of the cellulose ester resin. Is more preferable. Further, the metal content is preferably from 0.1 to 1000 ppm, more preferably from 1 to 500 ppm, and still more preferably from 10 to 100 ppm. The metal content here does not include the metal content originally contained in the cellulose ester resin.
  • the content of the polyester-based additive in the cellulose ester resin composition of the present embodiment is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the cellulose ester resin. And more preferably 3 to 20 parts by mass.
  • the cellulose ester resin composition of the present embodiment contains the metal compound of the present invention and a polyester-based additive and a resin for an optical material such as a cellulose ester resin, and contains other various additives as necessary. It may be a resin composition consisting of:
  • the additive examples include, for example, the metal compound of the present invention, other modifiers other than the polyester-based additive, a thermoplastic resin, an ultraviolet absorber, a matting agent, a stabilizer, and a deterioration inhibitor (for example, an antioxidant, Peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, etc.), dyes and the like.
  • a deterioration inhibitor for example, an antioxidant, Peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, etc.
  • ester resins other than the polyester compound and the diester compound specified in the present invention examples include ester resins other than the polyester compound and the diester compound specified in the present invention, phosphate esters such as triphenyl phosphate (TPP), tricresyl phosphate, and cresyl diphenyl phosphate, dimethyl phthalate, Phthalates such as diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, trimethylolpropane tribenzoate, pentaerythritol tetraacetate, tributyl acetyl citrate and the like; It can be used within a range that does not impair the effects of the present invention.
  • phosphate esters such as triphenyl phosphate (TPP), tricresyl phosphate, and cresyl diphen
  • thermoplastic resin is not particularly limited, and examples thereof include polyester resins other than the ester resin of the present invention, polyester ether resins, polyurethane resins, acrylic resins, epoxy resins, and toluenesulfonamide resins.
  • the ultraviolet absorber is not particularly limited, and examples thereof include an oxybenzophenone-based compound, a benzotriazole-based compound, a salicylate-based compound, a benzophenone compound, a cyanoacrylate-based compound, and a nickel complex-based compound.
  • the ultraviolet absorber is preferably used in an amount of 0.01 to 2 parts by mass based on 100 parts by mass of the cellulose ester resin.
  • the matting agent examples include silicon oxide, titanium oxide, aluminum oxide, calcium carbonate, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, kaolin, and talc.
  • the matting agent is preferably used in an amount of 0.1 to 0.3 parts by mass based on 100 parts by mass of the cellulose ester resin.
  • the type and amount of the dye are not particularly limited as long as the object of the present invention is not impaired.
  • a molded article is obtained by molding the cellulose ester resin composition of the present invention.
  • the molded article of the cellulose ester resin composition of the present invention can be used as an optical film because of its excellent transparency.
  • the optical film of the present invention is a film obtained by molding the cellulose ester resin composition of the present invention. Although the thickness of the optical film of the present invention varies depending on the use, it is generally preferably in the range of 10 to 300 ⁇ m.
  • the optical film of the present invention may have properties such as optical anisotropy or optical isotropy, but when the optical film is used as a protective film for a polarizing plate, it does not inhibit light transmission. It is preferable to use an optically isotropic film.
  • the optical film of the present invention can be used for various applications.
  • the most effective use is, for example, a protective film for a polarizing plate that requires optical isotropy of a liquid crystal display, but it can also be used as a support for a protective film for a polarizing plate that requires an optical compensation function. it can.
  • the optical film of the present invention can be used for liquid crystal cells of various display modes. For example, IPS (In-Plane Switching), TN (Twisted Nematic), VA (Vertically Aligned), OCB (Optically Compensatory Bend) and the like can be exemplified. In addition, it is also used as a film for protecting a polarizing film in sunglasses and goggles used for preventing ultraviolet rays and glare.
  • the optical film of the present invention can be produced, for example, by a melt extrusion method. Specifically, the cellulose ester resin, the cellulose ester resin composition containing the cellulose ester resin modifier, and other various additives as necessary, for example, melt-kneaded in an extruder or the like. , A T-die or the like to form a film. Further, the optical film of the present invention, in addition to the molding method, for example, a resin solution obtained by dissolving the cellulose ester resin and the cellulose ester resin modifier in an organic solvent, on a metal support Then, the organic solvent is distilled off and dried, and the mixture is molded by a so-called solution casting method (solvent casting method).
  • solvent casting method solvent casting method
  • the film obtained by the solution casting method can be preferably used for optical applications, and includes a protective film for a polarizing plate, a retardation film, a reflecting plate, a viewing angle improving film, an antiglare film, a non-reflective film, and an antistatic film. It can be preferably used as a polarizing film protective film in a member of a liquid crystal display such as a film or a color filter or an antiglare product such as polarized sunglasses.
  • Polyester additive 1 107.6 g of propylene glycol (hereinafter abbreviated as “PG”) as a glycol component, 361.6 g of phthalic anhydride (hereinafter abbreviated as “PA”) as a dicarboxylic acid component, and isononyl alcohol (hereinafter abbreviated as “INA”) as an alcohol component 412.2 g and 0.06 g of tetraisopropyl titanate (TIPT) as an esterification catalyst were charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and stirred under a nitrogen stream.
  • PG propylene glycol
  • PA phthalic anhydride
  • INA isononyl alcohol
  • TIPT tetraisopropyl titanate
  • the temperature was raised stepwise to 220 ° C., and the reaction was continued at 230 ° C., followed by a dehydration condensation reaction for a total of 19 hours to obtain a polyester-based additive 1 (acid value 0.4, number average molecular weight 560).
  • Polyester additive 2 Contents including 405 g of PG as a glycol component, 79 g of adipic acid (AA) and 240 g of PA as a dicarboxylic acid, 586 g of benzoic acid (BzA) as a monocarboxylic acid, and 0.08 g of TIPT as an esterification catalyst, with a thermometer, a stirrer, and a reflux condenser.
  • the mixture was charged into a two-liter four-necked flask, and the temperature was increased stepwise to 230 ° C. while stirring under a nitrogen stream. Thereafter, the reaction was continued at 230 ° C., and the polyester additive 2 was subjected to a dehydration condensation reaction for a total of 19 hours. (Acid value 0.2, number average molecular weight 410) was obtained.
  • Polyester additive 3 401 g of PG as a glycol component, 327 g of AA as a dicarboxylic acid, 545 g of BzA as a monocarboxylic acid, and 0.08 g of TIPT as an esterification catalyst were charged into a two-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. The temperature was increased stepwise to 230 ° C. while stirring under a stream of air, and then the reaction was continued at 230 ° C., followed by a total of 19 hours of dehydration-condensation reaction to obtain a polyester additive 3 (acid value 0.4, number average molecular weight 400). I got
  • Polyester additive 4 448 g of ethylene glycol (hereinafter abbreviated as EG) as a glycol component, 812 g of AA as a dicarboxylic acid, and 0.04 g of TIPT as an esterification catalyst were placed in a two-liter four-neck flask equipped with a thermometer, a stirrer, and a reflux condenser. The temperature was gradually increased to 225 ° C. while stirring under a nitrogen stream, and then the reaction was continued at 225 ° C., and a total of 19 hours of dehydration-condensation reaction was carried out to obtain polyester additive 4 (acid value 0.2, number average Molecular weight 1350).
  • EG ethylene glycol
  • polyester additive 5 A mixture of the polyester 5 and the ester compound 1 in a weight ratio of 7/3 was used as a polyester additive 5.
  • Optical films were prepared using the polyester additives 1 to 5 and commercially available cellulose ester resins and metal compounds described below.
  • Cellulose ester resin Triacetyl cellulose (degree of acetylation: 60.7%) Diacetyl cellulose (55.5% acetylation)
  • Metal compound Calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) Lithium stearate (Li-St, manufactured by Nitto Kasei Kogyo Co., Ltd.) Sodium stearate (Na-St, manufactured by Nitto Kasei Kogyo Co., Ltd.) Aluminum stearate (Al-St, manufactured by Nitto Kasei Kogyo Co., Ltd.) Calcium stearate (Ca-St, manufactured by Nitto Kasei Kogyo Co., Ltd.) Zinc stearate (Zn-St, manufactured by Nitto Chemical Industry Co.,
  • a dope solution was prepared by adding and dissolving 100 parts of triacetyl cellulose (TAC) resin, 10 parts of a polyester-based additive, and 20 to 1000 ppm of a metal compound to a mixed solvent consisting of 810 parts of methylene chloride and 90 parts of methanol.
  • TAC triacetyl cellulose
  • the dope solution was cast on a glass plate to a thickness of 0.8 mm, dried at room temperature for 16 hours, and then dried at 50 ° C. for 30 minutes and further at 120 ° C. for 30 minutes to obtain a cellulose ester film. I got The following items regarding the storage stability of the obtained film were evaluated. Table 1 shows the results.
  • Example 19 A cellulose ester film was obtained in the same manner as in Example 16 except that diacetyl cellulose (DAC) resin was used instead of triacetyl cellulose resin. The following items regarding the storage stability of the obtained film were evaluated. Table 1 shows the results.
  • DAC diacetyl cellulose
  • a dope solution was prepared by adding 100 parts of triacetyl cellulose (TAC) resin, 10 parts of a polyester-based additive or triphenyl phosphate (TPP) to a mixed solvent consisting of 810 parts of methylene chloride and 90 parts of methanol and dissolving the same.
  • TAC triacetyl cellulose
  • TPP triphenyl phosphate
  • the dope solution was cast on a glass plate to a thickness of 0.8 mm, dried at room temperature for 16 hours, and then dried at 50 ° C. for 30 minutes and further at 120 ° C. for 30 minutes to obtain a cellulose ester film. I got The following items regarding the storage stability of the obtained film were evaluated. Table 1 shows the results.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Polarising Elements (AREA)

Abstract

An additive for cellulose ester resin is provided which improves storage stability. Specifically, an additive for cellulose ester resin is used which contains one or more metal compounds selected from fatty acid metal salts, metal hydroxides and metal carboxylate.

Description

セルロースエステル樹脂用添加剤及びセルロースエステル組成物Additive for cellulose ester resin and cellulose ester composition

　本発明は、セルロースエステル樹脂用添加剤及びセルロースエステル組成物に関する。 The present invention relates to an additive for a cellulose ester resin and a cellulose ester composition.

　セルロースエステルは、透明性、光学的等方性、強靭性であることから、例えば液晶ディスプレイや偏光サングラスレンズに用いられる偏光膜を保護するためのフィルムなど、光学フィルムとして広く使用されている。また、セルロースエステルフィルムは、適度な透湿性を示すことから、水糊を使用した偏光膜（ポリビニルアルコール（ＰＶＡ）／ヨウ素）との接着が容易であることから広く使用されている。セルロースエステルフィルムにはリン酸トリフェニル（ＴＰＰ）などのリン酸エステルやエステル系化合物が可塑剤および透湿性を制御する目的で使用される（特許文献１及び２）。 Because cellulose ester is transparent, optically isotropic and tough, it is widely used as an optical film such as a film for protecting a polarizing film used in a liquid crystal display or a polarized sunglass lens. Further, cellulose ester films are widely used because they exhibit appropriate moisture permeability and are easily bonded to a polarizing film (polyvinyl alcohol (PVA) / iodine) using water paste. Phosphate esters such as triphenyl phosphate (TPP) and ester compounds are used in cellulose ester films for the purpose of controlling a plasticizer and moisture permeability (Patent Documents 1 and 2).

　一方、セルロースエステルは、長期にわたる保管において徐々に加水分解が進行し、さらに湿熱環境下においてはその加水分解速度が加速することが知られている。特に、リン酸トリフェニル（ＴＰＰ）などのリン酸エステルを使用した場合に、加水分解が促進され、長期的な安定性が悪いことが問題となっている。リン酸エステルなどの既存可塑剤と比較し、セルロースエステルの安定性を向上させる観点から脂肪族系ポリエステルまたはフタル酸系ポリエステル系可塑剤が使用されているが、長期的なセルロースエステル組成物の安定性は十分ではない。 On the other hand, it is known that hydrolysis of cellulose esters gradually progresses during long-term storage, and that the hydrolysis rate is accelerated in a moist heat environment. In particular, when a phosphate ester such as triphenyl phosphate (TPP) is used, hydrolysis is promoted, and there is a problem that long-term stability is poor. Compared to existing plasticizers such as phosphate esters, aliphatic polyester or phthalic polyester polyester plasticizers are used from the viewpoint of improving the stability of cellulose esters, but the long-term stability of cellulose ester compositions Sex is not enough.

特開２０１３－１５１６９９号公報JP 2013-151699 A 国際公開第２０１０／０８７２１９号パンフレットInternational Publication No. 2010/087219 pamphlet

　過酷な環境下にあっても長期にわたって加水分解が抑制されたセルロースエステル樹脂の開発が求められている。 セ ル ロ ー ス There is a demand for the development of a cellulose ester resin in which hydrolysis is suppressed for a long time even under a severe environment.

　本発明は、保存安定性を向上させるセルロースエステル樹脂用添加剤及び保存安定性が向上したセルロースエステル組成物を提供することを課題とする。 An object of the present invention is to provide an additive for a cellulose ester resin that improves storage stability and a cellulose ester composition that has improved storage stability.

　本発明者は、様々な手段を検討した結果、セルロールエステル樹脂に、ポリエステル系添加剤と共に、特定の金属化合物を添加すると、湿熱条件下におけるセルロールエステル樹脂の加水分解が抑制されることを見出し、本発明を完成するに至った。 The present inventor has studied various means and found that, when a specific metal compound is added to a cellulose ester resin together with a polyester-based additive, hydrolysis of the cellulose ester resin under wet heat conditions is suppressed. As a result, the present invention has been completed.

　本発明は、以下に関するものである。
［１］脂肪酸金属塩、金属水酸化物及び炭酸金属塩から選択される一種以上の金属化合物を含む、セルロースエステル樹脂用添加剤。
［２］金属化合物が、炭素原子数２～３０の脂肪酸の金属塩である、［１］に記載のセルロースエステル樹脂用添加剤。
［３］金属化合物の金属が、リチウム、ナトリウム、アルミニウム、カルシウム、亜鉛及びバリウムからなる群から選択される、［１］又は［２］に記載のセルロースエステル樹脂用添加剤。
［４］金属化合物の金属が、カルシウム又はバリウムである、［１］～［３］のいずれかに記載のセルロースエステル樹脂用添加剤。
［５］１０～３０００ｐｐｍの含有量でセルロースエステル樹脂に添加するための、［１］～［４］のいずれかに記載のセルロースエステル樹脂用添加剤。
［６］多塩基酸と多価アルコールとを必須原料とするポリエステルを含むポリエステル系添加剤と併用して用いられる、［１］～［５］のいずれかに記載のセルロースエステル樹脂用添加剤。
［７］ポリエステルの末端がモノカルボン酸の残基又はモノアルコールの残基で封止されている、［６］に記載のセルロースエステル樹脂用添加剤。
［８］ポリエステル系添加剤が、多塩基酸とモノアルコールもしくは多価アルコールとモノカルボン酸を必須原料とするエステル化合物をさらに含む、［６］又は［７］に記載のセルロースエステル樹脂用添加剤。
［９］エステル化合物がジエステルである、［８］に記載のセルロースエステル樹脂用添加剤。
［１０］［６］から［９］のいずれかに記載のセルロースエステル樹脂用添加剤及びセルロースエステル樹脂を含む、セルロースエステル樹脂組成物。
［１１］［１０］に記載のセルロースエステル樹脂組成物の成形品。
［１２］光学フィルムである、［１１］に記載の成形品。 The present invention relates to the following.
[1] An additive for a cellulose ester resin containing one or more metal compounds selected from fatty acid metal salts, metal hydroxides and metal carbonates.
[2] The additive for cellulose ester resin according to [1], wherein the metal compound is a metal salt of a fatty acid having 2 to 30 carbon atoms.
[3] The additive for cellulose ester resin according to [1] or [2], wherein the metal of the metal compound is selected from the group consisting of lithium, sodium, aluminum, calcium, zinc, and barium.
[4] The additive for a cellulose ester resin according to any one of [1] to [3], wherein the metal of the metal compound is calcium or barium.
[5] The additive for a cellulose ester resin according to any one of [1] to [4], which is added to the cellulose ester resin at a content of 10 to 3000 ppm.
[6] The additive for a cellulose ester resin according to any one of [1] to [5], which is used in combination with a polyester-based additive containing a polyester containing a polybasic acid and a polyhydric alcohol as essential raw materials.
[7] The additive for cellulose ester resin according to [6], wherein the terminal of the polyester is sealed with a residue of a monocarboxylic acid or a residue of a monoalcohol.
[8] The additive for cellulose ester resin according to [6] or [7], wherein the polyester-based additive further includes an ester compound containing polybasic acid and monoalcohol or polyhydric alcohol and monocarboxylic acid as essential raw materials. .
[9] The additive for cellulose ester resin according to [8], wherein the ester compound is a diester.
[10] A cellulose ester resin composition comprising the cellulose ester resin additive according to any one of [6] to [9] and a cellulose ester resin.
[11] A molded article of the cellulose ester resin composition according to [10].
[12] The molded article according to [11], which is an optical film.

　本発明によれば、保存安定性を向上させるセルロースエステル樹脂用添加剤を提供することができる。 According to the present invention, it is possible to provide an additive for cellulose ester resin which improves storage stability.

　以下、本発明の一実施形態について詳細に説明する。本発明は、以下の実施形態に限定されるものではなく、本発明の効果を阻害しない範囲で適宜変更を加えて実施することができる。 Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention.

〔セルロースエステル樹脂用添加剤〕
　本発明のセルロースエステル樹脂用添加剤は、脂肪酸金属塩、金属水酸化物及び炭酸金属塩から選択される一種以上の金属化合物を含む。 (Additive for cellulose ester resin)
The additive for a cellulose ester resin of the present invention contains one or more metal compounds selected from fatty acid metal salts, metal hydroxides and metal carbonates.

　本発明のセルロースエステル樹脂用添加剤は、金属の脂肪酸塩、金属の水酸化物、及び金属の炭酸塩から選択される金属化合物を含む。 セ ル ロ ー ス The additive for a cellulose ester resin of the present invention contains a metal compound selected from fatty acid salts of metals, hydroxides of metals, and carbonates of metals.

［金属］
  本発明の一実施形態において、金属化合物に含まれる金属としては、アルカリ金属、アルカリ土類金属、亜鉛、アルミニウム、コバルト、ニッケル、マンガン、ジルコニウム、鉛、ビスマスから選択される一種以上の金属を用いることができる。アルカリ金属としては、例えばリチウム、ナトリウム、カリウムなどが挙げられる。アルカリ土類金属としては、カルシウム、バリウムなどが挙げられる。本実施形態においては、リチウム、ナトリウム、アルミニウム、カルシウム、亜鉛及びバリウムが好適に用いられ、カルシウム及びバリウムが特に好適に用いられる。 [metal]
In one embodiment of the present invention, as the metal contained in the metal compound, one or more metals selected from alkali metals, alkaline earth metals, zinc, aluminum, cobalt, nickel, manganese, zirconium, lead, and bismuth are used. be able to. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include calcium and barium. In the present embodiment, lithium, sodium, aluminum, calcium, zinc and barium are preferably used, and calcium and barium are particularly preferably used.

［脂肪酸］
　本発明の一実施形態における脂肪酸金属塩は、炭素原子数２～３０の脂肪酸と金属との塩であることが好ましく、炭素原子数４～２８の脂肪酸と金属との塩であることがより好ましく、炭素原子数６～２２の脂肪酸と金属との塩であることがさらに好ましい。また、脂肪酸として、飽和脂肪酸、不飽和脂肪酸、およびこれらの誘導体を用いることができるが、飽和脂肪酸を用いることが好ましい。脂肪酸の例としては、酢酸、プロピオン酸、酪酸、バレリアン酸、カプロン酸、アジピン酸、エナント酸、カプリル酸、２－エチルヘキサン酸、ペラルゴン酸、カプリン酸、セバシン酸、ネオデカン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、パルミトレイン酸、マルガリン酸、ステアリン酸、１２－ヒドロキシステアリン酸、ノナデシル酸、ヘンイコシル酸、トリコシル酸、オレイン酸、バクセン酸、リノール酸、リノレイン酸、エレオステアリン酸、アラキジン酸、ミード酸、アラキドン酸、ベヘン酸、リグノセリン酸、ネルボン酸、セロチン酸、モンタン酸、メリシン酸およびこれらの誘導体が挙げられるが、これに限定されるものではない。 [fatty acid]
The fatty acid metal salt in one embodiment of the present invention is preferably a salt of a fatty acid having 2 to 30 carbon atoms and a metal, more preferably a salt of a fatty acid having 4 to 28 carbon atoms and a metal. Further, a salt of a fatty acid having 6 to 22 carbon atoms with a metal is more preferable. Further, as the fatty acid, a saturated fatty acid, an unsaturated fatty acid, and a derivative thereof can be used, but a saturated fatty acid is preferably used. Examples of fatty acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, adipic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, sebacic acid, neodecanoic acid, undecylic acid, lauric acid Acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, 12-hydroxystearic acid, nonadecylic acid, henicosylic acid, tricosylic acid, oleic acid, vaccenic acid, linoleic acid, linoleic acid, Examples include, but are not limited to, eleostearic acid, arachidic acid, mead acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melicic acid and derivatives thereof.

［金属水酸化物］
　本発明の一実施形態において、水酸化ナトリウム、水酸化マグネシウム、水酸化カリウム、水酸化カルシウム、水酸化アルミニウム、水酸化バリウム、などの金属水酸化物を金属化合物として用いることができる。 [Metal hydroxide]
In one embodiment of the present invention, a metal hydroxide such as sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, aluminum hydroxide, barium hydroxide, or the like can be used as the metal compound.

［炭酸金属塩］
　本発明の一実施形態において、炭酸リチウム、炭酸ナトリウム、炭酸マグネシウム、炭酸カリウム、炭酸カルシウム、炭酸バリウムなどの炭酸金属塩を金属化合物として用いることができる。 [Metal carbonate]
In one embodiment of the present invention, a metal carbonate such as lithium carbonate, sodium carbonate, magnesium carbonate, potassium carbonate, calcium carbonate, and barium carbonate can be used as the metal compound.

〔ポリエステル系添加剤〕
　本発明の一実施形態において、セルロースエステル樹脂用添加剤は、多塩基酸と多価アルコールとを必須原料とするポリエステル系添加剤と併用して用いられる。本実施形態において、ポリエステル系添加剤は、ポリエステルを主成分とする添加剤であり、ポリエステル系添加剤１００質量部に対してポリエステルを少なくとも５０質量部、好ましくは少なくとも６０質量部、より好ましくは少なくとも６５質量部含有する添加剤である。 (Polyester additive)
In one embodiment of the present invention, the additive for cellulose ester resin is used in combination with a polyester-based additive containing polybasic acid and polyhydric alcohol as essential raw materials. In the present embodiment, the polyester-based additive is an additive containing a polyester as a main component, and at least 50 parts by mass of the polyester, preferably at least 60 parts by mass, more preferably at least 100 parts by mass of the polyester-based additive. It is an additive containing 65 parts by mass.

［ポリエステル］
　本実施形態におけるポリエステルは、多塩基酸と多価アルコールとを必須原料とする。 [polyester]
The polyester in the present embodiment uses a polybasic acid and a polyhydric alcohol as essential raw materials.

（多塩基酸）
本実施形態で用いられる多塩基酸としては、芳香族多価カルボン酸、脂肪族多価カルボン酸、オキシ多価カルボン酸、またはその誘導体などが挙げられる。
　芳香族多価カルボン酸としては、フタル酸、イソフタル酸、テレフタル酸、無水フタル酸、１，４－ナフタレンジカルボン酸、１，８－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸、２，６－ナフタレンジカルボン酸、２，７－ナフタレンジカルボン酸、４，４’－ビフェニルジカルボン酸、トリメリット酸、トリメシン酸、ピロメリット酸などが挙げられ、単独でも、２種以上を併用しても良い。これらの中でも、強度に優れる組成物が得られる観点から、フタル酸、イソフタル酸、テレフタル酸が好ましい。
　脂肪族多価カルボン酸としては、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、シュウ酸、デカンジカルボン酸、フマル酸、マレイン酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、１，２－ジカルボキシシクロヘキサン、１，２－ジカルボキシシクロヘキセンなどが挙げられ、単独でも、２種以上を併用しても良い。これらの中でも、セルロース樹脂との相溶性に優れる観点から、コハク酸、アジピン酸、セバシン酸、１，２－ジカルボキシシクロヘキサンであることが好ましい。
　オキシ多価カルボン酸としては、酒石酸、タルトロン酸、リンゴ酸、クエン酸のようなオキシ多価カルボン酸などが挙げられ、単独でも、２種以上を併用しても良い。 (Polybasic acid)
Examples of the polybasic acid used in the present embodiment include aromatic polycarboxylic acids, aliphatic polycarboxylic acids, oxypolycarboxylic acids, and derivatives thereof.
Examples of the aromatic polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6- Examples thereof include naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, trimellitic acid, trimesic acid, and pyromellitic acid. These may be used alone or in combination of two or more. Among these, phthalic acid, isophthalic acid, and terephthalic acid are preferred from the viewpoint of obtaining a composition having excellent strength.
Examples of the aliphatic polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, oxalic acid, decanedicarboxylic acid, fumaric acid, maleic acid, tetrahydrophthalic acid, Examples thereof include hexahydrophthalic acid, 1,2-dicarboxycyclohexane, and 1,2-dicarboxycyclohexene, and these may be used alone or in combination of two or more. Among these, succinic acid, adipic acid, sebacic acid, and 1,2-dicarboxycyclohexane are preferable from the viewpoint of excellent compatibility with the cellulose resin.
Examples of the oxypolycarboxylic acid include oxypolycarboxylic acids such as tartaric acid, tartronic acid, malic acid, and citric acid, and may be used alone or in combination of two or more.

　多塩基酸のカルボキシル基に含まれる炭素を除いた炭素原子数としては、特に限定されるものではないが、２～１２が好ましく、２～８がより好ましく、２～６がさらに好ましい。 The number of carbon atoms excluding carbon contained in the carboxyl group of the polybasic acid is not particularly limited, but is preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 6.

（多価アルコール）
本実施形態で用いられる多価アルコールとしては、例えば、鎖状の脂肪族多価アルコールや環式脂肪族多価アルコール、芳香族多価アルコールなどが挙げられる。
　鎖状の脂肪族多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，２－プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，３－プロパンジオール、２－メチル－１，３－プロパンジオール、２－ブチル－２－エチルプロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、ネオペンチルグリコール、１，６－ヘキサンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、２－エチル－１,３－ヘキサンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、２－メチル－１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、１，１２－ドデカンジオールなどの２価の脂肪族アルコール；グリセリン、１，２，３－ブタントリオール、１，２，４－ブタントリオール、１，２，３－ヘプタトリオール、１，２，４－ヘプタトリオール、１，２，５－ヘプタトリオール、２，３，４－ヘプタトリオール、トリメチロールプロパンなどの３価の脂肪族アルコール；ペンタエリトリトール、エリトリトールなどの４価の脂肪族アルコール；キシリトールなどの５価の脂肪族アルコール；ジペンタエリトリトール、ソルビトールなどの６価の脂肪族アルコールなどが挙げられ、単独でも、２種以上を併用しても良い。これらの中でも、セルロース樹脂との相溶性に優れる観点から、エチレングリコール、１，２－プロピレングリコール、１，３－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、２－メチル－１,３－プロパンジオール、１，５－ペンタンジオール、ジエチレングリコール、ジプロピレングリコールであることが好ましい。
　環式脂肪族多価アルコールとしては、例えば、１，２－シクロペンタンジオール、１，３－シクロペンタンジオール、シクロペンタンジメタノール、シクロヘキサンジオール、シクロヘキサンジメタノール、シクロヘプタンジオール、シクロヘプタンジメタノール、水素化ビスフェノールＡなどが挙げられ、単独でも、２種以上を併用しても良い。
　芳香族多価アルコールとしては、例えば、ハイドロキノン、レゾルシン、ビスフェノールＡ、ビスフェノールＡのエチレンオキサイド付加物、プロピレンオキサイド付加物、ビスフェノールＦ、ビスフェノールＦのエチレンオキサイド付加物、プロピレンオキサイド付加物、ビフェノール、ビフェノールのエチレンオキサイド付加物、１，２－ベンゼンジメタノール、１，３－ベンゼンジメタノール、１，４－ベンゼンジメタノールなどが挙げられ、単独でも、２種以上を併用しても良い。 (Polyhydric alcohol)
Examples of the polyhydric alcohol used in the present embodiment include a chain aliphatic polyhydric alcohol, a cycloaliphatic polyhydric alcohol, and an aromatic polyhydric alcohol.
Examples of the linear aliphatic polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 2- Methyl-1,3-propanediol, 2-butyl-2-ethylpropanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5 -Pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexane Diol, 1,7-heptanediol, 1,8-octanediol , 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and other dihydric aliphatic alcohols; glycerin, 1,2,3-butane Triol, 1,2,4-butanetriol, 1,2,3-heptatriol, 1,2,4-heptatriol, 1,2,5-heptatriol, 2,3,4-heptatriol, trimethylolpropane Trihydric aliphatic alcohols such as pentaerythritol and erythritol; pentavalent aliphatic alcohols such as xylitol; hexavalent aliphatic alcohols such as dipentaerythritol and sorbitol; One or two or more of them may be used in combination. Among them, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2-methyl-, from the viewpoint of excellent compatibility with the cellulose resin. Preferred are 1,3-propanediol, 1,5-pentanediol, diethylene glycol and dipropylene glycol.
Examples of the cycloaliphatic polyhydric alcohol include 1,2-cyclopentanediol, 1,3-cyclopentanediol, cyclopentanedimethanol, cyclohexanediol, cyclohexanedimethanol, cycloheptanediol, cycloheptanedimethanol, hydrogen Bisphenol A and the like may be used alone or in combination of two or more.
Examples of the aromatic polyhydric alcohol include hydroquinone, resorcinol, bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct, bisphenol F, ethylene oxide adduct of bisphenol F, propylene oxide adduct, biphenol, and biphenol. Examples thereof include an ethylene oxide adduct, 1,2-benzenedimethanol, 1,3-benzenedimethanol, and 1,4-benzenedimethanol. These may be used alone or in combination of two or more.

　多価アルコールの炭素原子数としては、特に限定されるものではないが、２～１２が好ましく、２～８がより好ましく、２～４がさらに好ましい。 The number of carbon atoms in the polyhydric alcohol is not particularly limited, but is preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 4.

　本発明の一実施形態におけるポリエステル系添加剤の数平均分子量（Ｍｎ）は、２００～２０００の範囲が好ましく、２５０～１５００の範囲がより好ましく、３００～１２００の範囲がさらに好ましい。 数 The number average molecular weight (Mn) of the polyester additive in one embodiment of the present invention is preferably in the range of 200 to 2,000, more preferably in the range of 250 to 1500, and still more preferably in the range of 300 to 1200.

　ここで、数平均分子量（Ｍｎ）はゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定に基づきポリスチレン換算した値である。なお、ＧＰＣの測定条件は以下の通りである。 Here, the number average molecular weight (Mn) is a value converted into polystyrene based on a gel permeation chromatography (GPC) measurement. In addition, the measurement conditions of GPC are as follows.

［ＧＰＣ測定条件］
　測定装置：東ソー株式会社製高速ＧＰＣ装置「ＨＬＣ－８３２０ＧＰＣ」
　カラム：東ソー株式会社製「ＴＳＫ　ＧＵＲＤＣＯＬＵＭＮ　ＳｕｐｅｒＨＺ－Ｌ」＋東ソー株式会社製「ＴＳＫ　ｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｍ」＋東ソー株式会社製「ＴＳＫ　ｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｍ」＋東ソー株式会社製「ＴＳＫ　ｇｅｌ　ＳｕｐｅｒＨＺ－２０００」＋東ソー株式会社製「ＴＳＫ　ｇｅｌ　ＳｕｐｅｒＨＺ－２０００」
　検出器：ＲＩ（示差屈折計）
　データ処理：東ソー株式会社製「ＥｃｏＳＥＣ　Ｄａｔａ　Ａｎａｌｙｓｉｓ　バージョン１．０７」
　カラム温度：４０℃
　展開溶媒：テトラヒドロフラン
　流速：０．３５ｍＬ／分
　測定試料：試料７．５ｍｇを１０ｍｌのテトラヒドロフランに溶解し、得られた溶液をマイクロフィルターでろ過したものを測定試料とした。
　試料注入量：２０μｌ
　標準試料：前記「ＨＬＣ－８３２０ＧＰＣ」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
　（単分散ポリスチレン）
　東ソー株式会社製「Ａ－３００」
　東ソー株式会社製「Ａ－５００」
　東ソー株式会社製「Ａ－１０００」
　東ソー株式会社製「Ａ－２５００」
　東ソー株式会社製「Ａ－５０００」
　東ソー株式会社製「Ｆ－１」
　東ソー株式会社製「Ｆ－２」
　東ソー株式会社製「Ｆ－４」
　東ソー株式会社製「Ｆ－１０」
　東ソー株式会社製「Ｆ－２０」
　東ソー株式会社製「Ｆ－４０」
　東ソー株式会社製「Ｆ－８０」
　東ソー株式会社製「Ｆ－１２８」
　東ソー株式会社製「Ｆ－２８８」 [GPC measurement conditions]
Measuring device: High-speed GPC device “HLC-8320GPC” manufactured by Tosoh Corporation
Column: “TSK GARDCOLUMN SuperHZ-L” manufactured by Tosoh Corporation + “TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZM-2000” manufactured by Tosoh Corporation + Tosoh Corporation “TSK gel SuperHZ-2000”
Detector: RI (differential refractometer)
Data processing: "EcoSEC Data Analysis Version 1.07" manufactured by Tosoh Corporation
Column temperature: 40 ° C
Developing solvent: tetrahydrofuran Flow rate: 0.35 mL / min Measurement sample: 7.5 mg of a sample was dissolved in 10 ml of tetrahydrofuran, and the obtained solution was filtered with a microfilter to obtain a measurement sample.
Sample injection volume: 20 μl
Standard sample: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of "HLC-8320GPC".
(Monodisperse polystyrene)
"A-300" manufactured by Tosoh Corporation
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
"F-288" manufactured by Tosoh Corporation

本実施形態のポリエステルは、末端がモノカルボン酸の残基又はモノアルコールの残基で封止されていてもよい。 The terminal of the polyester of the present embodiment may be blocked with a residue of a monocarboxylic acid or a residue of a monoalcohol.

（モノカルボン酸）
　本実施形態で用いられるモノカルボン酸としては、脂肪族モノカルボン酸、脂環族モノカルボン酸、芳香族モノカルボン酸などを用いることができる。
　脂肪族モノカルボン酸としては、酢酸、プロパン酸、ブタン酸、ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、２－エチルヘキシル酸、ノナン酸や、これらの誘導体が挙げられ、単独でも、２種以上を併用しても良い。これらの中でも、セルロース樹脂との相溶性に優れる観点から、酢酸であることが好ましい。
　脂環族モノカルボン酸としては、シクロペンタンカルボン酸、シクロヘキサンカルボン酸、シクロオクタンカルボン酸、またはそれらの誘導体が挙げられ、単独でも、２種以上を併用しても良い。
　芳香族モノカルボン酸としては、安息香酸や、ジメチル安息香酸、トリメチル安息香酸、テトラメチル安息香酸、エチル安息香酸、プロピル安息香酸、ブチル安息香酸、クミン酸、パラターシャリブチル安息香酸、オルソトルイル酸、メタトルイル酸、パラトルイル酸、エトキシ安息香酸、プロポキシ安息香酸、ナフトエ酸、ニコチン酸、フロ酸、アニス酸などの安息香酸のベンゼン環にアルキル基を導入したもの、２－ヒドロキシ安息香酸（サリチル酸）、３－ヒドロキシ安息香酸、４－ヒドロキシ安息香酸（パラヒドロキシ安息香酸）、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ安息香酸等のモノヒドロキシ安息香酸；２，３－ジヒドロキシ安息香酸（２－ピロカテク酸）、２，４－ジヒドロキシ安息香酸（β－レゾルシン酸）、２，５－ジヒドロキシ安息香酸（ゲンチジン酸）、２，６－ジヒドロキシ安息香酸（γ－レゾルシン酸）、３，４－ジヒドロキシ安息香酸（プロトカテク酸）、３，５－ジヒドロキシ安息香酸（α－レゾルシン酸）などのジヒドロキシ安息香酸、３，４，５－トリヒドロキシ安息香酸、２，４，６－トリヒドロキシ安息香酸などのトリヒドロキシ安息香酸、２－ヒドロキシ－１－ナフトエ酸、１－ヒドロキシ－２－ナフトエ酸、３－ヒドロキシ－２－ナフトエ酸、６－ヒドロキシ－２－ナフトエ酸などのモノヒドロキシナフタレンカルボン酸などの安息香酸のベンゼン環にヒドロキシル基を導入したもの、ビフェニルカルボン酸、ナフタレンカルボン酸、テトラリンカルボン酸などのベンゼン環を２個以上持つ芳香族モノカルボン酸、またはそれらの誘導体が挙げられ、単独でも、２種以上を併用しても良い。これらの中でも、セルロース樹脂との相溶性に優れる観点から、安息香酸、パラトルイル酸であることが好ましい。
　モノカルボン酸のカルボキシル基の炭素を除く炭素原子数としては、特に限定されるものではないが、１～１２が好ましく、１～８がより好ましい。 (Monocarboxylic acid)
As the monocarboxylic acid used in the present embodiment, an aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, an aromatic monocarboxylic acid, or the like can be used.
Examples of the aliphatic monocarboxylic acid include acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexylic acid, nonanoic acid, and derivatives thereof. May be used together. Among these, acetic acid is preferred from the viewpoint of excellent compatibility with the cellulose resin.
Examples of the alicyclic monocarboxylic acid include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof, and may be used alone or in combination of two or more.
Examples of aromatic monocarboxylic acids include benzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, tetramethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, cumic acid, para-tert-butylbenzoic acid, orthotoluic acid, Benzoic acid such as metatoluic acid, paratoluic acid, ethoxybenzoic acid, propoxybenzoic acid, naphthoic acid, nicotinic acid, furoic acid, and anisic acid having an alkyl group introduced into the benzene ring, 2-hydroxybenzoic acid (salicylic acid), 3 Monohydroxybenzoic acids such as -hydroxybenzoic acid, 4-hydroxybenzoic acid (parahydroxybenzoic acid), and 3,5-di-tert-butyl-4-hydroxybenzoic acid; 2,3-dihydroxybenzoic acid (2-pyrocatec) Acid), 2,4-dihydroxybenzoic acid (β-resorcinic acid), 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (γ-resorcinic acid), 3,4-dihydroxybenzoic acid (protocatechuic acid), 3,5-dihydroxybenzoic acid (α-resorcinic acid) Trihydroxybenzoic acid such as dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid Benzoic acid such as monohydroxynaphthalenecarboxylic acid such as acid, 3-hydroxy-2-naphthoic acid and 6-hydroxy-2-naphthoic acid having a hydroxyl group introduced into the benzene ring, biphenylcarboxylic acid, naphthalenecarboxylic acid, tetralin Aromatic monocarboxylic acids having two or more benzene rings, such as carboxylic acids, or Et derivatives and the like, alone or in combination of two or more thereof. Among these, benzoic acid and paratoluic acid are preferred from the viewpoint of excellent compatibility with the cellulose resin.
The number of carbon atoms excluding the carbon of the carboxyl group of the monocarboxylic acid is not particularly limited, but is preferably 1 to 12, and more preferably 1 to 8.

（モノアルコール）
　本実施形態で用いられるモノアルコールとしては、例えば、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、イソブタノール、ｔ－ブタノール、１－ペンタノール、イソペンチルアルコール、ｔｅｒｔ－ペンチルアルコール、シクロペンタノール、１－ヘキサノール、シクロヘキサノール、１－ヘプタノール、１－オクタノール、２－エチル－１－ヘキサノール、イソノニルアルコール、１－ノニルアルコール、アミルアルコール、デシルアルコール、ラウリルアルコール、乳酸メチル、乳酸エチルなどが挙げられ、単独でも、２種以上を併用しても良い。これらの中でも、原料の入手や合成が容易である観点から、１－ブタノール、シクロヘキサノール、２－エチル－１－ヘキサノール、イソノニルアルコールであることが好ましい。
　モノアルコールの炭素原子数としては、特に限定されるものではないが、１～１８が好ましく、２～１２がより好ましく、４～１０がさらに好ましい。 (Mono alcohol)
Examples of the monoalcohol used in the present embodiment include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert -Pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, decyl alcohol, lauryl alcohol, lactic acid Examples thereof include methyl and ethyl lactate, and they may be used alone or in combination of two or more. Among these, 1-butanol, cyclohexanol, 2-ethyl-1-hexanol and isononyl alcohol are preferred from the viewpoint of easy availability of raw materials and easy synthesis.
The number of carbon atoms of the monoalcohol is not particularly limited, but is preferably 1 to 18, more preferably 2 to 12, and still more preferably 4 to 10.

［エステル化合物］
本発明の一実施形態において、ポリエステル系添加剤は、多塩基酸とモノアルコールもしくは多価アルコールとモノカルボン酸を必須原料とするエステル化合物をさらに含む。本実施形態のエステル化合物は、二塩基酸とモノアルコールとを必須原料とするジエステルや、モノカルボン酸とグリコールを必須原料とするジエステルであってもよい。ここで、多塩基酸、多価アルコール、モノカルボン酸及びモノアルコールについては、ポリエステルにおける多塩基酸、多価アルコール、モノカルボン酸及びモノアルコールと同じであるので、説明を省略する。 [Ester compound]
In one embodiment of the present invention, the polyester-based additive further includes an ester compound containing polybasic acid and monoalcohol or polyhydric alcohol and monocarboxylic acid as essential raw materials. The ester compound of the present embodiment may be a diester containing dibasic acid and monoalcohol as essential raw materials, or a diester containing monocarboxylic acid and glycol as essential raw materials. Here, the polybasic acid, polyhydric alcohol, monocarboxylic acid, and monoalcohol are the same as the polybasic acid, polyhydric alcohol, monocarboxylic acid, and monoalcohol in the polyester, and thus description thereof is omitted.

（二塩基酸）
　本発明の一実施形態で用いられる二塩基酸としては、脂肪族ジカルボン酸や芳香族ジカルボン酸を用いることができる。
　脂肪族ジカルボン酸としては、例えば、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、デカンジカルボン酸、シクロヘキサンジカルボン酸、ダイマー酸、フマル酸、又はそれらの誘導体などが挙げられる。
　芳香族ジカルボン酸としては、フタル酸、イソフタル酸、テレフタル酸、１，４－ナフタレンジカルボン酸、１，５－ナフタレンジカルボン酸、１，８－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸、２，６－ナフタレンジカルボン酸、２，７－ナフタレンジカルボン酸、４，４’－ビフェニルジカルボン酸、又はそれらの誘導体などが挙げられる。
　二塩基酸のカルボキシル基を除く炭素原子数としては、特に限定されるものではないが、１～１２が好ましく、２～８がより好ましい。 (Dibasic acid)
As the dibasic acid used in one embodiment of the present invention, an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid can be used.
As the aliphatic dicarboxylic acid, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid, or a mixture thereof Derivatives and the like.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, Examples thereof include 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and derivatives thereof.
The number of carbon atoms excluding the carboxyl group of the dibasic acid is not particularly limited, but is preferably 1 to 12, and more preferably 2 to 8.

（グリコール）
　本発明の一実施形態で用いられるグリコールとしては、エチレングリコール、１，２－プロピレングリコール、１，３－プロパンジオール、２－メチルプロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、ネオペンチルグリコール、１，２－シクロペンタンジオール、１，３－シクロペンタンジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、水素化ビスフェノールＡ、ダイマージオール、ビスフェノールＡ、ビスフェノールＡのエチレンオキサイド付加物、プロピレンオキサイド付加物などが挙げられる。
　グリコールの炭素原子数としては、特に限定されるものではないが、２～１２が好ましく、２～８がより好ましく、２～４がさらに好ましい。 (Glycol)
The glycol used in one embodiment of the present invention includes ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methylpropanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,2-cyclopentanediol, 1,3-cyclopentane Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, hydrogenated bisphenol A, dimer diol, bisphenol A, bisphenol A Ethylene oxide adducts and propylene oxide adducts It is below.
The number of carbon atoms in the glycol is not particularly limited, but is preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 4.

　ポリエステル系添加剤中のエステル化合物の含有量は、ポリエステル系添加剤中５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下がさらに好ましい。 エ ス テ ル The content of the ester compound in the polyester-based additive is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less in the polyester-based additive.

［エステル化反応］
　本発明の一実施形態において、ポリエステル系添加剤やエステル化合物は、必要に応じてエステル化触媒の存在下で原料を、例えば、１８０～２５０℃の温度範囲内で１０～２５時間、エステル化反応させることにより製造することができる。尚、エステル化反応の温度、時間などの条件は特に限定せず、適宜設定してよい。モノカルボン酸やジカルボン酸については、原料として酸そのものを使用してもよく、あるいは、そのエステル化合物、酸塩化物、ジカルボン酸の無水物等を原料としても良い。
　エステル化触媒としては、例えば、テトライソプロピルチタネート、テトラブチルチタネート等のチタン系触媒；ジブチル錫オキサイド等のスズ系触媒；ｐ－トルエンスルホン酸等の有機スルホン酸系触媒などが挙げられる。
　エステル化触媒の使用量は、適宜設定すればよいが、通常、原料の全量１００質量部に対して、０．００１～０．１質量部の範囲で使用することが好ましい。 [Esterification reaction]
In one embodiment of the present invention, the polyester-based additive and the ester compound are prepared by subjecting the raw material to the esterification reaction in the presence of an esterification catalyst, if necessary, for example, in a temperature range of 180 to 250 ° C. for 10 to 25 hours. It can be manufactured by doing. The conditions such as the temperature and time of the esterification reaction are not particularly limited, and may be appropriately set. As for the monocarboxylic acid or dicarboxylic acid, the acid itself may be used as a raw material, or its ester compound, acid chloride, anhydride of dicarboxylic acid, or the like may be used as a raw material.
Examples of the esterification catalyst include a titanium catalyst such as tetraisopropyl titanate and tetrabutyl titanate; a tin catalyst such as dibutyltin oxide; and an organic sulfonic acid catalyst such as p-toluenesulfonic acid.
The amount of the esterification catalyst to be used may be appropriately set, but it is usually preferable to use the esterification catalyst in the range of 0.001 to 0.1 part by mass with respect to 100 parts by mass of the raw material.

〔セルロースエステル樹脂組成物〕
　本発明のセルロースエステル樹脂組成物は、セルロースエステル樹脂用添加剤及びセルロースエステル樹脂を含む。 (Cellulose ester resin composition)
The cellulose ester resin composition of the present invention contains a cellulose ester resin additive and a cellulose ester resin.

［セルロースエステル樹脂］
　セルロースエステル樹脂としては、綿花リンター、木材パルプ、ケナフ等から得られるセルロースの有する水酸基の一部、又は全部がエステル化されたものが挙げられる。 [Cellulose ester resin]
Examples of the cellulose ester resin include those obtained by esterifying a part or all of the hydroxyl groups of cellulose obtained from cotton linter, wood pulp, kenaf and the like.

　前記セルロースエステル樹脂の具体例としては、例えば、トリアセチルセルロースやジアセチルセルロース等のセルロースアセテート、セルロースアセテートプロピオネート、セルロースアセテートブチレート、セルロースアセテートプロピオネートブチレート、セルロースアセテートフタレート及び硝酸セルロース等が挙げられる。これらのセルロースエステル樹脂は、単独で用いることも２種以上併用することもできる。本発明のセルロースエステル樹脂組成物からなるフィルムを光学フィルム、特に偏光板保護フィルムとして使用する場合には、セルロースアセテートを使用することが、機械的物性及び透明性に優れたフィルムを得ることができるため好ましい。 Specific examples of the cellulose ester resin include, for example, cellulose acetate such as triacetyl cellulose and diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate, and the like. No. These cellulose ester resins can be used alone or in combination of two or more. When a film comprising the cellulose ester resin composition of the present invention is used as an optical film, particularly as a polarizing plate protective film, the use of cellulose acetate can provide a film having excellent mechanical properties and transparency. Therefore, it is preferable.

　前記セルロースアセテートとしては、平均酢化度（結合酢酸量）が５０．０～６２．５質量％の範囲のものであると、得られるセルロースエステル樹脂組成物からなる光学フィルムは機械的物性及び透明性に優れたフィルムとなるため好ましい。 When the cellulose acetate has an average degree of acetylation (the amount of bound acetic acid) in the range of 50.0 to 62.5% by mass, the obtained optical film comprising the cellulose ester resin composition has mechanical properties and transparency. This is preferable because the film has excellent properties.

　また、光学フィルムの耐透湿性を向上させるためには、セルロースアセテートの平均酢化度が５４～６２．５質量％の範囲であることが好ましい。平均酢化度がより高いトリアセチルセルロースを用いることで、耐透湿性に優れるセルロースエステル樹脂フィルムを得ることが出来る。また、光学フィルムを高い位相差値に調整するためには、セルロースアセテートの平均酢化度が５０．０～５８質量％の範囲であることが好ましい。 In order to improve the moisture resistance of the optical film, the average acetylation degree of the cellulose acetate is preferably in the range of 54 to 62.5% by mass. By using triacetyl cellulose having a higher average acetylation degree, a cellulose ester resin film having excellent moisture permeability can be obtained. Further, in order to adjust the optical film to have a high retardation value, the average acetylation degree of cellulose acetate is preferably in the range of 50.0 to 58% by mass.

　なお、平均酢化度は、セルロースアセテートの質量を基準として、該セルロースアセテートをケン化することによって生成する酢酸の質量割合である。 The average degree of acetylation is a mass ratio of acetic acid produced by saponifying the cellulose acetate with reference to the mass of the cellulose acetate.

　前記セルロースエステル樹脂は、数平均分子量が７０，０００～３００，０００の範囲のものであると、フィルムの機械的物性を向上することができるため好ましい。また、より高い機械的物性が必要な場合は、８０，０００～２００，０００の範囲のものを用いるとより好ましい。 セ ル ロ ー ス The cellulose ester resin preferably has a number average molecular weight in the range of 70,000 to 300,000 because the mechanical properties of the film can be improved. When higher mechanical properties are required, it is more preferable to use those having a range of 80,000 to 200,000.

　本発明のセルロースエステル樹脂組成物中の金属化合物の含有量としては、セルロースエステル樹脂１００質量部に対して、１０～３０００ｐｐｍであることが好ましく、５０～２０００ｐｐｍであることがより好ましく、２００～１０００ｐｐｍであることがさらに好ましい。
　また、金属含有量としては、０．１～１０００ｐｐｍであることが好ましく、１～５００ｐｐｍであることがより好ましく、１０～１００ｐｐｍであることがさらに好ましい。ここでいう金属含有量は、セルロースエステル樹脂に元来含まれている金属含有量は含まない。 The content of the metal compound in the cellulose ester resin composition of the present invention is preferably 10 to 3000 ppm, more preferably 50 to 2000 ppm, and more preferably 200 to 1000 ppm based on 100 parts by mass of the cellulose ester resin. Is more preferable.
Further, the metal content is preferably from 0.1 to 1000 ppm, more preferably from 1 to 500 ppm, and still more preferably from 10 to 100 ppm. The metal content here does not include the metal content originally contained in the cellulose ester resin.

　本実施形態のセルロースエステル樹脂組成物中のポリエステル系添加剤の含有量は、セルロースエステル樹脂１００質量部に対して０．１～５０質量部であることが好ましく、１～３０質量部であることがより好ましく、３～２０質量部であることがさらに好ましい。 The content of the polyester-based additive in the cellulose ester resin composition of the present embodiment is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the cellulose ester resin. And more preferably 3 to 20 parts by mass.

　本実施形態のセルロースエステル樹脂組成物は、本発明の金属化合物およびポリエステル系添加剤とセルロースエステル樹脂等の光学材料用樹脂を含むものであり、必要に応じてその他の各種添加剤等を含有してなる樹脂組成物であってもよい。 The cellulose ester resin composition of the present embodiment contains the metal compound of the present invention and a polyester-based additive and a resin for an optical material such as a cellulose ester resin, and contains other various additives as necessary. It may be a resin composition consisting of:

　前記添加剤としては、例えば、本発明の金属化合物、ポリエステル系添加剤以外のその他の改質剤、熱可塑性樹脂、紫外線吸収剤、マット剤、安定剤、劣化防止剤（例えば、酸化防止剤、過酸化物分解剤、ラジカル禁止剤、金属不活性化剤、酸捕獲剤等）、染料などが挙げられる。 Examples of the additive include, for example, the metal compound of the present invention, other modifiers other than the polyester-based additive, a thermoplastic resin, an ultraviolet absorber, a matting agent, a stabilizer, and a deterioration inhibitor (for example, an antioxidant, Peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, etc.), dyes and the like.

　前記その他の改質剤としては、本発明で規定するポリエステル化合物、ジエステル化合物以外のエステル樹脂や、トリフェニルホスフェート（ＴＰＰ）、トリクレジルホスフェート、クレジルジフェニルホスフェート等のリン酸エステル、ジメチルフタレート、ジエチルフタレート、ジブチルフタレート、ジ－２－エチルヘキシルフタレート等のフタル酸エステル、エチルフタリルエチルグリコレート、ブチルフタリルブチルグリコレート、トリメチロールプロパントリベンゾエート、ペンタエリスリトールテトラアセテート、アセチルクエン酸トリブチル等を、本発明の効果を損なわない範囲で使用することができる。 Examples of the other modifiers include ester resins other than the polyester compound and the diester compound specified in the present invention, phosphate esters such as triphenyl phosphate (TPP), tricresyl phosphate, and cresyl diphenyl phosphate, dimethyl phthalate, Phthalates such as diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, trimethylolpropane tribenzoate, pentaerythritol tetraacetate, tributyl acetyl citrate and the like; It can be used within a range that does not impair the effects of the present invention.

　前記熱可塑性樹脂としては、特に限定しないが、例えば、本発明のエステル樹脂以外のポリエステル樹脂、ポリエステルエーテル樹脂、ポリウレタン樹脂、アクリル樹脂、エポキシ樹脂、トルエンスルホンアミド樹脂等が挙げられる。 The thermoplastic resin is not particularly limited, and examples thereof include polyester resins other than the ester resin of the present invention, polyester ether resins, polyurethane resins, acrylic resins, epoxy resins, and toluenesulfonamide resins.

　前記紫外線吸収剤としては、特に限定しないが、例えば、オキシベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチル酸エステル系化合物、ベンゾフェノン化合物、シアノアクリレート系化合物、ニッケル錯塩系化合物等が挙げられる。前記紫外線吸収剤は、前記セルロースエステル樹脂１００質量部に対して、０．０１～２質量部の範囲で用いることが好ましい。 The ultraviolet absorber is not particularly limited, and examples thereof include an oxybenzophenone-based compound, a benzotriazole-based compound, a salicylate-based compound, a benzophenone compound, a cyanoacrylate-based compound, and a nickel complex-based compound. The ultraviolet absorber is preferably used in an amount of 0.01 to 2 parts by mass based on 100 parts by mass of the cellulose ester resin.

　前記マット剤としては、例えば、酸化珪素、酸化チタン、酸化アルミニウム、炭酸カルシウム、珪酸カルシウム、珪酸アルミニウム、珪酸マグネシウム、リン酸カルシウム、カオリン、タルク等が挙げられる。前記マット剤は、前記セルロースエステル樹脂１００質量部に対して、０．１～０．３質量部の範囲で用いることが好ましい。 マ ッ ト Examples of the matting agent include silicon oxide, titanium oxide, aluminum oxide, calcium carbonate, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, kaolin, and talc. The matting agent is preferably used in an amount of 0.1 to 0.3 parts by mass based on 100 parts by mass of the cellulose ester resin.

　前記染料としては、本発明の目的を阻害しない範囲であれば、種類や配合量など特に限定しない。 染料 The type and amount of the dye are not particularly limited as long as the object of the present invention is not impaired.

〔セルロースエステル樹脂組成物の成形品〕
　本発明のセルロースエステル樹脂組成物を成形することにより、成形品が得られる。本発明のセルロースエステル樹脂組成物の成形品は、透明性に優れることから光学フィルムとして使用することができる。 (Molded article of cellulose ester resin composition)
A molded article is obtained by molding the cellulose ester resin composition of the present invention. The molded article of the cellulose ester resin composition of the present invention can be used as an optical film because of its excellent transparency.

［光学フィルム］
　本発明の光学フィルムは、本発明のセルロースエステル樹脂組成物を成形することにより得られるフィルムである。本発明の光学フィルムの膜厚は、使用される用途により異なるが、一般に１０～３００μｍの範囲が好ましい。
　本発明の光学フィルムは、光学異方性あるいは光学等方性等の特性を有していてもよいが、前記光学フィルムを偏光板用保護フィルムに使用する場合には、光の透過を阻害しない光学等方性のフィルムを使用することが好ましい。
　本発明の光学フィルムは、種々の用途で用いることができる。最も有効な用途としては、例えば、液晶ディスプレイの光学等方性を必要とする偏光板用保護フィルムがあるが、光学補償機能を必要とする偏光板用保護フィルムの支持体にも使用することができる。
　本発明の光学フィルムは、種々の表示モードの液晶セルに用いることができる。例えばＩＰＳ（Ｉｎ－Ｐｌａｎｅ Ｓｗｉｔｃｈｉｎｇ）、ＴＮ（Ｔｗｉｓｔｅｄ Ｎｅｍａｔｉｃ）、ＶＡ（Ｖｅｒｔｉｃａｌｌｙ Ａｌｉｇｎｅｄ）、ＯＣＢ（Ｏｐｔｉｃａｌｌｙ Ｃｏｍｐｅｎｓａｔｏｒｙ Ｂｅｎｄ）等が例示できる。
その他にも、紫外線や眩輝防止に用いられるサングラスやゴーグルにおける偏光膜を保護するためのフィルムとしても用いられる。 [Optical film]
The optical film of the present invention is a film obtained by molding the cellulose ester resin composition of the present invention. Although the thickness of the optical film of the present invention varies depending on the use, it is generally preferably in the range of 10 to 300 μm.
The optical film of the present invention may have properties such as optical anisotropy or optical isotropy, but when the optical film is used as a protective film for a polarizing plate, it does not inhibit light transmission. It is preferable to use an optically isotropic film.
The optical film of the present invention can be used for various applications. The most effective use is, for example, a protective film for a polarizing plate that requires optical isotropy of a liquid crystal display, but it can also be used as a support for a protective film for a polarizing plate that requires an optical compensation function. it can.
The optical film of the present invention can be used for liquid crystal cells of various display modes. For example, IPS (In-Plane Switching), TN (Twisted Nematic), VA (Vertically Aligned), OCB (Optically Compensatory Bend) and the like can be exemplified.
In addition, it is also used as a film for protecting a polarizing film in sunglasses and goggles used for preventing ultraviolet rays and glare.

［光学フィルムの製造方法］
　本発明の光学フィルムは、例えば、溶融押出法により製造することができる。具体的には、前記セルロースエステル樹脂、セルロースエステル樹脂用改質剤、及び必要に応じてその他の各種添加剤等を含有してなるセルロースエステル樹脂組成物を、例えば、押出機等で溶融混練し、Ｔダイ等を用いてフィルム状に成形することにより得ることができる。
　また、本発明の光学フィルムは、前記成形方法の他に、例えば、前記セルロースエステル樹脂と前記セルロースエステル樹脂用改質剤とを有機溶剤中溶解して得られた樹脂溶液を、金属支持体上に流延させ、次いで、前記有機溶剤を留去し乾燥させる、いわゆる溶液流延法（ソルベントキャスト法）で成形することによって得ることができる。
　前記溶液流延法によれば、表面に凹凸が形成されにくく、表面平滑性に優れるフィルムが得られる。その為、該溶液流延法により得られるフィルムは光学用途に好ましく用いることが出来、偏光板用保護フィルム、位相差フィルム、反射板、視野角向上フィルム、防眩フィルム、無反射フィルム、帯電防止フィルム、カラーフィルター等の液晶ディスプレイの部材や偏光サングラスなどの防眩用品における偏光膜保護フィルムとして好ましく使用できる。 [Production method of optical film]
The optical film of the present invention can be produced, for example, by a melt extrusion method. Specifically, the cellulose ester resin, the cellulose ester resin composition containing the cellulose ester resin modifier, and other various additives as necessary, for example, melt-kneaded in an extruder or the like. , A T-die or the like to form a film.
Further, the optical film of the present invention, in addition to the molding method, for example, a resin solution obtained by dissolving the cellulose ester resin and the cellulose ester resin modifier in an organic solvent, on a metal support Then, the organic solvent is distilled off and dried, and the mixture is molded by a so-called solution casting method (solvent casting method).
According to the solution casting method, a film having less unevenness on the surface and excellent surface smoothness can be obtained. Therefore, the film obtained by the solution casting method can be preferably used for optical applications, and includes a protective film for a polarizing plate, a retardation film, a reflecting plate, a viewing angle improving film, an antiglare film, a non-reflective film, and an antistatic film. It can be preferably used as a polarizing film protective film in a member of a liquid crystal display such as a film or a color filter or an antiglare product such as polarized sunglasses.

　以下に実施例を示して本発明を更に具体的に説明するが、これらの実施例により本発明の解釈が限定されるものではない。 The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

〔ポリエステル系添加剤の合成〕
［合成例１：ポリエステル系添加剤１］
　グリコール成分としてプロピレングリコール（以下「ＰＧ」と略す）１０７．６ｇ、ジカルボン酸成分として無水フタル酸（以下「ＰＡ」と略す）３６１．６ｇ、アルコール成分としてイソノニルアルコール（以下「ＩＮＡ」と略す）４１２．２ｇ及びエステル化触媒としてテトライソプロピルチタネート（ＴＩＰＴ）０．０６ｇを、温度計、攪拌器、還流冷却器を付した内容積２リットルの四ツ口フラスコに仕込み、窒素気流下で攪拌しながら２２０℃まで段階的に昇温し、その後２３０℃で反応を継続させ、合計１９時間脱水縮合反応させてポリエステル系添加剤１（酸価０．４、数平均分子量５６０）を得た。 (Synthesis of polyester additive)
[Synthesis Example 1: Polyester additive 1]
107.6 g of propylene glycol (hereinafter abbreviated as “PG”) as a glycol component, 361.6 g of phthalic anhydride (hereinafter abbreviated as “PA”) as a dicarboxylic acid component, and isononyl alcohol (hereinafter abbreviated as “INA”) as an alcohol component 412.2 g and 0.06 g of tetraisopropyl titanate (TIPT) as an esterification catalyst were charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and stirred under a nitrogen stream. The temperature was raised stepwise to 220 ° C., and the reaction was continued at 230 ° C., followed by a dehydration condensation reaction for a total of 19 hours to obtain a polyester-based additive 1 (acid value 0.4, number average molecular weight 560).

［合成例２：ポリエステル系添加剤２］
　グリコール成分としてＰＧ４０５ｇ、ジカルボン酸としてアジピン酸（ＡＡ）７９ｇ、ＰＡ２４０ｇ、モノカルボン酸として安息香酸（ＢｚＡ）５８６ｇ及びエステル化触媒としてＴＩＰＴ０．０８ｇを、温度計、攪拌器、還流冷却器を付した内容積２リットルの四ツ口フラスコに仕込み、窒素気流下で攪拌しながら２３０℃まで段階的に昇温し、その後２３０℃で反応を継続させ、合計１９時間脱水縮合反応させてポリエステル系添加剤２（酸価０．２、数平均分子量４１０）を得た。 [Synthesis Example 2: Polyester additive 2]
Contents including 405 g of PG as a glycol component, 79 g of adipic acid (AA) and 240 g of PA as a dicarboxylic acid, 586 g of benzoic acid (BzA) as a monocarboxylic acid, and 0.08 g of TIPT as an esterification catalyst, with a thermometer, a stirrer, and a reflux condenser. The mixture was charged into a two-liter four-necked flask, and the temperature was increased stepwise to 230 ° C. while stirring under a nitrogen stream. Thereafter, the reaction was continued at 230 ° C., and the polyester additive 2 was subjected to a dehydration condensation reaction for a total of 19 hours. (Acid value 0.2, number average molecular weight 410) was obtained.

［合成例３：ポリエステル系添加剤３］
　グリコール成分としてＰＧ４０１ｇ、ジカルボン酸としてＡＡ３２７ｇ、モノカルボン酸としてＢｚＡ５４５ｇ及びエステル化触媒としてＴＩＰＴ０．０８ｇを、温度計、攪拌器、還流冷却器を付した内容積２リットルの四ツ口フラスコに仕込み、窒素気流下で攪拌しながら２３０℃まで段階的に昇温し、その後２３０℃で反応を継続させ、合計１９時間脱水縮合反応させてポリエステル系添加剤３（酸価０．４、数平均分子量４００）を得た。 [Synthesis Example 3: Polyester additive 3]
401 g of PG as a glycol component, 327 g of AA as a dicarboxylic acid, 545 g of BzA as a monocarboxylic acid, and 0.08 g of TIPT as an esterification catalyst were charged into a two-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. The temperature was increased stepwise to 230 ° C. while stirring under a stream of air, and then the reaction was continued at 230 ° C., followed by a total of 19 hours of dehydration-condensation reaction to obtain a polyester additive 3 (acid value 0.4, number average molecular weight 400). I got

［合成例４：ポリエステル系添加剤４］
　グリコール成分としてエチレングリコール（以下ＥＧと略す）４４８ｇ、ジカルボン酸としてＡＡ８１２ｇ、及びエステル化触媒としてＴＩＰＴ０．０４ｇを、温度計、攪拌器、還流冷却器を付した内容積２リットルの四ツ口フラスコに仕込み、窒素気流下で攪拌しながら２２５℃まで段階的に昇温し、その後２２５℃で反応を継続させ、合計１９時間脱水縮合反応させてポリエステル系添加剤４（酸価０．２、数平均分子量１３５０）を得た。 [Synthesis Example 4: Polyester additive 4]
448 g of ethylene glycol (hereinafter abbreviated as EG) as a glycol component, 812 g of AA as a dicarboxylic acid, and 0.04 g of TIPT as an esterification catalyst were placed in a two-liter four-neck flask equipped with a thermometer, a stirrer, and a reflux condenser. The temperature was gradually increased to 225 ° C. while stirring under a nitrogen stream, and then the reaction was continued at 225 ° C., and a total of 19 hours of dehydration-condensation reaction was carried out to obtain polyester additive 4 (acid value 0.2, number average Molecular weight 1350).

［合成例５：ポリエステル５］
　グリコール成分としてＰＧ３８３ｇ、ジカルボン酸としてＡＡ３８１ｇ、ＰＡ１２９ｇ、及びエステル化触媒としてＴＩＰＴ０．０５ｇを、温度計、攪拌器、還流冷却器を付した内容積２リットルの四ツ口フラスコに仕込み、窒素気流下で攪拌しながら２１０℃まで段階的に昇温し、その後２１０℃で反応を継続させ、合計１９時間脱水縮合反応させてポリエステル５（酸価０．４、数平均分子量７６０）を得た。 [Synthesis Example 5: Polyester 5]
PG 383 g as a glycol component, AA 381 g as a dicarboxylic acid, PA 129 g, and TIPT 0.05 g as an esterification catalyst were charged into a two-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. The temperature was raised stepwise to 210 ° C. with stirring, and then the reaction was continued at 210 ° C., and a total of 19 hours of dehydration condensation reaction was performed to obtain polyester 5 (acid value 0.4, number average molecular weight 760).

［合成例６：エステル化合物１］
グリコール成分としてＰＧ６４８ｇ、ジプロピレングリコール１０９ｇ、モノカルボン酸成分として安息香酸１９８０ｇ、及び、テトライソプロピルチタネート０．２ｇを温度計、攪拌器、還流冷却器を付した内容積３リットルの四ツ口フラスコに仕込み、２４０℃まで８時間かけて昇温した。その後、２４０℃で１０時間反応させた。反応後、１９０℃にて未反応原料を減圧除去し、常温液体のジエステルであるエステル化合物１（酸価０．１、数平均分子量２９０）を得た。 [Synthesis Example 6: Ester compound 1]
648 g of PG as a glycol component, 109 g of dipropylene glycol, 1980 g of benzoic acid as a monocarboxylic acid component, and 0.2 g of tetraisopropyl titanate were placed in a three-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. It was charged and heated to 240 ° C. over 8 hours. Thereafter, the reaction was performed at 240 ° C. for 10 hours. After the reaction, unreacted raw materials were removed at 190 ° C. under reduced pressure to obtain an ester compound 1 (acid value: 0.1, number average molecular weight: 290), which is a diester at room temperature.

［ポリエステル系添加剤５］
　上記ポリエステル５とエステル化合物１を重量比で７／３となるように配合したものを、ポリエステル系添加剤５とした。 [Polyester additive 5]
A mixture of the polyester 5 and the ester compound 1 in a weight ratio of 7/3 was used as a polyester additive 5.

〔光学フィルムの調製〕
　上記ポリエステル系添加剤１～５と、以下に記載の市販のセルロースエステル樹脂及び金属化合物とを用いて、光学フィルムを調製した。
［セルロースエステル樹脂］
　トリアセチルセルロース（酢化度６０．７％）
　ジアセチルセルロース（酢化度５５．５％）
［金属化合物］
　水酸化カルシウム（和光純薬(株)製）
　リチウムステアレート（Li-St、日東化成工業(株)製）
　ナトリウムステアレート（Na-St、日東化成工業(株)製）
　アルミニウムステアレート（Al-St、日東化成工業(株)製）
　カルシウムステアレート（Ca-St、日東化成工業(株)製）
　ジンクステアレート（Zn-St、日東化成工業(株)製）
　バリウムステアレート（Ba-St、日東化成工業(株)製）
　２－エチルヘキサン酸カルシウム（DIC－OCTOATE、DIC(株)製）
　２－エチルヘキサン酸/ネオデカン酸カルシウム（DICNATE、DIC(株)製）
　ラウリン酸カルシウム（CS-3、日東化成工業(株)製）
　モンタン酸カルシウム（CS-8CP、日東化成工業(株)製）
　１２－ヒドロキシステアリン酸カルシウム（CS-6、日東化成工業(株)製） (Preparation of optical film)
Optical films were prepared using the polyester additives 1 to 5 and commercially available cellulose ester resins and metal compounds described below.
[Cellulose ester resin]
Triacetyl cellulose (degree of acetylation: 60.7%)
Diacetyl cellulose (55.5% acetylation)
[Metal compound]
Calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.)
Lithium stearate (Li-St, manufactured by Nitto Kasei Kogyo Co., Ltd.)
Sodium stearate (Na-St, manufactured by Nitto Kasei Kogyo Co., Ltd.)
Aluminum stearate (Al-St, manufactured by Nitto Kasei Kogyo Co., Ltd.)
Calcium stearate (Ca-St, manufactured by Nitto Kasei Kogyo Co., Ltd.)
Zinc stearate (Zn-St, manufactured by Nitto Chemical Industry Co., Ltd.)
Barium stearate (Ba-St, manufactured by Nitto Kasei Kogyo Co., Ltd.)
Calcium 2-ethylhexanoate (DIC-OCTOATE, manufactured by DIC Corporation)
2-ethylhexanoic acid / calcium neodecanoate (DICNATE, manufactured by DIC Corporation)
Calcium laurate (CS-3, manufactured by Nitto Kasei Kogyo Co., Ltd.)
Calcium montanate (CS-8CP, manufactured by Nitto Kasei Kogyo Co., Ltd.)
Calcium 12-hydroxystearate (CS-6, manufactured by Nitto Kasei Kogyo Co., Ltd.)

［実施例１～１８、２０］
　トリアセチルセルロース（ＴＡＣ）樹脂１００部、ポリエステル系添加剤１０部、金属化合物２０～１０００ｐｐｍを、メチレンクロライド８１０部及びメタノール９０部からなる混合溶剤に加えて溶解し、ドープ液を調製した。このドープ液をガラス板上に厚さ０．８ｍｍとなるように流延し、室温で１６時間乾燥させた後、５０℃で３０分、さらに１２０℃で３０分乾燥させることで、セルロースエステルフィルムを得た。得られたフィルムの保存安定性に関する下記の項目について評価した。結果を表１に示す。 [Examples 1 to 18, 20]
A dope solution was prepared by adding and dissolving 100 parts of triacetyl cellulose (TAC) resin, 10 parts of a polyester-based additive, and 20 to 1000 ppm of a metal compound to a mixed solvent consisting of 810 parts of methylene chloride and 90 parts of methanol. The dope solution was cast on a glass plate to a thickness of 0.8 mm, dried at room temperature for 16 hours, and then dried at 50 ° C. for 30 minutes and further at 120 ° C. for 30 minutes to obtain a cellulose ester film. I got The following items regarding the storage stability of the obtained film were evaluated. Table 1 shows the results.

［実施例１９］
トリアセチルセルロース樹脂の代わりに、ジアセチルセルロース（ＤＡＣ）樹脂を使用した以外は、実施例１６と同様にしてセルロースエステルフィルムを得た。得られたフィルムの保存安定性に関する下記の項目について評価した。結果を表１に示す。 [Example 19]
A cellulose ester film was obtained in the same manner as in Example 16 except that diacetyl cellulose (DAC) resin was used instead of triacetyl cellulose resin. The following items regarding the storage stability of the obtained film were evaluated. Table 1 shows the results.

［比較例１］
　トリアセチルセルロース（ＴＡＣ）樹脂１００部を、メチレンクロライド８１０部及びメタノール９０部からなる混合溶剤に加えて溶解し、ドープ液を調製した。このドープ液をガラス板上に厚さ０．８ｍｍとなるように流延し、室温で１６時間乾燥させた後、５０℃で３０分、さらに１２０℃で３０分乾燥させることで、セルロースエステルフィルムを得た。得られたフィルムの保存安定性に関する下記の項目について評価した。結果を表１に示す。 [Comparative Example 1]
100 parts of triacetyl cellulose (TAC) resin was added to and dissolved in a mixed solvent consisting of 810 parts of methylene chloride and 90 parts of methanol to prepare a dope solution. The dope solution was cast on a glass plate to a thickness of 0.8 mm, dried at room temperature for 16 hours, and then dried at 50 ° C. for 30 minutes and further at 120 ° C. for 30 minutes to obtain a cellulose ester film. I got The following items regarding the storage stability of the obtained film were evaluated. Table 1 shows the results.

［比較例２～４］
　トリアセチルセルロース（ＴＡＣ）樹脂１００部、ポリエステル系添加剤またはトリフェニルホスフェート（ＴＰＰ）１０部を、メチレンクロライド８１０部及びメタノール９０部からなる混合溶剤に加えて溶解し、ドープ液を調製した。このドープ液をガラス板上に厚さ０．８ｍｍとなるように流延し、室温で１６時間乾燥させた後、５０℃で３０分、さらに１２０℃で３０分乾燥させることで、セルロースエステルフィルムを得た。得られたフィルムの保存安定性に関する下記の項目について評価した。結果を表１に示す。 [Comparative Examples 2 to 4]
A dope solution was prepared by adding 100 parts of triacetyl cellulose (TAC) resin, 10 parts of a polyester-based additive or triphenyl phosphate (TPP) to a mixed solvent consisting of 810 parts of methylene chloride and 90 parts of methanol and dissolving the same. The dope solution was cast on a glass plate to a thickness of 0.8 mm, dried at room temperature for 16 hours, and then dried at 50 ° C. for 30 minutes and further at 120 ° C. for 30 minutes to obtain a cellulose ester film. I got The following items regarding the storage stability of the obtained film were evaluated. Table 1 shows the results.

［比較例５］
　トリアセチルセルロース（ＴＡＣ）樹脂１００部、ＴＰＰ１０部、金属化合物５００ｐｐｍを、メチレンクロライド８１０部及びメタノール９０部からなる混合溶剤に加えて溶解し、ドープ液を調製した。このドープ液をガラス板上に厚さ０．８ｍｍとなるように流延し、室温で１６時間乾燥させた後、５０℃で３０分、さらに１２０℃で３０分乾燥させることで、セルロースエステルフィルムを得た。得られたフィルムの保存安定性に関する下記の項目について評価した。結果を表１に示す。 [Comparative Example 5]
100 parts of triacetyl cellulose (TAC) resin, 10 parts of TPP, and 500 ppm of a metal compound were added to a mixed solvent consisting of 810 parts of methylene chloride and 90 parts of methanol and dissolved to prepare a dope solution. The dope solution was cast on a glass plate to a thickness of 0.8 mm, dried at room temperature for 16 hours, and then dried at 50 ° C. for 30 minutes and further at 120 ° C. for 30 minutes to obtain a cellulose ester film. I got The following items regarding the storage stability of the obtained film were evaluated. Table 1 shows the results.

〔保存安定性の評価〕
［酢酸発生量］
　得られたフィルム１．２ｇを、２５ｍｌのサンプル瓶に入れ、８５℃×湿度９０％の条件下に３３６時間存在させたときに発生する酢酸量を検知管（北川式ガス検知管　酢酸用）で調べた。
　酢酸発生量が２５ｐｐｍ以下を◎、５０ｐｐｍ以下を○、それより多いものを×とした。
［透明性］
　フィルムの透明性はＨＡＺＥ値を測定することにより判断した。ＨＡＺＥ値は濁度計（日本電色工業株式会社製「ＮＤＨ　５０００」）を用いて、ＪＩＳ　Ｋ　７１０５に準じて測定した。得られる値が０％に近い程、透明であること表す。 [Evaluation of storage stability]
[Amount of acetic acid generated]
1.2 g of the obtained film was placed in a 25 ml sample bottle, and the amount of acetic acid generated when the film was allowed to exist for 336 hours under the condition of 85 ° C. × 90% humidity was measured with a detector tube (Kitakawa gas detector tube for acetic acid). Examined.
◎: 25 ppm or less of acetic acid generation, 酢 酸: 50 ppm or less, and x: more than 50 ppm.
[transparency]
The transparency of the film was determined by measuring the HAZE value. The HAZE value was measured using a turbidimeter (“NDH 5000” manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K 7105. The closer the value obtained is to 0%, the more transparent it is.

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

　表１に示す通り、金属化合物とポリエステル系添加剤とを組み合わせて用いた場合に、酢酸の発生量が少なく、優れた耐加水分解性を示した。ポリエステル系添加剤のみや、ＴＰＰと金属化合物との組み合わせでは、安定化効果は確認できなかった。 通 り As shown in Table 1, when the metal compound and the polyester-based additive were used in combination, the amount of acetic acid generated was small and excellent hydrolysis resistance was exhibited. No stabilizing effect could be confirmed with only the polyester-based additive or the combination of TPP and the metal compound.

Claims (12)

　脂肪酸金属塩、金属水酸化物及び炭酸金属塩から選択される一種以上の金属化合物を含む、セルロースエステル樹脂用添加剤。 (4) An additive for a cellulose ester resin, comprising one or more metal compounds selected from fatty acid metal salts, metal hydroxides and metal carbonates. 　金属化合物が、炭素原子数２～３０の脂肪酸の金属塩である、請求項１に記載のセルロースエステル樹脂用添加剤。 添加 The additive for cellulose ester resin according to claim 1, wherein the metal compound is a metal salt of a fatty acid having 2 to 30 carbon atoms. 　金属化合物の金属が、リチウム、ナトリウム、アルミニウム、カルシウム、亜鉛及びバリウムからなる群から選択される、請求項１又は２に記載のセルロースエステル樹脂用添加剤。 The additive for a cellulose ester resin according to claim 1 or 2, wherein the metal of the metal compound is selected from the group consisting of lithium, sodium, aluminum, calcium, zinc, and barium. 　金属化合物の金属が、カルシウム又はバリウムである、請求項１から３のいずれか一項に記載のセルロースエステル樹脂用添加剤。 (4) The additive for cellulose ester resin according to any one of (1) to (3), wherein the metal of the metal compound is calcium or barium. 　１０～３０００ｐｐｍの含有量でセルロースエステル樹脂に添加するための、請求項１から４のいずれか一項に記載のセルロースエステル樹脂用添加剤。 The additive for a cellulose ester resin according to any one of claims 1 to 4, which is added to the cellulose ester resin at a content of 10 to 3000 ppm. 　多塩基酸と多価アルコールとを必須原料とするポリエステルを含むポリエステル系添加剤と併用して用いられる、請求項１から５のいずれか一項に記載のセルロースエステル樹脂用添加剤。 The additive for a cellulose ester resin according to any one of claims 1 to 5, which is used in combination with a polyester-based additive containing a polyester containing a polybasic acid and a polyhydric alcohol as essential raw materials. 　ポリエステルの末端がモノカルボン酸の残基又はモノアルコールの残基で封止されている、請求項６に記載のセルロースエステル樹脂用添加剤。 The additive for cellulose ester resin according to claim 6, wherein the terminal of the polyester is sealed with a residue of a monocarboxylic acid or a residue of a monoalcohol. 　ポリエステル系添加剤が、多塩基酸とモノアルコールもしくは多価アルコールとモノカルボン酸を必須原料とするエステル化合物をさらに含む、請求項６又は７に記載のセルロースエステル樹脂用添加剤。 The additive for a cellulose ester resin according to claim 6 or 7, wherein the polyester-based additive further comprises an ester compound containing polybasic acid and monoalcohol or polyhydric alcohol and monocarboxylic acid as essential raw materials. 　エステル化合物がジエステルである、請求項８に記載のセルロースエステル樹脂用添加剤。 The additive for cellulose ester resin according to claim 8, wherein the ester compound is a diester. 　請求項６から９のいずれか一項に記載のセルロースエステル樹脂用添加剤及びセルロースエステル樹脂を含む、セルロースエステル樹脂組成物。 A cellulose ester resin composition comprising the cellulose ester resin additive according to any one of claims 6 to 9 and a cellulose ester resin. 　請求項１０に記載のセルロースエステル樹脂組成物の成形品。 A molded article of the cellulose ester resin composition according to claim 10. 　光学フィルムである、請求項１１に記載の成形品。 The molded article according to claim 11, which is an optical film.
PCT/JP2019/031356 2018-09-03 2019-08-08 Additive for cellulose ester resin, and cellulose ester composition Ceased WO2020049947A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201980057461.3A CN112673062A (en) 2018-09-03 2019-08-08 Additive for cellulose ester resin and cellulose ester composition
JP2020541082A JP6897880B2 (en) 2018-09-03 2019-08-08 Additive for Cellulose Ester Resin and Cellulose Ester Composition
KR1020217004000A KR102454821B1 (en) 2018-09-03 2019-08-08 Additives for Cellulose Ester Resins and Cellulose Ester Compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-164333 2018-09-03
JP2018164333 2018-09-03

Publications (1)

Publication Number Publication Date
WO2020049947A1 true WO2020049947A1 (en) 2020-03-12

Family

ID=69722481

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/031356 Ceased WO2020049947A1 (en) 2018-09-03 2019-08-08 Additive for cellulose ester resin, and cellulose ester composition

Country Status (5)

Country Link
JP (1) JP6897880B2 (en)
KR (1) KR102454821B1 (en)
CN (1) CN112673062A (en)
TW (1) TWI807088B (en)
WO (1) WO2020049947A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112646298A (en) * 2020-11-24 2021-04-13 常州绿之源高分子材料有限公司 Environment-friendly PVA washing bag with sterilization function
CN112679893A (en) * 2020-11-24 2021-04-20 常州绿之源高分子材料有限公司 High-strength normal-temperature insoluble PVA shopping bag

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114835883B (en) * 2022-04-01 2023-04-04 佛山市国化新材料科技有限公司 Carboxylic acid micro-nano cellulose-based alkyd resin and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005162874A (en) * 2003-12-02 2005-06-23 Sony Corp RESIN COMPOSITION, MOLDED ARTICLE, ELECTRIC PRODUCT, METHOD FOR PRODUCING RESIN COMPOSITION
JP2013199084A (en) * 2012-03-26 2013-10-03 Konica Minolta Inc Method of manufacturing optical film and optical film, polarizer, and liquid crystal display device
JP2013538931A (en) * 2010-10-06 2013-10-17 インヴィスタ テクノロジーズ エスアエルエル Polymer composition comprising cellulose ester
JP2016155948A (en) * 2015-02-25 2016-09-01 Dic株式会社 Modifier for cellulose ester resin, cellulose ester resin composition, optical film and liquid crystal display device
WO2018030455A1 (en) * 2016-08-12 2018-02-15 株式会社Ｔｂｍ Resin composition

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2710845A (en) * 1952-06-26 1955-06-14 Hercules Powder Co Ltd Cellulose esters stabilized with a resinous polymeric epoxide and a metal salt
GB1063637A (en) * 1962-03-29 1967-03-30 Eastman Kodak Co Stabilised cellulose ester compositions
EP2392613B1 (en) 2009-01-29 2015-04-29 Adeka Corporation Cellulosic resin composition and cellulosic resin film
JP2011052205A (en) 2009-08-05 2011-03-17 Konica Minolta Opto Inc Optical film and polarizing plate using the same
JP2013100401A (en) * 2011-11-08 2013-05-23 Konica Minolta Advanced Layers Inc Anti-fogging thin film
KR102263372B1 (en) * 2013-01-25 2021-06-11 디아이씨 가부시끼가이샤 Polyester-based modifier composition for cellulose ester resin, cellulose ester optical film, and protective film for polarizing plate
US10280290B2 (en) * 2014-12-03 2019-05-07 Dic Corporation Cellulos ester resin modifier, cellulos ester resin composition, optical film, method for producing polarizing-plate protective film, and liquid crystal display device
US10208161B2 (en) * 2015-03-31 2019-02-19 Adeka Corporation Resin modifier and resin composition using same
JP2017071728A (en) * 2015-10-09 2017-04-13 三井化学株式会社 Polyester resin composition, method for manufacturing reflector and method for manufacturing light-emitting diode (led) element
WO2017208895A1 (en) * 2016-06-02 2017-12-07 大八化学工業株式会社 Modifying agent for cellulose ester resin, cellulose ester resin composition, and optical film
JP6880597B2 (en) * 2016-08-10 2021-06-02 三菱ケミカル株式会社 A resin composition, a film formed by molding the resin composition, and a bag formed by molding the film.
CN108948214B (en) * 2018-08-31 2021-01-08 四川普什醋酸纤维素有限责任公司 New application of metal salt and method for improving stability of cellulose acetate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005162874A (en) * 2003-12-02 2005-06-23 Sony Corp RESIN COMPOSITION, MOLDED ARTICLE, ELECTRIC PRODUCT, METHOD FOR PRODUCING RESIN COMPOSITION
JP2013538931A (en) * 2010-10-06 2013-10-17 インヴィスタ テクノロジーズ エスアエルエル Polymer composition comprising cellulose ester
JP2013199084A (en) * 2012-03-26 2013-10-03 Konica Minolta Inc Method of manufacturing optical film and optical film, polarizer, and liquid crystal display device
JP2016155948A (en) * 2015-02-25 2016-09-01 Dic株式会社 Modifier for cellulose ester resin, cellulose ester resin composition, optical film and liquid crystal display device
WO2018030455A1 (en) * 2016-08-12 2018-02-15 株式会社Ｔｂｍ Resin composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112646298A (en) * 2020-11-24 2021-04-13 常州绿之源高分子材料有限公司 Environment-friendly PVA washing bag with sterilization function
CN112679893A (en) * 2020-11-24 2021-04-20 常州绿之源高分子材料有限公司 High-strength normal-temperature insoluble PVA shopping bag

Also Published As

Publication number Publication date
JPWO2020049947A1 (en) 2021-02-15
TW202024204A (en) 2020-07-01
CN112673062A (en) 2021-04-16
TWI807088B (en) 2023-07-01
KR20210030430A (en) 2021-03-17
KR102454821B1 (en) 2022-10-17
JP6897880B2 (en) 2021-07-07

Similar Documents

Publication Publication Date Title
KR101569126B1 (en) Additive for cellulose ester resin, cellulose ester resin composition using same and optical film
JP6536149B2 (en) Modifier for Cellulose Ester Resin, Cellulose Ester Resin Composition, Optical Film, and Liquid Crystal Display Device
WO2020049947A1 (en) Additive for cellulose ester resin, and cellulose ester composition
JP6614469B2 (en) Ester resin, antiplasticizer, cellulose ester resin composition, optical film and liquid crystal display device
JP6631753B2 (en) Ester resin, anti-plasticizer, cellulose ester resin composition, optical film and liquid crystal display
US10280290B2 (en) Cellulos ester resin modifier, cellulos ester resin composition, optical film, method for producing polarizing-plate protective film, and liquid crystal display device
JP6874912B2 (en) Ester resin, anti-plasticizer, cellulose ester resin composition, optical film and liquid crystal display device
JP6582440B2 (en) Cellulose ester resin modifier, cellulose ester resin composition, optical film and liquid crystal display device
JP6836724B2 (en) Modified agent for cellulose ester resin, cellulose ester resin composition, optical film and liquid crystal display device
JP6849153B2 (en) Ester resin, anti-plasticizer, cellulose ester resin composition, optical film and liquid crystal display device
JP6628013B2 (en) Ester resin, plasticizer, cellulose ester resin composition, optical film and liquid crystal display
JP7697276B2 (en) Modifier for cellulose ester resin, cellulose ester resin composition, optical film and display device
JP2017095631A (en) Cellulose ester resin modifier, cellulose ester resin composition, optical film and liquid crystal display device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19858357

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2020541082

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20217004000

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19858357

Country of ref document: EP

Kind code of ref document: A1