Classifications

• • 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
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B3/00—Preparation of cellulose esters of organic acids
  • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/08—Cellulose derivatives
  • C08L1/10—Esters of organic acids, i.e. acylates
  • C08L1/12—Cellulose acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B3/00—Preparation of cellulose esters of organic acids
  • C08B3/22—Post-esterification treatments, including purification
  • C08B3/24—Hydrolysis or ripening
• • 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
  • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • 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
  • C08J2301/12—Cellulose acetate
• • 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
  • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2467/06—Unsaturated polyesters
• • 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
  • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
  • C08K2003/222—Magnesia, i.e. magnesium oxide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/06—Biodegradable

Definitions

• the present invention relates to cellulose acetate and cellulose acetate compositions.
• Cellulose acetate is a typical biodegradable resin.
• Cellulose acetate is excellent in that it can be obtained from natural materials such as wood and cotton, which does not compete with food and feed.
• Non-Patent Document 1 the viable cell count in the PM medium under the freshwater condition of 0.5% (0.08M) NaCl and the seawater condition of 3% (0.5M) NaCl, and the identified bacterial fauna of the isolated bacteria were investigated. There is. Then, as a result, the viable cell count in the case of fresh water conditions, a 2.6 ⁇ 10 7 Cells / ml, was 9.7 ⁇ 10 5 Cells / ml for seawater conditions, 3.7% of the fresh water conditions It is stated that the viable cell count was shown.
• Patent Document 1 states, "A polymer composition containing at least one basic additive having a pH of 13 or less and 7 or more when measured in a 1 wt% aqueous solution at 20 ° C. Was found to exhibit improved biodegradability over compositions without at least one additive. ”, And cellulose acetate is disclosed as a polymer.
• Patent Document 2 has the following description.
• a cellulose acetate optical film that exhibits optical performance when stretched cellulose acetate is obtained to obtain excellent stretchability and excellent optical performance after stretching.
• Cellulose diacetate having a total acetyl group substitution degree of 2.27 to 2.56, a dispersion degree Mw / Mn of more than 3.0 and 7.5 or less, and a 6-position substitution degree of 0.65 to 0.85.
• a cellulose diacetate for a retardation film which comprises a vinegarization degree distribution half-value range of 1.0 to 2.3 and a viscosity average degree of polymerization of 182 or more and 213 or less.
• the cellulose diacetate for a retardation film of the present invention preferably has a 6% viscosity of 120 to 230 mPa ⁇ s, and preferably has a weight average molecular weight Mw of 205,000 or more and 235,000 or less.
• Non-Patent Document 1 this is an environment in which seawater contains less fungi (fungi) and bacteria (bacteria) than soil and freshwater river water, and biodegradation is difficult. It depends. That is, the abundance ratio of bacteria, fungi, etc. that contribute to biodegradation is small, and as a result, it is difficult to biodegrade in seawater.
• An object of the present invention is to provide cellulose acetate having excellent biodegradability in seawater.
• the first of the present disclosure is that the total degree of acetyl substitution is 2.7 or less, and the ratio ⁇ of the total degree of acetyl substitution to the sum of the degree of acetyl substitution at the 2-position and the degree of acetyl substitution at the 3-position is
• the present invention relates to cellulose acetate, which is 2.0 or more and has a sulfuric acid component amount of more than 20 ppm and 400 ppm or less.
• the amount of the sulfuric acid component is preferably 80 ppm or more and 380 ppm or less.
• the amount of the sulfuric acid component is preferably 150 ppm or more and 350 pm or less.
• the ratio ⁇ of the total degree of acetyl substitution to the sum of the degree of acetyl substitution at the 2-position and the degree of acetyl substitution at the 3-position is preferably 2.5 or less.
• the second of the present disclosure contains cellulose acetate and an additive, and the cellulose acetate has a total acetyl substitution degree of 2.7 or less, and the acetyl substitution at the 2-position with respect to the acetyl substitution degree at the 6th position in the total acetyl substitution degree.
• the ratio ⁇ of the sum of the degree and the degree of acetyl substitution at the 3-position is 2.0 or more
• the additive is a substance having a pH of 8 or more in a 1% by weight aqueous solution at 20 ° C. and 2% by weight in water at 20 ° C.
• the present invention relates to a cellulose acetate composition, which is one or more selected from the group consisting of substances that dissolve and substances that are excellent in biodegradability in the ocean.
• the amount of sulfuric acid component of the cellulose acetate is preferably more than 20 ppm and 400 ppm or less.
• the content of the additive is preferably 5 to 40% by weight.
• the substance having a pH of 8 or more in the 1 wt% aqueous solution at 20 ° C. is preferably magnesium oxide.
• the substance that dissolves in water at 20 ° C. in an amount of 2% by weight or more is preferably triacetin.
• the pH of the slurry obtained by mixing with water at 20 ° C. is preferably 7 to 13.
• the cellulose acetate of the present disclosure has a total acetyl substitution degree of 2.7 or less, and the ratio ⁇ of the sum of the 2-position acetyl substitution degree and the 3-position acetyl substitution degree to the 6-position acetyl substitution degree in the acetyl total substitution degree is ⁇ . It is 2.0 or more, and the amount of the sulfuric acid component is more than 20 ppm and more than 400 ppm.
• Cellulose acetate has a total acetyl substitution degree of 2.7 or less, preferably 2.6 or less, more preferably 2.5 or less, and even more preferably 2.2 or less.
• the total degree of acetyl substitution may be 0.1 or more, preferably 1.8 or more.
• Cellulose acetate is inferior in biodegradability in seawater if the total degree of acetyl substitution is too large, and inferior in moldability if it is too small.
• the total acetyl substitution degree is the sum of the acetyl substitution degrees at the 2, 3 and 6 positions of the glucose ring of cellulose acetate measured below.
• the degree of acetyl substitution at the 2, 3 and 6 positions of the glucose ring of cellulose acetate can be measured by the NMR method according to the method of Tezuka (Tezuka, Carbonydr. Res. 273, 83 (1995)). That is, the free hydroxyl group of the cellulose acetate sample is propionylylated in pyridine with propionic anhydride. The obtained sample is dissolved in deuterated chloroform and the 13 C-NMR spectrum is measured.
• the carbon signal of the acetyl group appears in the region of 169 ppm to 171 ppm in the order of 2, 3, and 6 from the high magnetic field, and the signal of the carbonyl carbon of the propionyl group appears in the region of 172 ppm to 174 ppm in the same order.
• the degree of acetyl substitution at the 2, 3 and 6 positions of the glucose ring in the original cellulose acetate can be obtained. ..
• the degree of acetyl substitution can be analyzed by 1 H-NMR as well as 13 C-NMR.
• the ratio ⁇ of the sum of the acetyl substitution degree at the 2-position and the acetyl substitution degree at the 3-position to the acetyl substitution degree at the 6th position is 2.0 or more, and the value of ⁇ is 2.1 or more. It may be 2.2 or more, and it may be 2.3 or more. There is no particular upper limit, but it may be 2.5 or less. Cellulose acetate is inferior in biodegradability in seawater when the value of ⁇ is less than 2.0.
• the cellulose acetate of the present disclosure has a sulfuric acid component content of more than 20 ppm and not more than 400 ppm.
• the amount of the sulfuric acid component is preferably 50 ppm or more and 380 ppm or less, more preferably 80 ppm or more and 380 ppm or less, further preferably 100 ppm or more and 350 ppm or less, and particularly preferably 150 ppm or more and 350 ppm or less.
• the amount of sulfuric acid component is in this range, cellulose acetate has better biodegradability in seawater. The larger the amount of sulfuric acid component, the higher the biodegradability in seawater. Further, if the amount of sulfuric acid component is too large, it becomes difficult to produce cellulose acetate.
• Sulfuric acid component amount is SO4 2-equivalent amount of sulfur dioxide was sublimed from dried cellulose acetate.
• the cellulose acetate composition of the present disclosure may contain an optional component in addition to the cellulose acetate.
• Optional components of the cellulose acetate composition include additives, substances with high safety in the marine environment, and the like.
• the additive is selected from the group consisting of, for example, a substance having a pH of 8 or more in a 1 wt% aqueous solution at 20 ° C, a substance dissolving in 2 wt% or more in water at 20 ° C, and a substance having excellent biodegradability in the ocean. Included are one or more additives that are made.
• the composition containing the cellulose acetate of the present disclosure the following cellulose acetate composition is preferable.
• the cellulose acetate has a total acetyl substitution degree of 2.7 or less, and has a 2-position acetyl substitution degree and a 3-position acetyl substitution degree with respect to the 6-position acetyl substitution degree in the acetyl total substitution degree.
• the sum ratio ⁇ of degrees is 2.0 or more;
• the additive is a substance having a pH of 8 or more in a 1 wt% aqueous solution at 20 ° C, and a substance that dissolves 2 wt% or more in water at 20 ° C, in the ocean. 1 or more selected from the group consisting of substances having excellent biodegradability.
• a substance having a pH of 8 or more in a 1 wt% aqueous solution at 20 ° C. A substance having a pH of 8 or more in a 1 wt% aqueous solution at 20 ° C. can be paraphrased as a basic additive.
• the pH of the 1 wt% aqueous solution at 20 ° C. is preferably 8.5 or more, and more preferably 8.5 to 11.
• the pH of a 1 wt% aqueous solution at 20 ° C. is measured according to standard procedures, for example, with a glass pH electrode.
• the "1 wt% aqueous solution at 20 ° C.” does not need to have all the solutes dissolved in water.
• the aqueous solution refers to a liquid solute is dissolved in water (H 2 O). That is, it means a solution in which the solvent is water. Since water molecules are polar molecules, the substance that becomes the solute of the aqueous solution is said to be an ionic crystal or a polar molecular substance.
• the "aqueous solution” includes a suspension. That is, it includes a slurry and a colloidal solution, which are dispersion systems in which solid particles are dispersed in a liquid.
• the "1 wt% aqueous solution at 20 ° C.” is an aqueous solution in which a part of the basic additive is dissolved when the basic additive is added in 1 wt% to water. It also includes those in which the remaining basic additive portion is a suspension.
• the solid particles may be colloidal particles (about 100 nm or less), but may be larger particles.
• a suspension of colloidal particles may be referred to as a colloidal solution, and a suspension of particles larger than the colloidal particles may simply be referred to as a suspension.
• Suspensions of particles larger than colloidal particles unlike colloidal solutions, settle into a steady state over time. Solid particles can be seen under a microscope and may subside over time when placed in a quiet location.
• the basic additive in the aqueous solution is an inorganic substance that becomes an ion in the aqueous solution
• the surface is adsorbed and charged with ions due to the influence of the surface charge of the particles, which affects the ion distribution in the vicinity of the surface. Due to this effect, a distribution of ions called an electric double layer around the surface of the basic additive is generated, which is different from that in the solution (solvent) outside the interface of the particles.
• the electric double layer is formed of a fixed layer in which ions are most strongly adsorbed on the particle surface and a diffusion layer away from the fixed layer.
• the pH of the dispersion medium changes depending on the surface charge of the basic additive as described above even when it is not dissolved in water.
• substances (basic additives) having a pH of 8 or more in a 1 wt% aqueous solution at 20 ° C. include alkaline earth metals or alkali metal oxides, hydroxides, carbonates, acetates, ammonium salts, and aluminates. , Silate, or metasilicate; ZnO; and basic Al 2 O 3 and the like.
• the basic additive oxide of an alkaline earth metal or alkali metal hydroxides, carbonates, ammonium salts, aluminates, silicates, or metasilicates; than and basic Al 2 O 3; ZnO 1 or more selected from the group is preferable.
• the basic additive is selected from the group consisting of alkaline earth metals or alkali metal oxides, hydroxides, aluminates, silicates, or metasilicates; ZnO; and basic Al 2 O 3. 1 or more is more preferable.
• the basic additive one or more selected from the group consisting of alkaline earth metal or alkali metal oxide, aluminate, silicate, or metasilicate; ZnO; and basic Al 2 O 3 is further added. preferable.
• alkaline earth metals or alkali metal oxides one or more selected from the group consisting of alkaline earth metals or alkali metal oxides, aluminates, silicates, and metasilicates is more preferable.
• an oxide of an alkaline earth metal is particularly preferable.
• Magnesium oxide (MgO) is one of the most preferred.
• Examples of the alkaline earth metal or the oxide of the alkali metal include magnesium oxide (MgO) and calcium oxide (CaO).
• alkaline earth metal or the hydroxide of the alkali metal examples include Mg (OH) 2 and Ca (OH) 2 .
• alkaline earth metal or the carbonate of the alkali metal examples include MgCO 3 , CaCO 3 , NaHCO 3 , Na 2 CO 3 , and K 2 CO 3 .
• Examples of the alkaline earth metal or the acetate of the alkali metal include magnesium acetate and calcium acetate.
• alkali earth metal or alkali metal aluminate examples include sodium aluminate and the like.
• Sodium aluminate is an inorganic compound containing sodium and aluminum. What is called sodium aluminate includes sodium aluminum dioxide (aluminum dioxide) which is a compound oxide: NaAlO 2 and sodium tetrahydroxydoaluminate which is a hydroxy complex: Na [Al (OH) 4 ] and the like.
• alkaline earth metal or the silicate of the alkali metal examples include sodium silicate (Na 2 SiO 3 ) and the like.
• Silicic acid is a general term for compounds of silicon, oxygen, and hydrogen represented by the general formula [SiO x (OH) 4-2 x ] n.
• Examples of the alkaline earth metal or the metasilicate of the alkali metal include magnesium aluminometasilicate. It is represented by the general formula Al 2 O 3 , MgO, 2SiO 2 , xH 2 O (where x indicates the number of water of crystallization and 1 ⁇ x ⁇ 10).
• Magnesium aluminate metasilicate itself is known, and a commercially available product can also be used.
• magnesium aluminometasilicate which is a pharmaceutical standard outside the Japanese Pharmacopoeia, can be preferably used.
• Magnesium aluminate metasilicate is marketed as an antacid as Neucillin®.
• Other preferred basic substances include basic polymers and oligomers; basic amino acids and proteins; and basic saccharides.
• the basic additives of the present disclosure do not necessarily have to be water soluble, but may have a solubility of 10-5 to 70 g / 100 mL water at 20 ° C.
• the basic additives of the present disclosure preferably have a solubility of 10-6 g or more / 100 mL water at 20 ° C., more preferably 10-5 g or more / 100 mL water solubility at 20 ° C. It is more preferable to have a solubility of 10 -4 g or more / 100 mL water.
• the basic additive preferably has a solubility of 10 g or less / 100 mL water at 20 ° C, more preferably 1 g or less / 100 mL of water at 20 ° C, and 0.1 g or less / 100 mL at 20 ° C. It is more preferred to have water solubility.
• additives with a solubility of about 10-4 g / 100 mL (20 ° C.) in water are MgO, ZnO and Mg (OH) 2 .
• An example of an additive having a solubility of about 10-2 g / 100 mL (20 ° C.) in water is MgCO 3 .
• additives with a solubility of about 0.1 g / 100 mL (20 ° C) in water are CaO and Ca (OH) 2 .
• the substance that dissolves in water at 20 ° C. in an amount of 2% by weight or more may be a high molecular weight substance or a low molecular weight substance as long as it is water-soluble.
• the polymer substance examples include hydrophilic polymers.
• the hydrophilic polymer is a polymer having a hydrophilic functional group.
• the hydrophilic polymer is not particularly limited, and is, for example, a polymer having an OH group such as polyvinyl alcohol and partially saponified polyvinyl acetate; polyacrylic acid, polymethacrylic acid, acrylic acid, methacrylic acid and other polymers.
• Polymers with COOH groups such as copolymers of monomers; polymers with polyether skeletons such as polyethylene glycol, 1,3-polypropylene glycol, and 1,4 polybutylene glycol; and polyvinylpyrrolidone, polyacrylamide, poly- Polymerization having a monomer having an amide skeleton in the molecule such as N-methylacrylamide, poly-N, N-dimethylacrylamide, polyacryloylmorpholin, poly-N-vinylmorpholin and poly-N-vinylmorpholin-N-oxide. Things;
• the hydrophilic polymer may be used alone or in combination of two or more.
• Polymeric material is a polymer having a repeating unit, the number of atoms constituting the recurring unit as N2, OH group contained in the repeating unit, amido group, an amino group, COOH group, and NR 3 + groups
• N1 / N2 is preferably 0.01 or more and 0.55 or less, and more preferably 0.1 or more and 0.5 or less. This is because high hydrophilicity can be imparted.
• R of NR 3 + group include CH 3 , CH 2, CH 3, and the like.
• the polymer substance is preferably an amide group-containing vinyl polymer.
• the amide group-containing vinyl polymer is obtained by polymerizing a vinyl-based monomer having an amide group.
• the amide group-containing vinyl polymer is more preferably polyvinylpyrrolidone or a vinylpyrrolidone copolymer. This is because it has excellent compatibility with cellulose acetate.
• low molecular weight substances examples include polysaccharides and plasticizers of cellulose acetate.
• the polysaccharide is composed of at least one type of polysaccharide (A) selected from oligosaccharides (powdered oligosaccharides), reduced starch syrup, and cluster dextrin, and at least one type of crystalline sugar alcohol (B). Examples include the polysaccharides that have been used.
• the following can be used as at least one type of polysaccharide selected from oligosaccharides (powdered oligosaccharides), reducing starch syrup, and cluster dextrin.
• the oligosaccharide (A1) may be a homooligosaccharide or a heterooligosaccharide.
• Examples of the oligosaccharide (A1) include oligosaccharides of disaccharide to tensaccharide and oligosaccharide of disaccharide to hexasaccharide.
• the oligosaccharide (A1) may be anhydrous. Further, in the oligosaccharide (A1), the monosaccharide and the sugar alcohol may be bound to each other.
• the oligosaccharide (A1) may be an oligosaccharide composition composed of a plurality of sugar components, or may be an oligosaccharide composition produced by decomposition of a polysaccharide. Even such an oligosaccharide composition may be simply referred to as oligosaccharide (A1).
• Oligosaccharide (A1) is usually solid at room temperature.
• the oligosaccharide (A1) (or oligosaccharide composition) can be used alone or in combination of two or more. Since the oligosaccharide (A1) is generally derived from a natural product, the burden on the environment can be reduced.
• disaccharide examples include homooligosaccharides such as trehalose, maltose, isomaltose, cellobiose, gentiobiose, and melibiose; and heterooligosaccharides such as lactose, sucrose, and palatinose.
• homooligosaccharides such as trehalose, maltose, isomaltose, cellobiose, gentiobiose, and melibiose
• heterooligosaccharides such as lactose, sucrose, and palatinose.
• trisaccharides examples include homo-oligosaccharides such as maltotriose, isomaltotriose, panose, and cellotriose; and manninotriose, soratorioce, melezitose, planteose, gentianose, umbelliferose, lactosucrose, and raffinose. Heterooligosaccharides can be mentioned.
• tetrasaccharides examples include homo-oligosaccharides such as maltotetraose and isomalt tetraose; and hetero-oligosaccharides such as stachyose, cellotetraose, scordose, liquinose, or tetraose in which a sugar or sugar alcohol is bound to the reducing end of panose.
• hetero-oligosaccharides such as stachyose, cellotetraose, scordose, liquinose, or tetraose in which a sugar or sugar alcohol is bound to the reducing end of panose.
• tetraosaccharides in which a monosaccharide or a sugar alcohol is bound to the reducing end of panose is disclosed in, for example, Japanese Patent Application Laid-Open No. 10-215892, and glucose, fructose, mannose, etc.
• monosaccharides such as xylose or arabinose;
• pentasaccharides examples include homo-oligosaccharides such as maltopentaose and isomalt pentaose; and hetero-oligosaccharides such as pentaose in which a disaccharide is bound to the reducing end of panose.
• Pentaose in which a disaccharide is bound to the reducing end of panose is disclosed in, for example, Japanese Patent Application Laid-Open No. 10-215892, and pentaose in which a disaccharide such as sucrose, lactose, cellobiose, or trehalose is bound to the reducing end of panose.
• a disaccharide such as sucrose, lactose, cellobiose, or trehalose
• hexasaccharide examples include homooligosaccharides such as maltohexaose and isomalt hexaose.
• oligosaccharides composed of at least tetrasaccharides are preferable from the viewpoint of melt viscosity characteristics, melt mixing with resin components, or kneadability.
• oligosaccharides or oligosaccharide compositions examples include starch sugar (starch glycated product), galactooligosaccharide, coupling sugar, fructooligosaccharide, xylooligosaccharide, soybean oligosaccharide, chitin oligosaccharide, and chitosan oligosaccharide.
• starch sugar is an oligosaccharide composition obtained by reacting starch with an acid, glucoamylase, or the like, and may be a mixture of oligosaccharides in which a plurality of glucoses are bound.
• starch sugar examples include reduced starch saccharified products manufactured by Towa Kasei Kogyo Co., Ltd. (trade name: PO-10, content of tetrasaccharides of 90% by weight or more) and the like.
• the galactooligosaccharide is an oligosaccharide composition obtained by allowing ⁇ -galactosidase or the like to act on lactose, and may be a mixture of galactose lactose and galactose- (glucose) n (n is an integer of 1 to 4).
• Coupling sugar is an oligosaccharide composition obtained by reacting starch and sucrose with a cyclodextrin synthase (CGTase), even if it is a mixture of (glucose) n -sucrose (n is an integer of 1 to 4).
• CCTase cyclodextrin synthase
• the fructooligosaccharide (fructooligosaccharide) is an oligosaccharide composition obtained by reacting sugar with fructofuranosidase, and may be a mixture of sucrose- (fructose) n (n is an integer of 1 to 4).
• the above-mentioned substance that dissolves in water at 20 ° C. in an amount of 2% by weight or more preferably contains a plasticizer of cellulose acetate.
• Plasticizers include dimethylphthalate; diethylphthalate; dibutylphthalate; dioctylphthalate; diisononylphthalate; butylbenzylphthalate; butylphthalylbutylglycolate; tris (2-ethylhexyl) trimellitate; triethylphosphate, triphenylphosphate, tricresyl phosphate.
• P-Phthalate bis diphenyl phosphate
• other phosphate derivatives diisobutyl adipate; bis (2-ethylhexyl) adipate; triethyl citrate; acetyltriethyl citrate; plasticizer containing citrate (eg, Citroflex®).
• a glycerin ester-based plasticizer can be used.
• a lower fatty acid ester of glycerin in other words, an ester compound of glycerin and a fatty acid having 2 to 4 carbon atoms can be used.
• the fatty acid having 2 carbon atoms is acetic acid
• the fatty acid having 3 carbon atoms is propionic acid
• the fatty acid having 4 carbon atoms is butyl acid.
• the glycerin ester-based plasticizer may be one in which all three hydroxyl groups of glycerin are esterified with the same fatty acid, two hydroxyl groups may be esterified with the same fatty acid, and three of glycerin. All of the hydroxyl groups of the above may be esterified with different fatty acids.
• Glycerin ester plasticizers are non-toxic and easily biodegradable, so they have a small impact on the environment. Further, by adding a glycerin ester-based plasticizer to the cellulose acetate, the glass transition temperature of the obtained cellulose acetate composition can be lowered. Therefore, it is possible to impart excellent thermoformability to the raw material.
• examples of the glycerin ester-based plasticizer include triacetin in which three hydroxyl groups of glycerin are esterified with acetic acid, diacetin in which two hydroxyl groups are esterified with acetic acid, and the like. Be done.
• triacetin glycerol triacetate in which all three hydroxyl groups of glycerin are esterified (in other words, acetylated) with acetic acid is particularly preferable.
• Triacetin is a component that is recognized as safe for human consumption, and is easily biodegraded, so it has a small impact on the environment.
• the cellulose acetate composition obtained by adding triacetin to cellulose acetate has improved biodegradability as compared with the case where cellulose acetate is used alone.
• the glass transition temperature of cellulose acetate can be efficiently lowered. Therefore, excellent thermoformability can be imparted to the raw material.
• Triacetin should be chemically pure and highly pure. Further, for example, a plasticizer containing 80% by weight or more or 90% by weight or more of triacetin and containing monoacetin and / or diacetin as a balance may be used.
• the biodegradability of cellulose acetate can be promoted by adding a substance having excellent biodegradability in the ocean.
• substances having excellent biodegradability in the ocean include compounds having excellent biodegradability in the ocean.
• a substance having excellent biodegradability in the ocean may be insoluble in water.
• the compound having excellent biodegradability in the ocean include a substance that decomposes 50% or more, preferably 70% or more, with respect to the cellulose to be compared after 180 days by the method specified in ASTM D6691.
• examples include poly [hydroxybutyrate-co-hydroxyhexanoate] (PHBH), polyhydroxyalkanoates such as polyhydroxybutyrate, and thermoplastic starch resins (including acetylated starch).
• the biodegradation process of the cellulose acetate and the cellulose acetate composition of the present disclosure is as follows.
• the mechanism of biodegradation of cellulose acetate is that when each acetyl group of cellulose acetate is hydrolyzed and the degree of substitution decreases, an enzyme that decomposes cellulose (for example, ⁇ -glucosidase (EC 3.2.1.21)) acts.
• ⁇ -glucosidase (EC 3.2.1.21) is an enzyme that catalyzes the reaction that hydrolyzes the ⁇ -glycoside bond of sugar, and is ⁇ -D-glucoside glucohydrolase. , Also called amigdase.
• the ⁇ -glucosidase bond that constitutes the high molecular chain of cellulose acetate is hydrolyzed to a monosaccharide or a low-molecular-weight polysaccharide, which is then decomposed by normal microbial metabolism. Therefore, it is biodegradable. It is effective to promote the elimination of the acetyl group in order to promote the elimination of the acetyl group.
• the sulfuric acid component is too large, there is a concern that it will decompose during use as a product until it is immersed in the ocean.
• these actions are compared between those having the same total substitution degree, it seems that the same tendency is exhibited regardless of the total substitution degree.
• the degree of biodegradability is excellent when the total degree of acetyl substitution is 2.7 or less.
• the ratio ⁇ of the sum of the acetyl substitution degree at the 2-position and the acetyl substitution degree at the 3-position to the acetyl substitution degree at the 6th position is 2.0 or more, particularly 2.1 or more, and further. , 2.15 or more, preferably 2.2 or more.
• the decomposition mechanism of the cellulose acetate composition of the present disclosure is as follows. This mechanism is speculated, but in weakly basic seawater, a substance (basic additive) with a pH of 8 or more in a 1 wt% aqueous solution at 20 ° C. promotes hydrolysis (deacetylase) of cellulose acetate. Seem.
• the deacetylase effect of this basic substance is remarkable in cellulose acetate having a large amount of acetyl groups at the 2nd and 3rd positions from the 6th position, and further in cellulose acetate having a large amount of sulfuric acid components.
• the degree of substitution of the cellulose acetate constituting the cellulose acetate composition is lowered, which can contribute to the improvement of biodegradability. It is preferable that these properties are not expressed when used as a product, but are rapidly expressed after contact with seawater. Therefore, it is preferably dispersed in the cellulose acetate composition as solid particles, and the particle size of the basic substance is preferably as fine as possible and has a large specific surface area.
• magnesium aluminometasilicate, magnesium oxide and the like can be preferably used because they are highly safe such as being used as pharmaceuticals. ..
• the cellulose acetate composition of the present disclosure can also contain a substance that dissolves in water at 20 ° C. in an amount of 2% by weight or more.
• a substance that dissolves in water at 20 ° C. in an amount of 2% by weight or more.
• Such a substance can be dissolved in seawater when the cellulose acetate composition is put into seawater. Then, it escapes from the cellulose acetate composition and forms structural voids in the molded product composed of the cellulose acetate composition. Then, microorganisms easily enter the voids, and the surface area of the molded product composed of the cellulose acetate composition increases. As a result, it can contribute to the improvement of biodegradability.
• the substance include triacetin and diacetin. Since triacetin and diacetin also act as plasticizers for cellulose acetate, they can also contribute to the improvement of thermoformability.
• the content of the additive in the cellulose acetate composition is preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less as the total content.
• the content of the additive is preferably 5% by weight or more, more preferably 10% by weight or more.
• the content of the basic additive (a substance having a pH of 8 or more in a 1% by weight aqueous solution at 20 ° C.) in the cellulose acetate composition is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, and 3 to 15%. By weight% is more preferred, and 5-10% by weight is particularly preferred. If the amount of the basic additive is too large, problems such as moldability may occur, such as difficulty in molding the cellulose acetate or the cellulose acetate composition.
• the content of the water-soluble additive (a substance that dissolves in water at 20 ° C. in an amount of 2% by weight or more) in the cellulose acetate composition is preferably 5 to 30% by weight, more preferably 7.5 to 28% by weight, and 10 to 10 to 25% by weight is more preferable. If the amount of the water-soluble additive is too large, the strength of the cellulose acetate composition is reduced.
• the content of the substance having excellent biodegradability in the ocean in the cellulose acetate composition is preferably 5 to 40% by weight.
• the cellulose acetate composition of the present disclosure can be used in combination with other substances to improve the biodegradability of the mixture as a whole.
• the composition contains, for example, an acidic substance, and when immersed in water, a neutralization reaction occurs and the composition is neutral to acidic. In the case of, the effect of adding a basic substance may not be obtained.
• the pH of the slurry obtained by mixing with water at 20 ° C. is preferably 7 to 13, preferably 8 to 12.
• cellulose acetate In the biodegradation of cellulose acetate of the present disclosure, it is considered that first, the acetyl group is eliminated, the value of the degree of acetyl substitution becomes small, and the cellulose acetate approaches cellulose, and is decomposed by the action of microorganisms. Therefore, as the additive, an additive that promotes the decomposition of this cellulose acetate is preferable.
• Cellulose acetate has a cellulose type II crystal structure (more accurately, it is referred to as a cellulose acetate type II crystal structure). Acetylation of the raw material cellulose can convert cellulose type I to type II.
• the cellulose type II crystal structure has an antiparallel chain structure in which the reducing ends are alternately located, and is not as strong as the cellulose type I crystal structure.
• Such a crystal structure of cellulose acetate also contributes to the excellent biodegradability of the cellulose acetate composition of the present disclosure in seawater. It is said that once the cellulose type I crystal structure is changed to the cellulose acetate type II crystal structure, the change to the type I crystal structure does not occur.
• the cellulose acetate composition of the present disclosure is suitable for thermoforming because it has excellent thermoforming properties.
• the shape of the molded product obtained by molding the cellulose acetate composition of the present disclosure is not particularly limited, and for example, a one-dimensional molded product such as a fiber; a two-dimensional molded product such as a film; and a particle shape containing pellets. , Tubes, hollow cylinders, and other three-dimensional molded products.
• the ratio of particles having a particle size of 2 mm or less is preferably 50% by weight or less. This is because it is more biodegradable.
• the ratio (% by weight) of particles having a particle size of 2 mm or less can be determined by using a sieve specified in JIS Z8801. That is, using a sieve and a saucer having an opening of 2 mm, the sample was attached to a low tap machine (manufactured by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute), and a 100 g sample was applied for 5 minutes. After vibrating, it can be obtained by calculating the ratio of the total weight of the particles on each sieve to the total weight (sample 100 g).
• the cellulose acetate or cellulose acetate composition of the present disclosure has excellent biodegradability in seawater, easily disposable products such as containers such as straws and cups, packaging materials, binders, and tobacco filters; clothing fibers.
• easily disposable products such as containers such as straws and cups, packaging materials, binders, and tobacco filters; clothing fibers.
• Non-woven fabric Non-woven fabric; Cosmetic beads, scrubs, and other products that partially flow into the natural world with water when used; and sanitary materials (diapers, sanitary products) and other products that are expected to be flushed into the toilet.
• the method for producing cellulose acetate of the present disclosure is not particularly limited, and examples thereof include the following methods.
• the step (a) of reacting cellulose with acetic anhydride in the presence of an acid catalyst and an acetic acid solvent to form a dope of cellulose acetate the produced cellulose acetate is hydrolyzed to reduce the total degree of acetyl substitution to 2.7 or less.
• a production method comprising a step (c) of precipitating hydrolyzed cellulose acetate with a precipitant.
• Step of Forming Dope of Cellulose Acetate In the step of producing a dope of cellulose acetate, it is a vinegarization reaction in which cellulose is reacted with acetic anhydride in the presence of an acid catalyst and an acetic acid solvent, in other words, cellulose is vinegarized.
• This cellulose is preferably subjected to an activation step.
• the activation step include pretreatment activation of the raw material cellulose by adding acetic acid or acetic acid containing 1 to 10% by weight of sulfuric acid (sulfur-containing acetic acid) to the raw material cellulose in one or two stages.
• cellulose pulp
• wood pulp conifer pulp, hardwood pulp
• cotton linter etc.
• These celluloses may be used alone or in combination of two or more, and for example, softwood pulp and cotton linter or hardwood pulp may be used in combination.
• Linter pulp is preferable because it has high cellulose purity and few coloring components, and thus the transparency of the molded product is high.
• Wood pulp is preferable because it can be stably supplied as a raw material and is advantageous in terms of cost as compared with linters.
• Examples of wood pulp include hardwood pre-hydrolyzed kraft pulp and the like.
• crushed pulp obtained by crushing hardwood pre-hydrolyzed kraft pulp or the like into a cotton-like shape can be used. The crushing can be performed using, for example, a disc refiner.
• the ⁇ -cellulose content of the raw material cellulose is preferably 90% by weight or more, more preferably 92% by weight or more, and more preferably 95% by weight, because it reduces the insoluble residue and does not impair the transparency of the molded product. It is more preferably% or more, and most preferably 97% by weight or more.
• the raw material cellulose is supplied in the form of a sheet and is difficult to handle in the subsequent steps, it is preferable to go through the step of crushing the raw material cellulose by a dry method.
• acetic acid and / or sulfur-containing acetic acid is added to 100 parts by weight of the raw material cellulose. Therefore, preferably 10 to 500 parts by weight can be added.
• acetic acid and / or acetic acid containing sulfur is added in one step, or acetic acid is added and after a certain period of time, acetic acid containing sulfur is added.
• Examples thereof include a method of adding acetic acid containing acetic acid or a method of adding acetic acid containing acetic acid after a lapse of a certain period of time, or a method of adding acetic acid containing sulfur containing acetic acid in two or more steps.
• Specific means of addition include a method of spraying and stirring.
• the mixture is allowed to stand at 17 to 40 ° C. for 0.2 to 48 hours, or 0.1 to 24 at 17 to 40 ° C. It can be carried out by time-sealing and stirring.
• the step (vinegarization reaction step) of reacting cellulose with acetic anhydride in the presence of an acid catalyst and an acetic acid solvent to form a dope of cellulose acetate will be described.
• Sulfuric acid is preferable as the acid catalyst.
• vinegarization can be started by adding cellulose to a mixture consisting of acetic acid, acetic anhydride and sulfuric acid, or by adding a mixture of acetic acid and acetic anhydride and sulfuric acid to cellulose.
• the dope of cellulose acetate means a solution obtained by dissolving cellulose acetate or a mixture containing cellulose acetate in a solvent.
• the mixture thereof is not particularly limited as long as it contains acetic acid and acetic anhydride, but the ratio of acetic acid to acetic anhydride is 200 to 400 parts by weight based on 300 to 600 parts by weight of acetic acid. It is preferably parts, and more preferably 240 to 280 parts by weight of acetic anhydride with respect to 350 to 530 parts by weight of acetic acid.
• the ratio of cellulose, a mixture of acetic acid and acetic anhydride, and sulfuric acid in the vinegarization reaction is preferably 500 to 1,000 parts by weight, preferably 500 to 1,000 parts by weight, based on 100 parts by weight of cellulose.
• the amount of sulfuric acid is preferably 0.5 to 15 parts by weight, more preferably 5 to 14 parts by weight, and even more preferably 7 to 11 parts by weight. Increasing the amount of concentrated sulfuric acid increases the amount of sulfuric acid component.
• the vinegarization reaction of cellulose can be carried out by stirring for 30 minutes to 36 hours from the time when vinegarization is started at 20 to 55 ° C.
• the vinegarization reaction of cellulose is carried out, for example, by raising the temperature to 20 to 55 ° C., which takes 5 minutes to 36 hours from the start of vinegarization under stirring conditions, or from the outside under stirring conditions. It can be carried out without applying any heat to the inside and outside of the reaction system.
• the reaction is in a solid-liquid non-uniform system, and it is better to raise the temperature as long as possible in order to promote the vinegarization reaction while suppressing the depolymerization reaction and reduce unreacted substances. From the viewpoint, it is preferable to raise the temperature in 2 hours or less, more preferably 1 hour or less.
• the time required for the vinegarization reaction (hereinafter, also referred to as vinegarization time) is preferably 30 to 200 minutes.
• the vinegarization time refers to the time from the time when the raw material cellulose is charged into the reaction system and the reaction with acetic anhydride is started until the neutralizing agent is charged.
• Step of hydrolyzing cellulose acetate (b) In the step (b) of hydrolyzing the produced cellulose acetate to reduce the total acetyl substitution degree to 2.7 or less, for example, during hydrolysis (neutralization), water (including water vapor) is used to stop the vinegarization reaction. ); Dilute acetic acid; or a neutralizing agent containing carbonates such as calcium, magnesium, iron, aluminum or zinc, acetates, hydroxides or oxides; etc. is added.
• the dilute acetic acid refers to an aqueous acetic acid solution of 1 to 50% by weight.
• Magnesium acetate and calcium acetate are preferable as the neutralizing agent. Since calcium and the like bind to sulfuric acid, the sulfate ion concentration in the doping of cellulose acetate can be increased. As a result, the amount of sulfuric acid component in the obtained cellulose acetate can be adjusted to exceed 20 ppm and to 400 ppm or less. Further, by increasing the amount of water added at the time of hydrolysis, the ratio ( ⁇ ) of the degree of substitution at the 2nd and 3rd positions to the degree of substitution at the 6th position can be increased.
• the time for the hydrolysis (saponification) reaction (hereinafter, also referred to as aging time) is not particularly limited, and the time may be appropriately adjusted according to the desired total degree of acetyl substitution.
• the aging time refers to the time from the start of addition of the neutralizing agent to the termination of the hydrolysis (saponification) reaction.
• the total degree of substitution can be reduced by lengthening the aging time.
• the hydrolysis (saponification) reaction is carried out by holding at an aging temperature of preferably 50 to 100 ° C., particularly preferably 70 to 90 ° C. for 20 to 120 minutes.
• the aging temperature means the temperature in the reaction system during the aging time.
• Step (c) of precipitating hydrolyzed cellulose acetate with a precipitant The step of precipitating the prepared cellulose acetate with a precipitant will be described.
• the precipitant may be appropriately selected according to the desired total degree of acetyl substitution.
• the precipitated cellulose acetate may be washed with a precipitating agent to remove free metal components, sulfuric acid components and the like. Then, in order to enhance the thermal stability of the cellulose acetate, in addition to washing with a precipitating agent, an alkali metal compound and / or an alkaline earth metal compound, particularly a calcium compound such as calcium hydroxide, is added as a stabilizer, if necessary. It may be added. Further, a stabilizer may be used when washing with a precipitant.
• the obtained cellulose acetate may be separated and dried if necessary.
• the separation of cellulose acetate is preferably dehydrated by filtration, centrifugation or the like.
• the drying treatment is not particularly limited as the method, and known methods can be used, and for example, drying can be performed under conditions such as blowing air and reducing pressure. Examples of the drying method include hot air drying.
• the additive can be contained by the following method.
• Cellulose acetate composition can be obtained by mixing cellulose acetate and additives with a solvent such as acetone and then removing the solvent.
• the cellulose acetate composition may be obtained by melting the cellulose acetate and kneading the additive.
• each acetyl substitution degree at the 2, 3 and 6 positions (DS2, DS3, DS6) was requested.
• the total acetyl substitution is the sum of the acetyl substitutions at the 2, 3 and 6 positions.
• the sum of the 2-position acetyl substitution degree and the 3-position acetyl substitution degree (DS2 + 3) and the ratio ⁇ of the sum of the 2-position acetyl substitution degree and the 3-position acetyl substitution degree to the 6-position acetyl substitution degree were calculated. ..
• ⁇ Amount of sulfuric acid component> The dried cellulose acetate or cellulose acetate composition baked in an electric furnace at 1300 ° C., the sublimated sulfurous acid gas was trapped in a 10% aqueous hydrogen peroxide, and titrated with N sodium hydroxide solution, the amount of SO4 2-Conversion It was measured as the amount of sulfuric acid component.
• the amount of sulfuric acid component is expressed in ppm as the amount of sulfuric acid component in 1 g of cellulose acetate or cellulose acetate composition in an absolutely dry state.
• ⁇ Slurry pH> 2.0 g of a fine powder of dried cellulose or cellulose acetate composition was accurately weighed, 80 ml of boiled distilled water was added and stirred, and the mixture was sealed and allowed to stand overnight, and then further stirred to settle the sample. About 10 ml of the supernatant was used as a sample solution, and the pH was measured with a corrected pH meter. As a blank, the pH of boiling distilled water is also measured, and the hydrogen ion concentration of the sample solution and the blank solution is calculated by the formula [H + ] 10- (pH) (pH indicates the measured pH value) [H + ]. s and [H + ] b (s indicates a sample, b indicates a blank) were calculated, respectively. When [H + ] s ⁇ [H + ] b , the slurry pH can be calculated by the following formula.
• ⁇ Biodegradability> The biodegradability was evaluated using a method of immersing in seawater and evaluating the biodegradability.
• a film was prepared by a general solvent casting method. 10 to 15 parts by weight of the cellulose or cellulose acetate composition obtained in Examples and Comparative Examples was dissolved in 85 to 90 parts by weight of acetone, and a predetermined amount of MgO was further added to prepare a dope. The dope was poured onto a glass plate and spread with a bar coater. The film was dried at 40 ° C. for 30 minutes, the film was peeled off from the glass plate, and dried at 80 ° C. for another 30 minutes to obtain an evaluation film having a thickness of 30 ⁇ m.
• the film (10 cm x 10 x m x 50 ⁇ m) prepared by the above method was placed in a stainless steel container and biodegraded by a method according to ASTM D6691.
• the seawater used was seawater collected from Hakata Bay in Kitakyushu.
• the biodegradability was evaluated by weight measurement. That is, 90 days and 180 days after the start of immersion, the entire contents of the stainless steel container were filtered with a filter having an opening of 10 ⁇ m, and the film and the residue obtained by decomposing the film were collected on the filter. After rinsing the filter with 50 mL of distilled water, the residuals and the filter were dried under vacuum at 80 ° C. for 4 hr.
• Weight retention rate 100 x W1 / W2
• a neutralizing agent (24% aqueous magnesium acetate solution) was added over 3 minutes so that the amount of sulfuric acid (aged sulfuric acid) was adjusted to 2.5 parts by weight. Further, after raising the temperature of the reaction bath to 75 ° C., water was added to bring the reaction bath water (aged water) to a concentration of 52 mol%. The aging water concentration was expressed in mol% by multiplying the ratio of the reaction bath water to acetic acid by 100. Then, it was aged at 85 ° C. for 130 minutes, and the aging was stopped by neutralizing sulfuric acid with magnesium acetate to obtain a reaction mixture containing cellulose acetate.
• Comparative Example 2 Cellulose acetate was obtained in the same manner as in Comparative Example 1 except that the aging time was 100 minutes. The results of evaluating each physical property are shown in Table 1.
• the hydrolysis reaction was stopped by neutralizing sulfuric acid with magnesium acetate to obtain a reaction mixture containing cellulose acetate.
• the time from the time when the pulp is added to the mixed solution to the time when the neutralizing agent is added is defined as the esterification time.
• Precipitation was carried out with about 300 parts by weight of a 10% dilute acetic acid aqueous solution with respect to 100 parts by weight of the reaction mixture containing cellulose acetate.
• calcium hydroxide was added as a stabilizer, and the mixture was filtered and dried to obtain cellulose acetate.
• Table 1 The results of evaluating each physical property are shown in Table 1.
• the peak temperature was adjusted from 8.9 ° C to 38 ° C below freezing in 62 minutes.
• the neutralizing agent 24 wt% magnesium acetate
• the sulfuric acid amount aged sulfuric acid amount
• the esterification process was completed.
• the reaction bath was heated to 50.9 ° C. and hydrolyzed for 50 minutes. The hydrolysis reaction was stopped by neutralizing sulfuric acid with magnesium acetate to obtain a reaction mixture containing cellulose acetate.
• the time from the time when the pulp is added to the mixed solution to the time when the neutralizing agent is added is defined as the esterification time.
• Precipitation was carried out with about 300 parts by weight of a 10% dilute acetic acid aqueous solution with respect to 100 parts by weight of the reaction mixture containing cellulose acetate. After washing with water, calcium hydroxide was added as a stabilizer, and the mixture was filtered and dried to obtain cellulose acetate.
• Table 1 The results of evaluating each physical property are shown in Table 1.
• acetic acid 417.85 parts of acetic acid, 282.98 parts of acetic anhydride and 8.72 parts of sulfuric acid are mixed with the cellulose activated through the second activation step, held at 15 ° C. or lower for 20 minutes, and then ascended.
• the temperature of the reaction system was raised to 35 ° C. at a temperature rate of 0.31 ° C./min and held for 80 minutes for acetylation.
• 0.15 parts by weight of acetic acid, 22.98 parts by weight of water, and 7.30 parts by weight of magnesium acetate were mixed and held at a temperature of 61 ° C. for 95 minutes, then 7.48 parts by weight of magnesium acetate and 20.94 parts by weight of acetic acid.
• Examples 1 to 8, Comparative Examples 6 to 11 Sheet-shaped cellulose (hardwood pulp) was treated with a discifier to make it cotton-like. 32.71 parts by weight of acetic acid was sprayed on 100 parts by weight of cotton-like cellulose (moisture content: 8.0% by weight), stirred well, and allowed to stand at a temperature of 24 ° C. for 60 minutes (activation step). 358.51 parts by weight of acetic acid, 214.99 parts by weight of acetic anhydride and A part by weight of sulfuric acid were mixed with the activated cellulose, held at 15 ° C. for 20 minutes, and then reacted at a heating rate of 0.31 ° C./min. The temperature of the system was raised to 45 ° C.
• the amount of water B added to the aging reaction was in the range of 1 to 50 parts by weight, and the degree of substitution at the 2, 3 and 6 positions was adjusted.
• the aging reaction time C was set in the range of 5 to 120 minutes, and the degree of substitution of the cellulose acetate to be synthesized was adjusted. From the above, cellulose acetate was obtained.
• the results of evaluating each physical property are shown in Table 1.
• Example 9 9.5 parts by weight of cellulose acetate having a degree of substitution of 2.46 synthesized in Example 1 is heated at 110 ° C. for 2 hours to dry, and then added to 90 parts by weight of acetone and stirred at 25 ° C. for 6 hours to dissolve the cellulose acetate.
• As an additive 0.5 part by weight of a powder of magnesium aluminometasilicate, which is a basic additive, was added thereto, and the mixture was further stirred at 25 ° C. for 6 hours to prepare a dope for film preparation. This dope was poured onto a glass plate, cast on a bar coater, dried at 40 ° C. for 30 minutes, then peeled off from the glass plate, dried at 80 ° C. for another 30 minutes, and a cellulose acetate composition film having a thickness of 30 ⁇ m.
• Table 1 The results of evaluating each physical property are shown in Table 1.
• Example 10 A cellulose acetate composition film having a thickness of 30 ⁇ m was obtained in the same manner as in Example 9 except that magnesium oxide was used as a basic additive and the amount of cellulose acetate added was 9.6 parts by weight and 0.4 parts by weight. .. The results of evaluating each physical property are shown in Table 1.
• Example 11 Cellulose acetate composition having a thickness of 30 ⁇ m in the same manner as in Example 9 except that 2.5 parts by weight of triacetin and 7.5 parts by weight of cellulose acetate were used as water-soluble additives instead of basic additives. I got a film. The results of evaluating each physical property are shown in Table 1.
• Example 12 The same as in Example 9 except that 0.5 parts by weight of magnesium oxide, which is a basic additive, 2.0 parts by weight of triacetin, which is a water-soluble additive, and 7.5 parts by weight of cellulose acetate were used as additives. A cellulose acetate composition film having a thickness of 30 ⁇ m was obtained. The results of evaluating each physical property are shown in Table 1.
• Example 13 As an additive, 0.8 parts by weight of PHBH and 9.2 parts by weight of cellulose acetate were used as an additive as a substance having excellent biodegradability in the ocean, and melt kneaded at 240 ° C. using a twin-screw kneader. Then, a cellulose acetate composition film having a thickness of about 30 ⁇ m was obtained with a T-die mold of a lab plast mill. The results of evaluating each physical property are shown in Table 1.

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