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
  • C08K3/18—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
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
• • 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
  • 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

Definitions

• the present invention relates to a cellulose acetate resin composition made from non-edible cellulose, and to a molded article made using the same.
• Bioplastics made from plants and other renewable organic resources, can contribute to combating oil depletion and global warming, and are therefore beginning to be used in durable products such as electronic devices and automobiles, in addition to general products such as packaging, containers, and textiles.
• concerns about future food shortages have led to a demand for the development of new bioplastics made from non-edible plant resources.
• Cellulose acetate is a biomass material obtained by esterifying the hydroxyl groups of cellulose derived from non-edible plant resources such as wood fiber and cotton with acetic acid.
• resin compositions based on cellulose acetate are imparted with thermoplasticity by adding a plasticizer.
• Patent Document 1 describes a resin composition composed of cellulose acetate, a plasticizer, and a bleed-out inhibitor.
• flame retardant measures are necessary, and it is known that flame retardants, particularly metal hydroxides, can be added to the resin composition.
• the object of the present invention is to provide a cellulose-based resin composition that can form a molded article that has excellent flame retardancy and mechanical strength and suppresses the exudation of plasticizer.
• the resin composition of the present invention comprises: Component A: cellulose acetate, Component B: a plasticizer which is a phosphoric acid ester; Component C: polyester, Component D: a metal hydroxide, A resin composition comprising: The content of the component B is 20 to 30% by mass relative to 100% by mass of the total content of the components A, B and C, The content of the component C is 0.5 to 10 mass% relative to 100 mass% of the total content of the components A, B and C, The content of the component D in the entire composition is 0.5 to 20 mass %.
• the present invention provides a cellulose-based resin composition that can be used to form molded articles that have excellent flame retardancy and mechanical strength and suppress the exudation of plasticizers.
• the resin composition of the present invention comprises Component A: cellulose acetate, Component B: a plasticizer which is a phosphoric acid ester; Component C: polyester, Component D: a metal hydroxide, A resin composition comprising: The content of the component B is 20 to 30% by mass relative to 100% by mass of the total content of the components A, B and C, The content of the component C is 0.5 to 10 mass% relative to 100 mass% of the total content of the components A, B and C, The content of the component D in the entire composition is 0.5 to 20 mass %.
• the resin composition of the present invention contains cellulose acetate as component A.
• cellulose acetate one in which acetyl groups have been introduced into at least a portion of the hydroxyl groups of cellulose as a raw material can be used.
• Cellulose is a linear polymer formed by the polymerization of ⁇ -D-glucose molecules ( ⁇ -D-glucopyranose) via ⁇ (1 ⁇ 4) glycosidic bonds, as shown in the following formula (1) (n in the formula is a natural number).
• Cellulose is the main component of plants, and can be obtained by separating and processing other components such as lignin from plants.
• cotton e.g. cotton linters
• pulp e.g. wood pulp
• the shape, size and form of cellulose or its derivatives used as raw materials are preferably in powder form with an appropriate particle size and shape in terms of reactivity, solid-liquid separation and ease of handling.
• fibrous or powdered material with a diameter of 1 to 100 ⁇ m (preferably 10 to 50 ⁇ m) and a length of 10 ⁇ m to 100 mm (preferably 100 ⁇ m to 10 mm) can be used.
• the degree of polymerization of cellulose is preferably in the range of 50 to 5,000, more preferably 100 to 3,000, and even more preferably 100 to 1,000. If the degree of polymerization is too low, the strength, heat resistance, etc. of the produced resin may be insufficient. Conversely, if the degree of polymerization is too high, the melt viscosity of the produced resin may become too high, causing problems in molding.
• Each glucose unit that constitutes cellulose has three hydroxyl groups.
• the cellulose acetate of the present invention is cellulose to which acetyl groups have been introduced, utilizing these hydroxyl groups. By introducing acetyl groups into cellulose, the intermolecular forces (intermolecular bonds) of cellulose can be reduced, improving the plasticity of the resin composition.
• the acetyl group can be introduced by reacting a hydroxy group in cellulose with an acylating agent.
• the acetyl group corresponds to an organic group that is introduced in place of the hydrogen atom of the hydroxy group of cellulose.
• the acylating agent is a compound that has at least one functional group that can react with the hydroxy group in cellulose, and examples of such an acylating agent include compounds that have a carboxyl group, a carboxylic acid halide group, or a carboxylic acid anhydride group. Specific examples include aliphatic monocarboxylic acids, their acid halides, and their acid anhydrides.
• the average number of acetyl groups introduced per glucose unit of cellulose (DS Ac ) (acetyl group introduction ratio), i.e., the average number of hydroxy groups substituted with acetyl groups per glucose unit (hydroxy group substitution degree), can be set in the range of 0.1 to 3.0.
• DS Ac is preferably 2.0 or more, more preferably 2.2 or more, and even more preferably 2.4 or more.
• DS Ac is preferably 2.9 or less, more preferably 2.8 or less.
• the average number of remaining hydroxyl groups per glucose unit of cellulose acetate can be set in the range of 0 to 2.9. Hydroxy groups may remain from the viewpoint of the maximum strength and heat resistance of the resin composition, and for example, the hydroxyl group residual degree may be 0.01 or more, and even 0.1 or more.
• the hydroxyl group residual degree of the final product cellulose acetate is preferably 1.0 or less, more preferably 0.8 or less, and particularly preferably 0.6 or less.
• the hydroxyl group residual degree is preferably 0.6 or less, more preferably 0.5 or less, more preferably 0.4 or less, and particularly preferably 0.2 or less.
• the molecular weight of cellulose acetate is preferably in the range of 10,000 to 400,000, more preferably in the range of 50,000 to 350,000, even more preferably in the range of 100,000 to 300,000, and even more preferably in the range of 150,000 to 250,000. If the molecular weight is too large, the fluidity of the resin composition will decrease, making processing difficult, and it may also be difficult to mix uniformly. Conversely, if the molecular weight is too small, the physical properties of the resin composition, such as impact resistance, may decrease. This weight average molecular weight can be determined by gel permeation chromatography (GPC) (commercially available standard polystyrene can be used as the standard sample).
• GPC gel permeation chromatography
• the content of component A is not particularly limited, but is preferably 45% by mass or more, more preferably 50% by mass or more, and particularly preferably 55% by mass or more, relative to 100% by mass of the total content of components A, B, and C. Also, the content of component A is preferably 80% by mass or less, more preferably 78% by mass or less, and particularly preferably 75% by mass or less, relative to 100% by mass of the total content of components A, B, and C.
• the resin composition of the present invention contains, as Component B, a plasticizer which is a phosphoric acid ester.
• Component B may be used alone or in combination of two or more.
• Component B functions as a plasticizer and a flame retardant, and can impart processing stability and flame retardancy to the resin composition.
• Examples of Component B include, but are not limited to, one or more phosphoric acid esters selected from the group consisting of triphenyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate, cresyl di-2,6-xylenyl phosphate, and compounds represented by the following formula (2).
• component B is triphenyl phosphate from the viewpoint of flame retardancy and high compatibility with cellulose acetate. Triphenyl phosphate is less likely to volatilize and has high compatibility with component A.
• the content of component B is preferably 20% by mass or more, more preferably 22% by mass or more, and more preferably 25% by mass or more, based on 100% by mass of the total content of components A, B, and C.
• the content of component B is preferably 30% by mass or less, more preferably 29% by mass or less, and more preferably 28% by mass or less, based on 100% by mass of the total content of components A, B, and C.
• the content of component B is preferably 15 to 35 mass%, more preferably 17 to 32 mass%, and particularly preferably 20 to 30 mass%, relative to 100 mass% of the total content of components A and B. If the content of component B is too high, seepage from the molded product may occur, and if the content of component B is too low, the impact strength may be insufficient.
• the resin composition of the present invention may contain other plasticizers within the scope of the present invention without impairing the effects of the present invention.
• plasticizers include phthalate esters such as dibutyl phthalate, diaryl phthalate, diethyl phthalate, dimethyl phthalate, di-2-methoxyethyl phthalate, ethylphthalyl/ethyl glycolate, and methylphthalyl/ethyl glycolate; tartaric acid esters such as dibutyl tartrate; adipic acid esters such as dioctyl adipate and diisononyl adipate; polyhydric alcohol esters such as triacetin, diacetyl glycerin, tripropionitrile glycerin, and glycerin monostearate; dibutyl adipate, dioctyl adipate, dibutyl azelate, and dioc
• aliphatic dicarboxylic acid dialkyl esters such as ethyl citrate and dioctyl sebacate; citric acid esters such as triethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate; epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; castor oil and its derivatives; benzoic acid esters such as ethyl O-benzoylbenzoate; aliphatic dicarboxylic acid esters such as sebacic acid esters and azelaic acid esters; unsaturated dicarboxylic acid esters such as maleic acid esters; and others such as N-ethyl toluenesulfonamide, O-cresyl p-toluenesulfonate, and tripropionin.
• polyester refers to a polycondensate synthesized by polymerizing a carboxylic acid and/or an alcohol through an ester bond.
• polyester include a polycondensate synthesized by dehydration condensation of a dicarboxylic acid and a diol, and a polycondensate synthesized by dehydration condensation of a hydroxycarboxylic acid.
• dicarboxylic acids examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid, and adipic acid or succinic acid is preferable, and succinic acid is particularly preferable.
• diols examples include 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, heptaethylene glycol, 1,2-benzenedimethanol, etc., with 1,4-butanediol being preferred.
• hydroxycarboxylic acids include lactic acid, tartaric acid, citric acid, salicylic acid, gallic acid, 6-hydroxyhexanoic acid, etc., with lactic acid being preferred.
• polyesters By selecting a combination of a carboxylic acid and an alcohol, and a hydroxycarboxylic acid, it is possible to synthesize a variety of polyesters.
• the polyester polybutylene succinate, polybutylene succinate adipate, polylactic acid, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polybutylene adipate terephthalate, polycaprolactone, and mixtures thereof are preferred, and a polyester selected from the group consisting of polybutylene succinate, polybutylene succinate adipate, and polylactic acid is more preferred, with polybutylene succinate being particularly preferred.
• the content of component C is preferably 0.5% by mass or more, more preferably 1% by mass or more, and particularly preferably 3% by mass or more, relative to 100% by mass of the total content of components A, B, and C. Also, the content is preferably 10% by mass or less, more preferably 7% by mass or less, and particularly preferably 6% by mass or less, relative to 100% by mass of the total content of components A, B, and C.
• the content of component C within this range, the exudation (bleed-out) of component B can be suppressed. If the content of component C is too high, processing stability may be impaired, and if the content of component C is too low, the effect of suppressing the exudation of component B may be insufficient.
• the content of component C is preferably 6 to 8 mass%, more preferably 6.2 to 7.8 mass%, and particularly preferably 6.5 to 7.7 mass%, relative to 100 mass% of the total content of components A and C.
• the exudation (bleed-out) of component B can be suppressed. If the content of component C is too high, processing stability may be impaired, and if the content of component C is too low, the effect of suppressing the exudation of component B may be insufficient.
• component B can improve flame retardancy and mechanical strength (impact resistance), but if the content of component B is high, bleeding may occur in high temperature and high humidity environments. Therefore, by adding component C, bleeding can be suppressed and the amount of component B can be increased. Therefore, by containing components A, B, and C, the resin composition of the present invention achieves both mechanical strength and bleeding suppression.
• the resin composition of the present invention contains a metal hydroxide as component D. By containing a metal hydroxide, the resin composition can have improved flame retardancy.
• metal hydroxides examples include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, etc.
• aluminum hydroxide is particularly preferred because it has a high heat absorbing effect and excellent flame retardancy.
• the surface of the metal hydroxide may be surface treated with various organic substances such as epoxy resin and phenol resin.
• One type of metal hydroxide may be used alone, or two or more types may be used in combination.
• the 50% particle size (median size, D 50 ) of the metal hydroxide is not particularly limited, but is preferably 0.5 ⁇ m or more and 20 ⁇ m or less, more preferably 1 ⁇ m or more and 10 ⁇ m or less, and even more preferably 2 ⁇ m or more and 4 ⁇ m or less.
• the 50% particle size of the metal hydroxide is within this range, it has excellent dispersibility in the resin composition, which leads to improved flame retardancy and mechanical properties. If the 50% particle size of the metal hydroxide is too small, the viscosity of the resin composition may increase and the moldability may decrease. In addition, the increase in viscosity may increase the shear force during kneading or molding, which may cause deterioration of other components.
• the average particle size of the metal hydroxide can be determined, for example, by measuring the volume-based median size by a diffraction/scattering method.
• the content of component D is preferably 0.5% by mass to 20% by mass, and more preferably 0.5% by mass to 17.5% by mass, relative to 100% by mass of the total amount of the resin composition. If the content of component D is too low, the flame retardancy may be insufficient. On the other hand, if the content of component D is too high, the toughness may decrease, resulting in a resin composition with poor mechanical properties.
• the content of component D is preferably 0.5% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass, relative to 100% by mass of the total amount of the resin composition.
• the content of component D is preferably 10% by mass to 20% by mass, and more preferably 10% by mass to 17.5% by mass, relative to 100% by mass of the total amount of the resin composition.
• the resin composition of the present invention preferably further contains an anti-drip agent as component E.
• an anti-drip agent As the anti-drip agent, a fluorine-based anti-drip agent (fluorine-containing polymer) is preferable, and it is more preferable to contain a fluorine-containing polymer that forms a fiber structure (fibril structure) in the resin composition. By blending a fluorine-containing polymer, the effect of suppressing the drip phenomenon during combustion can be improved.
• Drip prevention agents include, for example, polytetrafluoroethylene, tetrafluoroethylene copolymers (e.g., tetrafluoroethylene/hexafluoropropylene copolymers, etc.), resins in which polytetrafluoroethylene is acrylic-modified, fluorine-based resins such as polyvinylidene fluoride and polyhexafluoropropylene, and perfluoroalkanesulfonic acid alkali metal salt compounds or perfluoroalkanesulfonic acid alkaline earth metal salts such as sodium perfluoromethanesulfonate, potassium perfluoro-n-butanesulfonate, potassium perfluoro-t-butanesulfonate, sodium perfluorooctane sulfonate, and calcium perfluoro-2-ethylhexanesulfonate.
• polytetrafluoroethylene e.g., tetra
• fluoropolymers such as fine powder fluoropolymers, aqueous dispersions of fluoropolymers, mixtures of powder fluoropolymers and acrylonitrile-styrene copolymers, and mixtures of powder fluoropolymers and polymethyl methacrylate can also be used as the fluorine-containing polymer.
• silicone compounds such as silicone rubbers and layered silicates such as talc may be blended as other drip prevention agents. These may be used alone or in combination of two or more.
• fluorine-based drip prevention agents having fibril-forming ability are preferred, with polytetrafluoroethylene being particularly preferred.
• the molecular weight of the fluorine-based drip prevention agent is preferably 1 to 10 million, more preferably 2 to 9 million, in terms of number average molecular weight calculated from the standard specific gravity.
• Such polytetrafluoroethylene may be in the form of a solid or an aqueous dispersion.
• the content of component E is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, more preferably 0.2 mass% or more, and even more preferably 0.3 mass% or more, relative to 100 mass% of the total amount of the resin composition, and is preferably 2 mass% or less, more preferably 1.5 mass% or less, and even more preferably 1.0 mass% or less.
• the flame retardancy is further improved.
• the content of component E is preferably 0.1 to 10 mass%, more preferably 0.3 to 7 mass%, and particularly preferably 0.5 to 5 mass%, relative to 100 mass% of component D.
• flame retardancy is further improved.
• Component F Inorganic or organic granular or fibrous filler>
• the resin composition of the present invention preferably contains an inorganic or organic granular or fibrous filler as component F. By adding these fillers, mechanical strength and rigidity can be further improved.
• fillers include mineral particles (talc, mica, calcined silica, kaolin, sericite, bentonite, smectite, clay, silica, quartz powder, glass beads, glass powder, glass flakes, milled fiber, wollastonite (or wollastonite), etc.), boron-containing compounds (boron nitride, boron carbide, titanium boride, etc.), metal carbonates (magnesium carbonate, heavy calcium carbonate, light calcium carbonate, etc.), metal silicates (calcium silicate, aluminum silicate, magnesium silicate, magnesium aluminosilicate, etc.), metal oxides (magnesium oxide, etc.), metal sulfates (calcium sulfate, barium sulfate, etc.), metal carbides (silicon carbide, aluminum carbide, titanium carbide, etc.), metal nitrides (aluminum nitride, silicon nitride, titanium nitride, etc.
• fibrous fillers examples include organic fibers (natural fibers, paper, etc.), inorganic fibers (glass fibers, asbestos fibers, carbon fibers, silica fibers, silica-alumina fibers, wollastonite, zirconia fibers, potassium titanate fibers, etc.), metal fibers, etc. These fillers can be used alone or in combination of two or more.
• the resin composition preferably contains glass fibers.
• the strength of the molded body is improved by including glass fibers in the resin composition.
• the glass fibers are not particularly limited, but the fiber length of the glass fibers before melt-kneading is preferably 0.5 mm or more, and preferably 30 mm or less, and more preferably 10 mm or less.
• the cross-sectional shape of the glass fibers is not particularly limited, and examples thereof include circular, elliptical, oval, and non-circular.
• the fiber diameter of the glass fibers may be, for example, 3 to 20 ⁇ m when the cross-sectional area is converted into a perfect circle.
• the content of the glass fibers relative to the total mass of the resin composition may be 0 mass%, but is preferably 0.5 mass% or more, more preferably 1 mass% or more, and even more preferably 3 mass% or more, and is also preferably 20 mass% or less, more preferably 10 mass% or less, and even more preferably 8 mass% or less.
• the content of component F is preferably 1 mass% or more, more preferably 2 mass% or more, and particularly preferably 3 mass% or more, relative to 100 mass% of the total amount of the resin composition. Also, relative to 100 mass% of the total amount of the resin composition, it is preferably 10 mass% or less, more preferably 8 mass% or less, and particularly preferably 5 mass% or less. By having the content of component F within this range, the resin composition can fully obtain the effect of improving the mechanical strength.
• the resin composition may contain a colorant such as a black colorant.
• the content of the colorant such as a black colorant is not limited, but can be set in the range of 0.01 to 10 phr (0.01 to 10 parts by mass per 100 parts by mass of the total mass of the components other than the colorant) relative to the total mass of the components other than the colorant.
• the content of the colorant is preferably 0.05 phr or more, and preferably 0.1 phr or more, relative to the total mass of the components other than the colorant.
• the content is preferably 5 phr or less, more preferably 3 phr or less, and even more preferably 2 phr or less.
• the content of the colorant is preferably 1 phr or less, more preferably 0.3 phr or less, even more preferably 0.2 phr or less, and particularly preferably 0.1 phr or less.
• the resin composition may contain a hydrolysis inhibitor.
• a hydrolysis inhibitor is a compound that can react with carboxylic acid generated by hydrolysis of cellulose acetate or polyester.
• Hydrolysis inhibitors include compounds having functional groups such as carbodiimide groups, epoxy groups, and oxazoline groups, and carbodiimide compounds having carbodiimide groups are preferred.
• the carbodiimide compound may be a compound having two or more carbodiimide groups in the molecule, i.e., a polyvalent carbodiimide compound.
• the polyvalent carbodiimide compound preferably has 30 or less carbodiimide groups in the carbodiimide compound.
• a high molecular weight polycarbodiimide produced by subjecting a diisocyanate to a decarboxylation condensation reaction in the presence of a carbodiimide catalyst may be used as the carbodiimide compound.
• carbodiimide compounds include monocarbodiimides such as aliphatic monocarbodiimides, alicyclic monocarbodiimides, and aromatic monocarbodiimides, and polycarbodiimides such as aliphatic polycarbodiimides, alicyclic polycarbodiimides, and aromatic polycarbodiimides.
• aliphatic monocarbodiimides examples include diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, and dioctylcarbodiimide.
• An example of an alicyclic monocarbodiimide is dicyclohexylcarbodiimide.
• Aromatic monocarbodiimides include N,N'-diphenylcarbodiimide and N,N'-di-2,6-diisopropylphenylcarbodiimide.
• Polycarbodiimides include those obtained by decarboxylation condensation reaction of the following diisocyanates:
• diisocyanates include 1,4-phenylene diisocyanate, 1,3,5-triisopropyl-phenylene-2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, 3,3'-dimethyl-4,4'-diphenylether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and tetra
• the number average molecular weight of the polycarbodiimide is not particularly limited, but it is preferable to use one having a molecular weight of, for example, preferably 200 or more, more preferably 300 or more, and preferably 20,000 or less.
• the carbodiimide compound may be either one that has an isocyanate group in the molecule or one that does not have an isocyanate group in the molecule, and can be selected appropriately.
• both ends of the molecule or any part in the molecule may have a functional group such as an isocyanate group, or the molecular chain may be branched, giving a molecular structure different from other parts.
• the carbodiimide compound may have a heterocycle or other functional group in the molecule.
• carbodiimide compounds such as the Carbodilite (registered trademark) series manufactured by Nisshinbo Chemical Co., Ltd. (e.g., Carbodilite HMV-15CA, HMV-5CA-LC, LA-1); STABAXOL I POWDER, STABAXOL P, STABAXOL P 100 manufactured by LANXESS; and TCC-NP manufactured by Teijin Limited.
• Carbodilite registered trademark
• STABAXOL I POWDER STABAXOL P
• STABAXOL P 100 manufactured by LANXESS
• TCC-NP manufactured by Teijin Limited.
• Examples of compounds containing epoxy groups include glycidyl ester compounds and glycidyl ether compounds.
• Examples of compounds containing oxazoline groups include bisoxazoline compounds.
• the hydrolysis inhibitors may be used alone or in combination of two or more.
• the content of the hydrolysis inhibitor is not particularly limited and may be 0% by mass relative to the total content of components A, B, and C, which is 100% by mass. However, for example, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less.
• the resin composition may contain, as other components, additives that are generally used in ordinary resin materials for molding, provided that the purpose of the present invention is not impaired.
• additives include colorants, antioxidants such as phenolic and phosphorus-based, light stabilizers, ultraviolet absorbers, antistatic agents, antibacterial and antifungal agents, and fillers.
• the resin composition may contain additives that are generally used in ordinary cellulose resins.
• the method for producing the resin composition of the present invention is not particularly limited, and for example, the resin composition can be obtained by melt-mixing component A, component B, component C, and component D, and other components as necessary, in a normal mixer.
• a compounding device such as a tumbler mixer, a ribbon blender, a single-screw or multi-screw mixer extruder, a kneading kneader, or a kneading roll can be used.
• the mixture can be granulated into an appropriate shape as necessary, and can be pelletized using a pelletizer, for example.
• the molded article formed using the resin composition according to the present invention can be molded into a desired shape by a normal molding method.
• the thickness of the molded article is not particularly limited, but from the viewpoint of strength, it is preferably 0.5 mm or more, more preferably 0.8 mm or more.
• the thickness of the molded article is preferably 1.0 mm or more, more preferably 1.6 mm or more, more preferably 2.0 mm or more, and even more preferably 3.2 mm or more.
• the upper limit of the thickness of the molded article is not particularly limited, and can be appropriately set according to the required shape, strength, etc., but can be, for example, 10 mm or less, or even 5 mm or less.
• the resin composition according to the present invention can be molded into a molded article according to the intended purpose using conventional molding methods such as injection molding, injection compression molding, extrusion molding, and hot press molding.
• molded articles formed using the resin composition according to the present invention have excellent design properties, they can be applied to housings, exteriors, decorative panels, and decorative sheets, and can be used in place of components used in, for example, electronic devices, home appliances, building materials, furniture, and automobiles. For example, they can be used in housings and exterior parts of electronic devices and home appliances, interior components of building materials, and interior materials for automobiles.
• Applications for electronic devices or home appliances include housings for personal computers, landline phones, mobile phone terminals, smartphones, tablets, POS terminals, routers, projectors, speakers, lighting equipment, copiers, multifunction printers, calculators, remote controls, refrigerators, washing machines, humidifiers, dehumidifiers, video recorders/players, vacuum cleaners, air conditioners, rice cookers, electric shavers, electric toothbrushes, dishwashers, broadcasting equipment, clock dials and exteriors, and cases for mobile devices such as smartphones.
• Automotive applications include interior instrument panels, dashboards, cup holders, door trim, armrests, door handles, door locks, steering wheels, brake levers, ventilators, shift levers, etc.
• UL94V is a method in which a burner flame (20 ⁇ 1 mm flame) is applied to the lower end of a test specimen of a given size held vertically for 10 seconds, and the flame retardancy is evaluated based on the subsequent burning time and dripping properties, etc., and the grades are 5V-A, 5V-B, V-0, V-1, V-2, and HB, ranked from best to worst. V-2 or higher is considered to be good flame retardancy.
• V-0, V-1, and V-2 are as shown in Table 1 below. (Evaluation sample 1): Length 125 mm, width 13 mm, thickness 2.0 mm (Evaluation sample 2): Length 125 mm, width 13 mm, thickness 3.2 mm
• the flaming combustion time is the length of time the test specimen continues to burn with a flame after the ignition source (burner) is removed, where t1 is the burning time after the first flame application, t2 is the burning time after the second flame application, and t3 is the afterglow (flameless combustion) time after the second flame application.
• the second flame application is performed by immediately applying the burner flame to the test specimen for 10 seconds if the flame goes out after the first flame application.
• the ignition of cotton by drips is determined by whether the marking cotton located 300 ⁇ 10 mm below the bottom end of the test specimen is ignited by drips from the test specimen.
• a Charpy impact test was carried out using an evaluation sample having a shape of JIS K 7162 test piece 1A in accordance with JIS K7111-1 (notched: Type A (notch cutter tip R 0.25 mm)).
• ⁇ Deflection temperature under load test> In accordance with JIS K 7191-2-2007, the oil temperature was raised at a constant rate (120°C/h), and a bending stress of 1.80 MPa was applied to an evaluation sample having a length of 80 mm, a width of 10 mm, and a thickness of 4.0 mm. The temperature at which the specified deflection amount was reached was defined as the deflection temperature under load (support distance: 100 mm).
• ⁇ Flexural modulus test> Using an evaluation sample having a length of 80 mm, a width of 10 mm and a thickness of 4.0 mm, the flexural modulus (GPa) was measured in accordance with JIS K 7171 (the average value of two samples was used).
• Test Example 5 which contained Component C and Component D, seepage was suppressed. It was also confirmed that Test Example 5, which contained Component C and Component D, had a higher flexural modulus than Test Examples 2 to 4, which did not contain Component D (metal oxide). Test Example 5 also had good flame retardancy.
• component E antioxidant-drip agent
• the amount of component E is preferably 0.1 to 0.5 mass% of the entire composition.
• the content of component D is preferably 10 to 20 mass% of the entire composition.
• component F an inorganic or organic granular or fibrous filler. Furthermore, it was found that the amount of component F is preferably 1 to 10 mass% of the entire composition.
• Component A cellulose acetate
• Component B a plasticizer which is a phosphoric acid ester
• Component C polyester
• Component D a metal hydroxide
• a resin composition comprising: The content of the component B is 20 to 30% by mass relative to 100% by mass of the total content of the components A, B and C, The content of the component C is 0.5 to 10 mass% relative to 100 mass% of the total content of the components A, B and C, A cellulose-based resin composition, wherein the content of component D relative to the entire composition is 0.5 to 20 mass %.
• Appendix 2 The cellulose-based resin composition according to Appendix 1, wherein the component B is at least one selected from the group consisting of triphenyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate, cresyl di-2,6-xylenyl phosphate, and a compound represented by the following formula (2):
• Appendix 3 The resin composition according to claim 1 or 2, wherein the component C is at least one selected from the group consisting of polybutylene succinate, polybutylene succinate adipate, and polylactic acid.
• Appendix 4 The cellulose-based resin composition according to any of the preceding appendices, wherein component D is aluminum hydroxide.
• (Appendix 5) The cellulose-based resin composition according to any one of the preceding appendices, wherein the content of component D relative to the total amount of the composition is 0.5 to 10 mass%.
• Component E The cellulose-based resin composition of any of the preceding paragraphs, further comprising an anti-drip agent.
• (Appendix 7) The cellulose-based resin composition according to claim 6, wherein the content of component E relative to the total amount of the composition is 0.01 to 2 mass%.
• (Appendix 8) The cellulose-based resin composition according to claim 6, wherein the content of component D relative to the entire composition is 10 to 20 mass%.
• Component F The cellulose-based resin composition described in any of the preceding appendices, further comprising an inorganic or organic granular or fibrous filler.
• Component F The cellulose-based resin composition according to any one of the preceding appendices, wherein the content of the component B is 22 to 29% by mass relative to 100% by mass of the total content of the components A, B and C.
• Appendix 11 The cellulose-based resin composition according to any one of the preceding appendices, wherein the content of the component B is 25 to 28% by mass relative to 100% by mass of the total content of the components A, B and C.
• (Appendix 12) The cellulose-based resin composition according to any one of the preceding appendices, wherein the content of the component C is 1 to 7% by mass relative to 100% by mass of the total content of the components A, B and C.
• (Appendix 13) The cellulose-based resin composition according to any one of the preceding appendices, wherein the content of the component C is 3 to 6% by mass relative to 100% by mass of the total content of the components A, B and C.
• Component E A cellulose-based resin composition according to any one of the preceding appendices, comprising an anti-drip agent, and the content of component D is 10 to 17.5% by mass relative to 100% by mass of the total content of components A, B and C.
• Component E The cellulose-based resin composition according to any one of the preceding appendices, which does not contain an anti-drip agent and has a content of 0.5 to 5 mass% of the component D relative to a total content of 100 mass% of the components A, B and C.
• Appendix 16 The cellulose-based resin composition according to any one of claims 9 to 15, wherein the content of component F is 1 to 10 mass% relative to 100 mass% of the total content of components A, B and C.
• Appendix 17 4. The cellulose-based resin composition of any of the preceding paragraphs, further comprising a hydrolysis inhibitor.
• Component A cellulose acetate
• Component B a plasticizer which is a phosphoric acid ester
• Component C polyester
• Component D a metal hydroxide
• a resin composition comprising:
• the component B is at least one selected from the group consisting of triphenyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate, cresyl di-2,6-xylenyl phosphate, and a compound represented by the following formula (2):
• the component C is at least one selected from the group consisting of polybutylene succinate, polybutylene succinate adipate, and polylactic acid
• Component D is aluminum hydroxide
• the content of the component B is 20 to 30% by mass relative to 100% by mass
• Appendix 20 A molded article formed using the cellulose-based resin composition according to any one of the preceding appendices.
• Appendix 21 The molded article according to claim 20, which is any one of a housing, an exterior material, an interior material, a decorative plate, and a decorative sheet in electronic devices, home appliances, building materials, furniture, and automobiles.
• the electronic device or home appliance is any one of a personal computer, a landline phone, a mobile phone terminal, a smartphone, a tablet, a POS terminal, a router, a projector, a speaker, a lighting fixture, a copier, a multifunction printer, a calculator, a remote control, a refrigerator, a washing machine, a humidifier, a dehumidifier, a video recorder/player, a vacuum cleaner, an air conditioner, a rice cooker, an electric shaver, an electric toothbrush, a dishwasher, a broadcasting equipment, and a clock.

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• 2023
  • 2023-11-14 WO PCT/JP2023/040922 patent/WO2024106426A1/ja not_active Ceased
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