Classifications

• • 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
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/672—Dicarboxylic acids and dihydroxy compounds
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
  • C08K2003/265—Calcium, strontium or barium carbonate
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
  • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

• the present invention relates to a biodegradable resin composition and molded articles of the composition.
• Disposable containers, disposable packaging materials, etc. are generally molded from resin compositions containing general-purpose plastics and inorganic fillers, and the inorganic fillers impart various functions such as impact resistance, bending resistance, dimensional stability, and moisture permeability. It is
• Patent Documents 1 and 2 In order to improve functionality and reduce the amount of plastic in the resin composition containing the inorganic filler, it is required to further increase the amount of inorganic filler filled. On the other hand, when the amount of inorganic filler is increased, there is a problem that the fluidity of the composition is lowered and the moldability is lowered. This problem has been solved by adding a fluidity modifier (Patent Documents 1 and 2).
• the problem to be solved by the present invention is to provide a biodegradable resin composition with high fluidity.
• the present inventors found that by using a polyester having a specific structure and physical properties as a fluidity modifier, biodegradation containing an inorganic filler and a biodegradable resin The present inventors have completed the present invention by finding that high fluidity can be imparted to a flexible resin composition.
• the present invention provides a biodegradable resin composition containing a biodegradable resin, an inorganic filler, and a fluidity modifier, wherein the fluidity modifier has a carboxyl group at least one end.
• a biodegradable resin composition which is a polyester having an acid value of more than 50.
• the present invention can provide a biodegradable resin composition with high fluidity.
• the biodegradable resin composition of the present invention contains a biodegradable resin, an inorganic filler, and a fluidity modifier, wherein the fluidity modifier has a carboxyl group at at least one end and an acid value of It is a polyester that is greater than 50.
• biodegradable resin means a resin that can be decomposed to the molecular level by the action of microorganisms present in soil, water, oceans, and the like.
• the biodegradable resin is generally highly polar and has the property of being easily increased in viscosity due to entanglement of molecular chains.
• the biodegradable composition of the present invention contains a polyester having a specific acid value and a carboxyl group at at least one terminal as a fluidity modifier. In this polyester, the carboxyl group is adsorbed to the inorganic filler, and at the same time, the acid value of the polyester itself ensures compatibility with the highly polar biodegradable resin, which is thought to increase the fluidity of the inorganic filler.
• the fluidity modifier contained in the biodegradable resin composition of the present invention has a carboxyl group at at least one end and an acid value of is more than 50, preferably a polyester having a repeating unit represented by the following general formula (A) and a repeating unit represented by the following general formula (G), or the following general formula (L) , a repeating unit represented by the following general formula (A), and a repeating unit represented by the following general formula (G).
• A is an aliphatic dibasic acid residue having 2 to 12 carbon atoms or an aromatic dibasic acid residue having 6 to 15 carbon atoms
• G is an aliphatic diol residue having 2 to 9 carbon atoms
• L is a hydroxycarboxylic acid residue having 2 to 18 carbon atoms.
• polyester of the present invention which is the fluidity modifier of the present invention, is not particularly limited, and may be a random copolymer containing the above repeating unit. It may be a block copolymer containing.
• the polyester of the present invention is more preferably a polyester represented by the following general formula (1) and/or a polyester represented by the following general formula (2).
• a 1 , A 2 and A 3 are each independently an aliphatic dibasic acid residue having 2 to 12 carbon atoms or an aromatic dibasic acid residue having 6 to 15 carbon atoms
• G 1 and G 2 are each independently an aliphatic diol residue having 2 to 9 carbon atoms
• n represents the number of repetitions and is an integer in the range of 0-20.
• a 1 and G 1 may be the same or different for each parenthesized repeating unit.
• the "dibasic acid residue” is an organic group obtained by removing the basic acid functional group from the dibasic acid.
• the dibasic acid residue refers to the remaining organic groups other than the carboxyl group of the dicarboxylic acid.
• the number of carbon atoms in the dicarboxylic acid residue does not include the carbon atoms in the carboxyl group.
• the term "diol residue” refers to organic groups remaining after removal of hydroxyl groups from diols.
• hydroxycarboxylic acid residue refers to organic groups remaining after removing a hydroxyl group and a carboxyl group from a hydroxycarboxylic acid.
• the number of carbon atoms in the hydroxycarboxylic acid residue does not include the carbon atoms in the carboxyl group.
• the aliphatic dibasic acid residues having 2 to 12 carbon atoms of A, A 1 , A 2 and A 3 may contain an alicyclic structure and/or an ether bond (--O--).
• the aliphatic dibasic acid residue having 2 to 12 carbon atoms of A, A 1 , A 2 and A 3 is preferably an aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms, and the 2 carbon atom -12 aliphatic dicarboxylic acid residues include succinic acid residue, adipic acid residue, maleic acid residue, pimelic acid residue, suberic acid residue, azelaic acid residue, sebacic acid residue, cyclohexanedicarboxylic acid residues, dodecanedicarboxylic acid residues, hexahydrophthalic acid residues, and the like.
• the aliphatic dibasic acid residue having 2 to 12 carbon atoms of A, A 1 , A 2 and A 3 is preferably an aliphatic dicarboxylic acid residue having 2 to 10 carbon atoms, more preferably succinic acid. residues, sebacic acid residues, maleic acid residues and adipic acid residues, more preferably succinic acid residues, sebacic acid residues and maleic acid residues.
• aromatic dibasic acid residues having 6 to 15 carbon atoms of A, A 1 , A 2 and A 3 are preferably aromatic dicarboxylic acid residues having 6 to 15 carbon atoms.
• An acid residue and the like can be mentioned.
• A, A 1 , A 2 and A 3 are preferably aliphatic dibasic acid residues having 2 to 12 carbon atoms, more preferably aliphatic dicarboxylic acid residues having 2 to 12 carbon atoms, More preferably, it is an aliphatic dicarboxylic acid residue having 2 to 10 carbon atoms.
• Aliphatic diol residues having 2 to 9 carbon atoms for G, G 1 and G 2 include ethylene glycol residues, 1,2-propylene glycol residues, 1,3-propylene glycol residues, 1,2- propanediol residue, 1,3-propanediol residue, 1,2-butanediol residue, 1,3-butanediol residue, 2-methyl-1,3-propanediol residue, 1,4-butane diol residue, 1,5-pentanediol residue, 2,2-dimethyl-1,3-propanediol (neopentyl glycol) residue, 2,2-diethyl-1,3-propanediol (3,3- dimethylol-pentane) residue, 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane) residue, 3-methyl-1,5-pentanediol residue, 1, 6-he
• the C 2-9 aliphatic diol residues of G, G 1 and G 2 may contain an alicyclic structure and/or an ether bond (--O--).
• Examples of the aliphatic diol residue having 2 to 9 carbon atoms containing an alicyclic structure include 1,3-cyclopentanediol residue, 1,2-cyclohexanediol residue, and 1,3-cyclohexanediol residue. , 1,4-cyclohexanediol residue, 1,2-cyclohexanedimethanol residue, 1,4-cyclohexanedimethanol residue and the like.
• Examples of the aliphatic diol residue having 2 to 9 carbon atoms containing an ether bond include diethylene glycol residue, triethylene glycol residue, tetraethylene glycol residue, dipropylene glycol residue, tripropylene glycol residue, and the like. is mentioned.
• the aliphatic diol residues having 2 to 9 carbon atoms of G, G 1 and G 2 are preferably aliphatic diol residues having 3 to 8 carbon atoms, more preferably ethylene glycol residues and diethylene glycol residues. , 1,2-propylene glycol residue, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,4-butanediol or 1,3-butanediol residue.
• hydroxycarboxylic acid residues having 2 to 18 carbon atoms for L include propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, caprylic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, and pentadecyl.
• Acids, palmitic acid, margaric acid, hydroxycarboxylic acid residues in which one hydroxyl group is substituted in the fatty chain of aliphatic carboxylic acids having 3 to 19 carbon atoms such as stearic acid specific examples include lactic acid residues. , 9-hydroxystearic acid residue, 12-hydroxystearic acid residue, 6-hydroxycaproic acid residue and the like.
• the hydroxycarboxylic acid residue having 2 to 18 carbon atoms in L is preferably an aliphatic hydroxycarboxylic acid residue having 4 to 18 carbon atoms, more preferably a 12-hydroxystearic acid residue.
• n is an integer in the range of 0-20, preferably an integer in the range of 1-20, more preferably an integer in the range of 5-20.
• the number average molecular weight (Mn) of the polyester of the present invention is, for example, in the range of 100 to 5,000, preferably in the range of 300 to 4,000, more preferably in the range of 500 to 3,000. , more preferably in the range of 800 to 2,400.
• the above number average molecular weight (Mn) is a value converted to polystyrene based on gel permeation chromatography (GPC) measurement, and is measured by the method described in Examples.
• the polyester of the present invention may have an acid value of more than 50, preferably 51 or more.
• the upper limit of the acid value of the polyester of the present invention is not particularly limited, it is, for example, 400 or less, preferably 200 or less, 150 or less, 120 or less, 100 or less, and 95 or less, in that order.
• the acid value of the polyester is confirmed by the method described in Examples.
• the hydroxyl value of the polyester of the present invention may be, for example, 0 or more, preferably in the range of 10-100, more preferably in the range of 20-80, still more preferably in the range of 30-70.
• the hydroxyl value of the polyester is confirmed by the method described in Examples.
• the properties of the polyester of the present invention vary depending on the number average molecular weight, composition, etc., but it is usually liquid, solid, pasty, etc. at room temperature.
• the content of the fluidity modifier of the present invention is not particularly limited. It is in the range of 0.1 to 10 parts by mass of the fluidity modifier of the present invention with respect to 100 parts by mass of the filler, more preferably 0.1 to 10 parts by mass of the fluidity modifier of the present invention with respect to 100 parts by mass of the inorganic filler. It is in the range of 5.0 parts by mass.
• the polyesters of the present invention are obtained using reactants containing aliphatic and/or aromatic dibasic acids, aliphatic diols, and optional hydroxycarboxylic acids.
• the reaction raw material means a raw material that constitutes the polyester of the present invention, and does not contain a solvent or a catalyst that does not constitute the polyester.
• any hydroxycarboxylic acid means that a hydroxycarboxylic acid may or may not be used.
• the method for producing the polyester of the present invention is not particularly limited, and it can be produced by a known method, and can be produced by the production method described below.
• the reaction raw materials of the polyester of the present invention may contain an aliphatic dibasic acid and/or an aromatic dibasic acid, an aliphatic diol, and any hydroxycarboxylic acid, and may contain other raw materials.
• 90% by mass or more of the reaction raw material of the polyester of the present invention is aliphatic dibasic acid and/or aromatic dibasic acid, aliphatic diol, and any hydroxycarboxylic acid with respect to the total amount of the reaction raw material, More preferably, it consists only of aliphatic and/or aromatic dibasic acids, aliphatic diols, and optional hydroxycarboxylic acids.
• the aliphatic dibasic acid used in the production of the polyester of the present invention is an aliphatic dibasic acid corresponding to the aliphatic dibasic acid residues of A, A 1 , A 2 and A 3 having 2 to 12 carbon atoms. , the aliphatic dibasic acid to be used may be used singly or in combination of two or more.
• the aromatic dibasic acid used in the production of the polyester of the present invention is an aromatic dibasic acid corresponding to the aromatic dibasic acid residue having 6 to 15 carbon atoms of A, A 1 , A 2 and A 3 . , the aromatic dibasic acid to be used may be used singly or in combination of two or more.
• the aliphatic diol used in the production of the polyester of the present invention is an aliphatic diol corresponding to the aliphatic diol residue having 2 to 9 carbon atoms of G, G 1 and G 2 , and one type of aliphatic diol is used. It may be used alone or in combination of two or more.
• the hydroxycarboxylic acid used in the production of the polyester of the present invention is a hydroxycarboxylic acid corresponding to a hydroxycarboxylic acid residue having 2 to 18 carbon atoms in L, and the hydroxycarboxylic acid used may be used singly. , may be used in combination of two or more.
• the reactants to be used also include derivatives such as the above esters, acid chlorides, and acid anhydrides.
• hydroxycarboxylic acids also include compounds having a lactone structure such as ⁇ -caprolactone.
• the polyester of the present invention comprises an aliphatic dibasic acid and/or aromatic dibasic acid, an aliphatic diol, and any hydroxycarboxylic acid that constitute each residue of the polyester of the present invention, and a carboxyl group contained in the reaction raw material. can be produced by reacting under conditions in which the equivalent of is greater than the equivalent of the hydroxyl group.
• an aliphatic dibasic acid and/or aromatic dibasic acid, an aliphatic diol, and any hydroxycarboxylic acid that constitute each residue of the polyester of the present invention are added to the hydroxyl groups contained in the reaction raw materials.
• the obtained polyester is further added with an aliphatic dibasic acid and / or an aromatic dibasic acid. It can also be produced by reacting.
• polyesters of the present invention preferably contain one or more aliphatic dibasic acids selected from the group consisting of succinic acid, sebacic acid, maleic acid and adipic acid residues, ethylene glycol, diethylene glycol, 1,2-propanediol.
• the polyester of the present invention is more preferably one or more aliphatic dibasic acids selected from the group consisting of succinic acid and sebacic acid, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol , 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,4-butanediol and one or more aliphatic diols selected from 1,3-butanediol as reaction raw materials is. All of these reaction raw materials can be derived from biomass, and the obtained polyester can be a polyester having a biomass content of 100%. From the viewpoint of sustainability, it is preferable to use polyester with a biomass content of 100% as the biodegradable resin.
• the reaction of the reaction raw materials may optionally be carried out in the presence of an esterification catalyst, for example, at a temperature of 180 to 250° C. for 10 to 25 hours.
• an esterification catalyst for example, at a temperature of 180 to 250° C. for 10 to 25 hours.
• Conditions such as the temperature and time of the esterification reaction are not particularly limited and may be set as appropriate.
• esterification catalyst examples include titanium catalysts such as tetraisopropyl titanate and tetrabutyl titanate; zinc catalysts such as zinc acetate; tin catalysts such as dibutyltin oxide; and organic sulfonic acid catalysts such as p-toluenesulfonic acid. catalysts, and the like.
• the amount of the esterification catalyst used may be set appropriately, but it is usually used in the range of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials.
• the inorganic filler contained in the biodegradable resin composition of the present invention is not particularly limited, and examples include calcium carbonate, talc, silica, alumina, clay, antimony oxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, and silicic acid. Calcium, magnesium oxide, potassium titanate, barium titanate, titanium oxide, calcium oxide, magnesium oxide, manganese dioxide, boron nitride, aluminum nitride and the like.
• the said inorganic filler may be used individually by 1 type, and may use 2 or more types together.
• the inorganic filler is preferably one or more selected from the group consisting of calcium carbonate, silica, alumina, aluminum hydroxide, barium titanate, talc, boron nitride and aluminum nitride, more preferably calcium carbonate, alumina, It is one or more selected from the group consisting of aluminum hydroxide and talc.
• the particle size, fiber length, fiber diameter, and other shapes of the inorganic filler are not particularly limited, and may be appropriately adjusted according to the intended use.
• the surface treatment state of the inorganic filler is not particularly limited, and the surface may be modified with, for example, saturated fatty acid, depending on the intended use.
• the content of the inorganic filler is in the range of, for example, 1 to 200 parts by mass, 1 to 100 parts by mass, 5 to 70 parts by mass, and 10 to 60 parts by mass with respect to 100 parts by mass of the biodegradable resin. or 15 to 55 parts by mass.
• Biodegradable resins contained in the biodegradable resin composition of the present invention include polylactic acid (PLA), polyethylene succinate (PES), polyethylene terephthalate-succinate (PETS), polybutylene succinate (PBS), and polybutylene.
• PLA polylactic acid
• PES polyethylene succinate
• PETS polyethylene terephthalate-succinate
• PBS polybutylene succinate
• Adipate-terephthalate (PBAT), polyethylene adipate-terephthalate (PEAT), polybutylene succinate-terephthalate (PBST), polyethylene succinate-terephthalate (PEST), polybutylene succinate-adipate (PBSA), polybutylene succinate-carbonate (PEC), polybutylene succinate-adipate-terephthalate (PBSAT), polyethylene succinate-adipate-terephthalate (PESAT), polytetramethylene adipate-terephthalate (PTMAT), polyhydroxybutyric acid (PHB), polyhydroxybutyric acid-hydroxyhexane acid (PHBH), polycaprolactone (PCL), polycaprolactone-butylene succinate (PCLBS), cellulose acetate and the like.
• the biodegradable resin to be used may be determined according to the intended use, and the above biodegradable resins may be used singly or in combination of two or more.
• the biodegradable resin is preferably one or more selected from the group consisting of polylactic acid, polybutylene succinate, polybutylene adipate terephthalate, polyhydroxybutyric acid-hydroxyhexanoic acid, polybutylene succinate adipate and polyethylene terephthalate succinate. be.
• the biodegradable resin composition of the present invention may contain non-biodegradable resins as long as the effects of the present invention are not impaired.
• the non-biodegradable resin is not particularly limited, and includes polyolefin, polyester, polysulfide, polyvinyl chloride, modified polysulfide, silicone resin, modified silicone resin, acrylic urethane resin, epoxy resin, polyurethane, acrylic resin, polyester, and unsaturated resin. A polyester etc. are mentioned.
• the biodegradable resin composition of the present invention may further contain a plasticizer.
• the plasticizer include benzoic acid esters such as diethylene glycol dibenzoate; dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), phthalate phthalates such as diundecyl acid (DUP) and ditridecyl phthalate (DTDP); terephthalates such as bis(2-ethylhexyl) terephthalate (DOTP); isophthalic acids such as bis(2-ethylhexyl) isophthalate (DOIP) Ester; pyromellitic acid ester such as tetra-2-ethylhexyl pyromellitic acid (TOPM); di-2-ethylhexyl adipate (DOA), diison
• the content of the plasticizer is not particularly limited, but is, for example, in the range of 5 to 300 parts by mass of the plasticizer relative to 100 parts by mass of the inorganic filler, preferably 10 to 200 parts by mass of the plasticizer relative to 100 parts by mass of the inorganic filler. part range.
• the additives contained in the biodegradable resin composition of the present invention are not limited to the fluidity modifier and the plasticizer, and may contain additives other than these.
• examples of other additives include viscosity reducers, flame retardants, stabilizers, stabilizing aids, colorants, processing aids, fillers, antioxidants (antiaging agents), ultraviolet absorbers, and light stabilizers. , lubricants, antistatic agents, cross-linking aids, and the like.
• the method for producing the biodegradable resin composition of the present invention is not particularly limited.
• biodegradable resins, inorganic fillers and fluidity modifiers, and if necessary plasticizers, the above other additives are melted in a single-screw extruder, twin-screw extruder, Banbury mixer, Brabender, various kneaders, etc. It can be obtained by a method of melt-kneading using a kneader.
• the biodegradable resin composition of the present invention can be molded by various molding methods applied to general-purpose plastics.
• the molding method include compression molding (compression molding, laminate molding, stampable molding), injection molding, extrusion molding and co-extrusion molding (film molding by inflation method or T-die method, laminate molding, pipe molding, wire / cable molding , profiled material molding), hot press molding, blow molding (various blow molding), calendar molding, solid molding (uniaxial stretching molding, biaxial stretching molding, roll rolling molding, stretch orientation nonwoven fabric molding, thermoforming (vacuum molding, air pressure molding) molding), plastic processing, powder molding (rotational molding), various non-woven fabric moldings (dry method, adhesion method, entanglement method, spunbond method, etc.), and the like.
• Injection molding, extrusion molding, compression molding or hot press molding are preferably applied. As specific shapes, application to sheets, films, and containers is preferred.
• the molded product obtained above may be subjected to secondary processing.
• the secondary processing includes embossing, painting, adhesion, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating etc.).
• Molded articles obtained from the biodegradable resin composition of the present invention can contain a high amount of inorganic filler, so they can exhibit excellent heat resistance, chemical resistance and impact resistance, and the amount of plastic can be reduced. You can also reduce the weight of In addition, since the molded article is composed of a biodegradable resin and can be decomposed, it is a molded article with a small environmental load.
• Molded articles obtained from the biodegradable resin composition of the present invention are suitably used in a wide range of applications such as packaging materials for packaging liquids, granules, and solids, agricultural materials, and construction materials.
• Specific applications include injection molded products (e.g. fresh food trays, fast food containers, coffee capsule containers, cutlery, outdoor leisure products, etc.), extrusion molded products (e.g. films, sheets, fishing lines, fishing nets, vegetation). nets, secondary processing sheets, water-retaining sheets, etc.), hollow molded products (bottles, etc.), and the like.
• Applications are not limited to the above, agricultural films, coating materials, fertilizer coating materials, nursery pots, laminated films, boards, stretched sheets, monofilaments, nonwoven fabrics, flat yarns, staples, crimped fibers, creased tapes, splits Yarns, composite fibers, blown bottles, shopping bags, garbage bags, compost bags, cosmetic containers, detergent containers, bleach containers, ropes, binding materials, sanitary coverstock materials, cooler boxes, cushioning films, multifilaments, synthetic papers , surgical thread, suture thread, artificial bone, artificial skin, microcapsule, wound dressing, etc. for medical use.
• the values of acid value and hydroxyl value are values evaluated by the following methods.
• Method for measuring acid value It was measured by a method according to JIS K0070-1992.
• Method for measuring hydroxyl value It was measured by a method according to JIS K0070-1992.
• the number average molecular weight of polyester is a value converted to polystyrene based on GPC measurement, and the measurement conditions are as follows.
• [GPC measurement conditions] Measuring device: High-speed GPC device “HLC-8320GPC” manufactured by Tosoh Corporation Column: "TSK GURDCOLUMN SuperHZ-L” manufactured by Tosoh Corporation + "TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZ-2000” manufactured by Tosoh Corporation + “TSK gel SuperHZ-2000” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "EcoSEC Data Analysis version 1.07" manufactured by Tosoh Corporation Column temperature: 40°C Developing solvent: tetrahydrofuran Flow rate: 0.35 mL/min Measurement sample: 7.5 mg of the sample was dissolved in
• reaction product About 210 g of the obtained reaction product, 11.0 g of maleic anhydride was charged, the reaction was completed at 120 ° C., and fluidity modifier A' (acid value: 27, hydroxyl value: 85, number average molecular weight: 1 , 319).
• fluidity modifier B′ (acid value: 29, hydroxyl value: 73, number average molecular weight: 1, 290) was obtained.
• Example 1 Preparation and evaluation of biodegradable resin composition
• 100 parts by mass of polybutylene succinate (“Bio-PBS FZ71PM/PB” manufactured by Mitsubishi Chemical Co., Ltd.)
• 30 parts by mass of calcium bicarbonate (“Super S” manufactured by Maruo Calcium Co., Ltd.)
• Super S manufactured by Maruo Calcium Co., Ltd.
• a press sheet having a thickness of 1 mm was formed with a hot press.
• the resulting sheet was cut into 5 mm squares and dried in a gear oven at 80° C. for 2 hours to prepare a biodegradable resin composition pellet sample A.
• the obtained biodegradable resin composition pellet sample A was put into a melt indexer ("F-F01" manufactured by Toyo Seiki Co., Ltd., orifice inner diameter: 2.090 mm, cylinder temperature: 190 ° C.), and a load of 2160 g was applied. and the melt flow rate was measured after 4 minutes of preheating. Table 1 shows the results.
• Example 2-4 and Comparative Example 1-3 instead of the biodegradable resin composition pellet sample A, a biodegradable resin composition pellet sample having the composition shown in Table 1 was prepared in the same manner as in Example 1 and evaluated. Table 1 shows the results.
• Example 1-4 it can be seen that a high MFR is obtained by adding a polyester having a terminal carboxyl group and an acid value of more than 50 as a fluidity modifier.
• Comparative Example 1 has a low MFR because it does not contain a fluidity modifier.
• the fluidity modifier was a polyester having a terminal carboxyl group, the acid value was 50 or less, so a high MFR was not obtained.

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