Classifications

• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes

Definitions

• the present invention relates to a plasticizer, a thermoplastic polyurethane resin composition containing the plasticizer, and a molded article thereof.
• Plasticizers are used when molding polyvinyl chloride resin (PVC), thermoplastic polyurethane resin (TPU), acrylic resin, polysulfide resin, nitrile rubber (NBR), acrylic rubber (ACM), triacetyl cellulose (TAC), diacetyl cellulose (DAC), polylactic acid (PLA), polybutylene succinate (PBS), polyhydroxyalkanoate (PHA), etc. These plasticizers are added to lower the processing temperature during molding and make the molding process easier.
• PVC polyvinyl chloride resin
• TPU thermoplastic polyurethane resin
• NBR nitrile rubber
• ACM acrylic rubber
• TAC triacetyl cellulose
• DAC diacetyl cellulose
• PDA polylactic acid
• PBS polybutylene succinate
• PHA polyhydroxyalkanoate
• the performance required of a plasticizer includes a variety of colors when molded into a molded product, compatibility, heat resistance, etc., and plasticizers made of ester compounds that use benzoic acid as a reaction raw material are widely used (for example, Patent Documents 1-3).
• Thermoplastic polyurethanes used in the soles of sports shoes require particular flexibility, and because sports shoes have become collectibles in recent years, there is an increasing demand for their aesthetic appearance.
• thermoplastic polyurethane resins are alkylene glycol dibenzoates such as dipropylene glycol dibenzoate (DPGDB) and polyesters end-capped with benzoic acid, but thermoplastic polyurethane resin molded products obtained using these plasticizers can sometimes have a slight yellowish tinge.
• DPGDB dipropylene glycol dibenzoate
• benzoic acid ester plasticizers have the problem of having a distinctive odor.
• the problem to be solved by the present invention is to provide a plasticizer which reduces the coloration and odor of the resulting molded article.
• Another problem to be solved by the present invention is to provide a molded article in which coloring derived from a plasticizer is reduced.
• the present invention relates to the following plasticizers, etc.
• a plasticizer which is a diester made from glycol and benzoic acid as reaction raw materials, or a polyester made from glycol, dicarboxylic acid, and benzoic acid as reaction raw materials,
• a plasticizer comprising benzoic acid and a content of components other than benzoic acid of 1.0 mass% or less.
• the plasticizer according to 1, wherein the components other than benzoic acid are benzyl alcohol, benzaldehyde, biphenyl monocarboxylic acid, biphenyl dicarboxylic acid and benzyl benzoate.
• the plasticizer according to 1 or 2 wherein the glycol is an alkylene glycol having 2 to 18 carbon atoms and/or an oxyalkylene glycol having 2 to 18 carbon atoms. 4. The plasticizer according to any one of 1 to 3, wherein the glycol is at least one selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol. 5.
• thermoplastic polyurethane resin composition comprising a thermoplastic polyurethane resin and the plasticizer according to any one of 1 to 7. 10. A molded article of the thermoplastic polyurethane resin composition according to claim 9.
• the present invention can provide a plasticizer which reduces the coloration and odor of the resulting molded article.
• a molded article having reduced coloring derived from a plasticizer can be provided.
• the present invention is not limited to the following embodiment, and can be implemented by making appropriate modifications within the scope that does not impair the effects of the present invention.
• the compounds in the present specification may be derived from fossil resources or biological resources.
• the plasticizer of the present invention is a diester produced from the reaction raw materials of glycol and benzoic acid, and/or a polyester produced from the reaction raw materials of glycol, dicarboxylic acid, and benzoic acid, in which the content of components other than benzoic acid contained in the benzoic acid is 1.0 mass% or less.
• reaction raw materials as used herein means raw materials that constitute the diester and polyester of the present invention, and does not include solvents or catalysts that do not constitute polyesters.
• Benzoic acid is generally produced industrially by treating benzoyl chloride with a hot solution of calcium hypochlorite, by directly oxidizing toluene with manganese persulfate or manganese dioxide, or by decarboxylating phthalic acid.
• the reaction is carried out at high temperatures, and as a result, benzoic acids react with each other to produce biphenyl compounds (biphenyl monocarboxylic acid, biphenyl dicarboxylic acid, benzyl benzoate) as by-products, or insufficiently oxidized benzyl alcohol and benzaldehyde as by-products.
• a plasticizer with reduced odor can be obtained.
• the plasticizer of the present invention is a diester made from glycol and benzoic acid as reaction raw materials, and/or a polyester made from glycol, dicarboxylic acid, and benzoic acid as reaction raw materials.
• the diester which is the plasticizer of the present invention may be referred to as the "diester of the present invention”
• the polyester which is the plasticizer of the present invention may be referred to as the "polyester of the present invention”.
• the reactants for the diester of the present invention and the polyester of the present invention will be described below.
• the benzoic acid used as the reaction raw material is benzoic acid having a content of components other than benzoic acid of 1.0% by mass or less.
• the content of components other than benzoic acid contained in benzoic acid is preferably 0.7% by mass or less, 0.6% by mass or less, 0.5% by mass or less, and 0.3% by mass or less, in that order.
• the lower limit of the content of components other than benzoic acid contained in benzoic acid is not particularly limited, but is, for example, 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more. The lower limit may be appropriately set in consideration of the allowable cost for treating benzoic acid, etc.
• the content of components other than benzoic acid in benzoic acid is confirmed by the method described in the Examples.
• the above “components other than benzoic acid” preferably means benzyl alcohol, benzaldehyde, biphenyl monocarboxylic acid, biphenyl dicarboxylic acid and benzyl benzoate. That is, the total content of benzyl alcohol, benzaldehyde, biphenyl monocarboxylic acid, biphenyl dicarboxylic acid and benzyl benzoate contained in benzoic acid is preferably 1.0 mass % or less.
• the content of components other than benzoic acid in benzoic acid can be reduced to 1.0 mass% or less, for example, by combining a falling film crystallization process and a reduced pressure distillation process for benzoic acid.
• the falling film crystallization process is, for example, a process including the following steps (1) to (3): (1) Molten benzoic acid is poured into a temperature-controllable vertical tube, and the inside of the tube is cooled to solidify the benzoic acid. (2) The inside of the tube containing the solidified benzoic acid is heated (for example, to 120-125° C.) to approximately the melting point of benzoic acid (122.35° C.) to melt a portion of the solidified benzoic acid. (3) Collect the molten benzoic acid.
• This molten benzoic acid is a high-purity benzoic acid that does not contain biphenyl compounds (biphenyl monocarboxylic acid, biphenyl dicarboxylic acid, benzyl benzoate) that have a higher melting point than benzoic acid.
• Benzoic acid also contains components such as benzyl alcohol and benzaldehyde that have melting points similar to those of benzoic acid, but these can be removed by vacuum distillation, which should be carried out at least either before or after the falling film crystallization process.
• the reaction raw material benzoic acid may be further substituted with an alkyl group having 1-6 carbon atoms.
• the glycol used as the reaction raw material is preferably a glycol having 2 to 18 carbon atoms, more preferably an alkylene glycol having 2 to 18 carbon atoms or an oxyalkylene glycol having 2 to 18 carbon atoms.
• the alkylene glycols having 2 to 18 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,5-pentanediol, 2,2-diethyl-1,3-propanediol (3,3-dimethyl 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, 2-e
• the alkylene glycol having 2 to 18 carbon atoms is preferably an alkylene glycol having 3 to 10 carbon atoms, more preferably an alkylene glycol having 3 to 6 carbon atoms, and even more preferably 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, or 1,6-hexanediol.
• the oxyalkylene glycol having 2 to 18 carbon atoms is, for example, an alkylene glycol having 2 to 18 carbon atoms in which one of the carbon atoms has been replaced with an oxygen atom, and examples of such an oxyalkylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol.
• the oxyalkylene glycol having 2 to 18 carbon atoms is preferably an oxyalkylene glycol having 3 to 10 carbon atoms, more preferably an oxyalkylene glycol having 4 to 10 carbon atoms, and even more preferably diethylene glycol, triethylene glycol, or dipropylene glycol.
• the glycols used as reaction raw materials may be used alone or in combination of two or more types.
• the dicarboxylic acid used as the reaction raw material is preferably an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, more preferably an alkylene dicarboxylic acid having 4 to 14 carbon atoms, and even more preferably an alkylene dicarboxylic acid having 6 to 12 carbon atoms.
• alkylene dicarboxylic acid having 4 to 14 carbon atoms examples include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid (dodecanedioic acid), cyclohexanedicarboxylic acid, hexahydrophthalic acid, etc.
• succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanediacid are more preferred, adipic acid and sebacic acid are even more preferred, and adipic acid is particularly preferred.
• the dicarboxylic acid used as the reaction raw material may be used alone or in combination of two or more types.
• the plasticizer of the present invention uses glycol, dicarboxylic acid, and benzoic acid as reactive raw materials, but other reactive raw materials may be used as long as the effect of the present invention is not impaired.
• the reactant for preparing the diester of the present invention preferably consists essentially of glycol and benzoic acid, and more preferably consists only of glycol and benzoic acid.
• the reactant materials for the polyester of the present invention preferably consist essentially of glycol, dicarboxylic acid and benzoic acid, and more preferably consist only of glycol, dicarboxylic acid and benzoic acid.
• “consisting essentially of” means that the amount of reaction raw materials other than the above is, for example, 5% by mass or less, 3% by mass or less, or 1% by mass or less.
• the diester of the present invention is, for example, a compound represented by the following general formula (1)
• the polyester of the present invention is, for example, a compound represented by the following general formula (2).
• G is a glycol residue having 2 to 18 carbon atoms.
• A is the residue of an aliphatic dicarboxylic acid having 2 to 12 carbon atoms.
• B is a benzoic acid residue.
• p indicates the number of repetitions.
• the term “carboxylic acid residue” refers to the remaining organic group of a carboxylic acid, excluding the carboxyl group.
• the number of carbon atoms in the “carboxylic acid residue” does not include the carbon atoms in the carboxy group.
• the term “glycol residue” refers to an organic group remaining after removing a hydroxyl group from a glycol.
• the glycol residue having 2 to 18 carbon atoms for G is a group corresponding to the glycol having 2 to 18 carbon atoms which is a reactant for the diester and polyester of the present invention.
• the residue of an aliphatic dicarboxylic acid having 2 to 12 carbon atoms for A is a group corresponding to the aliphatic dicarboxylic acid having 4 to 14 carbon atoms which is a reaction raw material for the polyester of the present invention.
• the benzoic acid residue of B is a group corresponding to the benzoic acid which is a reactant for the diesters and polyesters of the present invention.
• the upper limit of p is not particularly limited, but is, for example, 30, and the average value of p is, for example, in the range of 3 to 20.
• the average value of p can be confirmed from the number average molecular weight of the polyester.
• the number average molecular weight (Mn) of the polyester of the present invention is, for example, in the range of 500 to 6,000, preferably in the range of 500 to 5,000, more preferably in the range of 500 to 4,000, and further preferably in the range of 500 to 3,000.
• the number average molecular weight (Mn) of the polyester of the present invention is confirmed by the method described in the Examples.
• the acid value of the polyester of the present invention is preferably 2.0 or less, and more preferably 1.0 or less.
• the hydroxyl value of the polyester of the present invention is preferably 15 or less, and more preferably 10 or less.
• the viscosity of the polyester of the present invention is preferably 7,000 mPa ⁇ s or less, and more preferably 5,000 mPa ⁇ s or less. The acid value, hydroxyl value and viscosity of the polyester of the present invention are confirmed by the methods described in the examples.
• the plasticizer of the present invention may be at least one of the diester of the present invention and the polyester of the present invention, and may be a plasticizer composition comprising both the diester of the present invention and the polyester of the present invention.
• the diester of the present invention can be produced, for example, by reacting benzoic acid with a glycol by a known method, and it is preferable to charge an excess amount of benzoic acid.
• the polyester of the present invention can be produced, for example, by the method shown below.
• Method 1 Benzoic acid, a dicarboxylic acid and a glycol are charged all at once and reacted.
• Method 2 A method in which a dicarboxylic acid is reacted with a glycol under conditions in which the equivalent of a hydroxyl group is greater than the equivalent of a carboxyl group to obtain a polyester having a hydroxyl group at the end of the main chain, and then the obtained polyester is reacted with benzoic acid.
• a diester of benzoic acid and glycol can also be by-produced, and a plasticizer composition can be obtained that is composed of both the polyester of the present invention and the diester of the present invention.
• thermoplastic polyurethane resin composition contains the plasticizer of the present invention and a thermoplastic polyurethane resin.
• the plasticizer of the present invention has high heat resistance, and a molded article obtained by hot molding the thermoplastic polyurethane resin composition of the present invention can be a molded article with reduced coloring derived from the plasticizer of the present invention.
• thermoplastic polyurethane resin may be a commercially available product, or may be produced by a known method.
• the thermoplastic polyurethane resin can be produced, for example, by reacting a polyisocyanate component with a polyol component.
• Polyisocyanate components include linear or branched (acyclic) aliphatic diisocyanates such as 1,5-pentamethylene diisocyanate (PDI) and 1,6-hexamethylene diisocyanate (HDI); 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4,4'-, 2,4'- or 2,2'-dicyclohexylmethane diisocyanate; cyclic aliphatic diisocyanates (alicyclic diisocyanates) such as 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane; aromatic polyisocyanates such as 2,4- or 2,6-tolylene diisocyanate, 4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate; and aromatic aliphatic diisocyanates such as 1,3- or 1,4-xylylene diis
• the polyol component can be classified into low molecular weight polyols, for example, with a number average molecular weight of 60 or more and less than 400, and high molecular weight polyols, with a number average molecular weight of 400 or more and 10,000 or less.
• Low molecular weight polyols include linear diols such as 1,2-ethanediol (ethylene glycol), 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol; and branched diols such as 1,2-propanediol (propylene glycol), 1,2-butanediol, 1,3-butanediol, and 2,2-dimethyl-1,3-propanediol (neopentyl glycol).
• linear diols such as 1,2-ethanediol (ethylene glycol), 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol
• branched diols such as 1,2-propanediol (propylene glycol), 1,2-butanedio
• high molecular weight polyols examples include polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxyethylene-polyoxypropylene copolymers, and polytetramethylene ether glycol; polyester polyols such as polycaprolactone diol; and polycarbonate diol.
• polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxyethylene-polyoxypropylene copolymers, and polytetramethylene ether glycol
• polyester polyols such as polycaprolactone diol
• polycarbonate diol examples include polycarbonate diol.
• the polyisocyanate components and polyol components used in the production of thermoplastic polyurethane resin may each be a single type or a combination of two or more types.
• the content of the plasticizer of the present invention in the thermoplastic polyurethane resin composition of the present invention is preferably in the range of 10 to 100 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin, from the viewpoint of compatibility with the thermoplastic polyurethane resin, etc.
• thermoplastic polyurethane resin composition of the present invention only needs to contain a thermoplastic polyurethane resin and the plasticizer of the present invention, and may also contain other additives.
• additives include flame retardants, stabilizers, stabilization aids, colorants, processing aids, fillers, antioxidants (antiaging agents), UV absorbers, light stabilizers, lubricants, antistatic agents, crosslinking aids, and the like.
• flame retardants examples include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, and zinc borate; phosphorus compounds such as cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, and trisdichloropropyl phosphate; and halogen compounds such as chlorinated paraffin.
• the blending amount is usually 0.1 to 20 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin.
• the stabilizer examples include metal soap compounds such as lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octoate, zinc laurate, zinc ricinoleate, and zinc stearate; organotin compounds such as dimethyltin bis-2-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutylmaleate, and dibutyltin dilaurate; antimony mercaptide compounds; and lanthanoid-containing compounds such as lanthanum oxide and lanthanum hydroxide.
• the blending amount is usually 0.1 to 20 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin.
• stabilizing aids include phosphite compounds such as triphenyl phosphite, monooctyl diphenyl phosphite, and tridecyl phosphite; beta diketone compounds such as acetyl acetone and benzoyl acetone; polyol compounds such as glycerin, sorbitol, pentaerythritol, and polyethylene glycol; perchlorate compounds such as barium perchlorate and sodium perchlorate; hydrotalcite compounds; and zeolites.
• the stabilizing aid is blended with the thermoplastic polyurethane resin composition, the blending amount is usually 0.1 to 20 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin.
• colorants include carbon black, lead sulfide, white carbon, titanium white, lithopone, safflower, antimony sulfide, chrome yellow, chrome green, cobalt blue, and molybdenum orange.
• the blending amount is usually 1 to 100 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin.
• processing aids include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bis stearic acid amide, butyl stearate, calcium stearate, and the like.
• the processing aid is blended with the thermoplastic polyurethane resin composition, the blending amount is usually 0.1 to 20 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin.
• fillers include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, and ferrite; fibers and powders of glass, carbon, metal, and the like; glass spheres, graphite, aluminum hydroxide, barium sulfate, magnesium oxide, magnesium carbonate, magnesium silicate, and calcium silicate.
• the blending amount is usually 1 to 100 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin.
• antioxidants examples include phenolic compounds such as 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol)propionate]methane, and 2-hydroxy-4-methoxybenzophenone; sulfur compounds such as alkyl disulfides, thiodipropionic acid esters, and benzothiazole; phosphoric acid compounds such as trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite; and organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate.
• the blending amount is usually 0.2 to 20 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin.
• the ultraviolet absorber examples include salicylate-based compounds such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenone-based compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone; benzotriazole-based compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, as well as cyanoacrylate-based compounds.
• the blending amount is usually 0.1 to 10 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin.
• Examples of the light stabilizer include hindered amine light stabilizers. Specific examples include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate (mixture), bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl)decanedioate, and bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate (mixture).
• the lubricant examples include silicone, liquid paraffin, paraffin wax, metal salts of fatty acids such as metal stearates and metal laurates; fatty acid amides, fatty acid waxes, and higher fatty acid waxes.
• the blending amount is usually 0.1 to 10 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin.
• the antistatic agent examples include anionic antistatic agents of the alkylsulfonate type, alkyl ether carboxylic acid type, or dialkyl sulfosuccinate type; nonionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, and diethanolamine derivatives; cationic antistatic agents such as quaternary ammonium salts of the alkylamidoamine type, alkyldimethylbenzyl type, and organic acid salts or hydrochlorides of alkylpyridinium type; and amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type.
• the blending amount is usually 0.1 to 10 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin.
• crosslinking aid examples include polyfunctional monomers such as tetraethylene glycol dimethacrylate, divinylbenzene diallyl phthalate, triallyl isocyanurate, trimethylolpropane triallylate, tetramethylolmethane tetramethacrylate, and trimethoxyethoxyvinylsilane.
• the blending amount is usually 0.5 to 30 parts by mass per 100 parts by mass of the thermoplastic polyurethane resin.
• thermoplastic polyurethane resin composition of the present invention can be produced by a known method.
• the thermoplastic polyurethane resin composition of the present invention can be prepared by mixing a thermoplastic polyurethane resin, the plasticizer of the present invention, and optional components (the other plasticizers and the other additives) using a kneader such as a blender, a planetary mixer, or a Banbury mixer.
• a kneader such as a blender, a planetary mixer, or a Banbury mixer.
• Thermoplastic polyurethane resin molded bodies can be obtained by molding the thermoplastic polyurethane resin composition of the present invention using known molding methods such as vacuum molding, compression molding, extrusion molding, calendar molding, press molding, blow molding, and powder molding.
• thermoplastic polyurethane resin molded product is not limited to the above.
• a polyisocyanate component and a polyol component which are raw materials for a thermoplastic polyurethane resin, and the plasticizer of the present invention are introduced into an extruder, and a polymerization reaction is carried out while melt-kneading in the extruder, thereby simultaneously producing a thermoplastic polyurethane resin and molding the thermoplastic polyurethane resin, thereby obtaining a plastic polyurethane resin molded product.
• Thermoplastic polyurethane resin molded products can be used for belts, tubes, hoses, wire coating materials, cable coating materials, fire hoses, packing materials, bumpers, seat materials, air mattresses, synthetic leather, shoe soles, watch bands, camera grips, smartphone cases, tablet cases, medical tubes, skis, rackets, etc.
• the acid value, viscosity and freezing point were evaluated by the following methods.
• ⁇ Method of measuring acid value> The measurement was performed according to a method in accordance with JIS K0070-1992.
• ⁇ Method of measuring viscosity> The measurement was performed according to a method in accordance with JIS K6901-1986.
• the number average molecular weight of the polyester is a value calculated in terms of polystyrene based on GPC measurement, and the measurement conditions are as follows.
• Measurement equipment Tosoh Corporation's high-speed GPC equipment "HLC-8420GPC”
• Detector RI (differential refractometer)
• Data processing Tosoh Corporation's "EcoSEC Data Analysis Version 1.07”
• Developing solvent tetrahydrofuran Flow rate: 0.35 mL/min
• Measurement sample 20 mg of a sample was dissolved in 10 ml of tetrahydrofuran, and the resulting solution was filtered through a microfilter to prepare a measurement sample.
• Sample injection volume 20 ⁇ l Standard material: "PStQuick MP-H" manufactured by Tosoh Corporation
• the benzoic acid A used in Synthesis Example 1 was benzoic acid that had been subjected to falling film crystallization and reduced pressure distillation, and it was confirmed by gas chromatography that the total content of components other than benzoic acid, such as benzyl alcohol, benzaldehyde, biphenyl compounds, and benzyl benzoate, in the benzoic acid was 0.5% by mass.
• the gas chromatography was carried out using a Shimadzu Corporation "GC-2030" under the following conditions.
• ester compound plasticizer A3 (acid value 0.5, viscosity 672 mPa ⁇ s (25°C)).
• the color numbers (Hazen unit color number, APHA) of the plasticizers prepared in the synthesis examples and comparative examples were evaluated based on JIS K0071-1: 2017. The results are shown in Table 1. A smaller color number means less coloring.
• Plasticizer Odor 100 g of plasticizer was placed in a 225 ml glass bottle and left at room temperature for approximately 2 hours, after which the suction port of a sensor (Shin Cosmos Electric Co., Ltd. Portable Odor Sensor XP-329) was inserted into an 8 mm hole in the inner lid to begin measurement, and the value after 3 minutes was read and the odor of the plasticizer was evaluated according to the following criteria. The smaller the sensor value, the less odor there was. 1: Sensor value is less than 100. 2: Sensor value is 100 or more and less than 300. 3: Sensor value is 300 or more and less than 500. 4: Sensor value is 500 or more.
• TPU Thermoplastic Polyurethane
• ⁇ Mixing pattern 1 A polyurethane resin composition was prepared by mixing 100 parts by mass of a polyurethane resin (Pandex T-8180N (ether type), manufactured by DIC Covestro Polymer Co., Ltd.), 20 parts by mass of a plasticizer, and 0.5 parts by mass of a lubricant (Licolub WE-4, manufactured by Clariant Chemicals Co., Ltd.).
• a polyurethane resin composition was prepared by mixing 100 parts by mass of a polyurethane resin (Pandex T-1180N (ether type), manufactured by DIC Covestro Polymer Co., Ltd.), 20 parts by mass of a plasticizer, and 0.5 parts by mass of a lubricant (Licolub WE-4, manufactured by Clariant Chemicals Co., Ltd.).
• a polyurethane resin Pandex T-1180N (ether type), manufactured by DIC Covestro Polymer Co., Ltd.
• a plasticizer 20 parts by mass of a plasticizer
• a lubricant Liicolub WE-4, manufactured by Clariant Chemicals Co., Ltd.
• the polyurethane resin composition prepared with two rolls heated to 140-150°C was mixed for 5 minutes, and then the mixed polyurethane resin composition was molded using a mold capable of producing a 1.0 mm thick molded product (1.0 mm thick mold) and a press machine heated to 140-150°C to produce a 1.0 mm thick sheet.
• dumbbell test piece of dumbbell shape No. 3 was prepared according to JIS K7311:1995.
• the 100% modulus (tensile stress at 100% elongation) and breaking elongation of this test piece were evaluated according to JIS K7311:1995.
• a tensile test was performed using a 1.0 mm thick sheet under the following conditions to evaluate the 100% modulus and breaking elongation.
• the results are shown in Table 1.
• the breaking elongation was calculated by subtracting the initial chuck distance of 20 mm from the chuck distance when the 1.0 mm thick sheet broke in tension, and dividing the result by the chuck distance of 20 mm, and expressing the result as a percentage.
• Measuring equipment Tensilon universal material testing machine (manufactured by Orientec Co., Ltd.) Sample shape: Dumbbell-shaped No. 3 Gauge distance: 20 mm Chuck distance: 60 mm Tensile speed: 200 mm/min Measurement atmosphere: temperature 23 degrees, humidity 50%
• the sheet obtained above was cut into a sheet sample having a length of 30 mm, a width of 30 mm, and a thickness of 1 mm, and the initial yellowness YI value (initial YI value) of the sheet sample was measured using a colorimeter ("TZ-7700" manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7373: 2006.
• the sheet sample was heated at 120°C for 72 hours, and the post-heating yellowness YI value (post-heating YI value) of the sheet sample was measured again.
• the difference between the initial YI value and the YI value after heating was taken as the ⁇ YI value.
• the ⁇ YI value is a numerical representation of the degree of yellowing, with a smaller value indicating less color change (yellowing).
• the amount of components other than benzoic acid in benzoic acid A and benzoic acid B in the examples and comparative examples differs by only about 1% by mass.
• the odor of the plasticizer obtained using that benzoic acid can be significantly reduced, and the coloring due to the plasticizer in the molded body using that plasticizer can also be significantly reduced.

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