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
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
  • C08G65/327—Polymers modified by chemical after-treatment with inorganic compounds containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
  • C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
• • 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
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

• the present invention relates to a resin additive containing a compound having a specific structure, a composition containing the resin additive, a molded article thereof, and a compound.
• Polyester resins, polycarbonate resins, and blends thereof have excellent mechanical strength and moldability and are therefore used in a wide range of applications, including electrical and electronic components, automotive components, fibers, and films.
• polyester resins and polycarbonate resins can suffer from adverse effects during processing or over time, such as discoloration, a decrease in crystallization temperature, and a decrease in mechanical strength.
• a method has been proposed for stabilizing the resins by blending them with phosphate ester compounds.
• Patent Document 1 proposes a method for producing polylactic acid resin, and describes how adding a catalyst deactivator during the production process can suppress thermal decomposition.
• Preferred catalyst deactivators in this invention include phosphorus-based compounds such as phosphate-based compounds and phosphite-based compounds. In the examples, it describes how the thermal stability of the resin is improved by blending dioctadecyl phosphate with polylactic acid resin.
• Patent Document 2 proposes a thermoplastic elastomer composition containing an ester exchange catalyst deactivator and an antioxidant for a thermoplastic polyester elastomer. It is disclosed that an acidic phosphate ester compound is preferable as the ester exchange catalyst deactivator in this invention. In the examples, it is described that mechanical strength and heat aging resistance are improved by blending an acidic phosphate ester compound such as dioctadecyl acid phosphate and an antioxidant with a polyester elastomer.
• Patent Documents 1 and 2 it is described that resin deterioration is suppressed by blending an acidic phosphate ester such as octadecyl acid phosphate.
• an acidic phosphate ester such as octadecyl acid phosphate.
• these acidic phosphate esters have insufficient heat resistance, and there are problems, such as the generation of smoke, during processing of the resin.
• the objective of the present invention is to provide a resin additive that has excellent heat resistance and excellent resin stabilization performance.
• the present invention is a resin additive that contains a compound represented by the following general formula (1):
• R 1 represents an alkyl group having 26 to 40 carbon atoms, an alkenyl group having 26 to 40 carbon atoms, or a group represented by the following general formula (2), and n represents an integer of 1 or 2. When n is 2, multiple R 1s may be the same or different.
• R2 represents hydrogen or an alkyl group having 1 to 18 carbon atoms
• m represents an integer such that the number average molecular weight of the group represented by general formula (2) is 100 to 10,000
• * represents a bond.
• R 1 in the general formula (1) is preferably an alkyl group having 28 to 36 carbon atoms.
• R 1 in the general formula (1) is preferably a group represented by the general formula (2).
• R 2 in the general formula (2) is preferably an alkyl group having 1 to 4 carbon atoms.
• m in the general formula (2) is an integer such that the number average molecular weight of the group represented by the general formula (2) is 400 to 5,000.
• the resin additive of the present invention preferably contains an acidic phosphate monoester in which n in the general formula (1) is 1 and an acidic phosphate diester in which n in the general formula (1) is 2.
• the content ratio of the acidic phosphate monoester and the acidic phosphate diester is preferably in the range of 100:1 to 100:10,000 in terms of mass ratio (acidic phosphate monoester:acidic phosphate diester).
• the present invention also relates to a composition containing a thermoplastic resin and the above-mentioned resin additive.
• thermoplastic resin is preferably one or more selected from polyester resins and polycarbonate resins.
• the present invention also relates to a molded article obtained from the above composition.
• the present invention also relates to a compound represented by the following general formula (1):
• R 1 represents an alkyl group having 26 to 40 carbon atoms, an alkenyl group having 26 to 40 carbon atoms, or a group represented by the following general formula (2), and n represents an integer of 1 or 2. When n is 2, multiple R 1s may be the same or different.
• R2 represents hydrogen or an alkyl group having 1 to 18 carbon atoms
• m represents an integer such that the number average molecular weight of the group represented by general formula (2) is 100 to 10,000
• * represents a bond.
• the present invention provides a resin additive having excellent heat resistance and excellent resin stabilization performance, a composition containing the resin additive, and a molded article obtained from the composition.
• the resin additive of the present invention contains a compound represented by the following general formula (1).
• R 1 represents an alkyl group having 26 to 40 carbon atoms, an alkenyl group having 26 to 40 carbon atoms, or a group represented by the following general formula (2), and n represents an integer of 1 or 2. When n is 2, multiple R 1s may be the same or different.
• R2 represents hydrogen or an alkyl group having 1 to 18 carbon atoms
• m represents an integer such that the number average molecular weight of the group represented by general formula (2) is 100 to 10,000
• * represents a bond.
• the resin additive of the present invention has the effect of providing excellent heat resistance and resin stabilization performance.
• the reason for this effect is not clear, but is presumed to be as follows.
• Thermoplastic resins usually contain catalyst residues. These catalyst residues cause problems such as a decrease in molecular weight due to hydrolysis, and hybridization of molecular bonds due to ester exchange reactions, resulting in changes in melt fluidity, discoloration, and reduced mechanical strength.
• a compound with the above structure it functions as a catalyst deactivator and can eliminate problems caused by catalyst residues. This has the effect of stabilizing the resin.
• the compound with the above structure has excellent heat resistance of the compound itself, reduces decomposition of thermoplastic resins during processing, and allows it to stably function as a resin additive. For these reasons, the resin additive has the effect of excellent heat resistance and resin stabilization performance.
• Examples of the alkyl group having 26 to 40 carbon atoms represented by R 1 in the above general formula (1) include linear or branched alkyl groups such as a hexacosyl group, an octacosyl group, a triacontyl group, a dotriacontyl group, a hextriacontyl group, a tetracontyl group, a 2-decylhexadecyl group, a 2-dodecylhexadecyl group, a 2-decyloctadecyl group, a 2-tetradecyloctadecyl group, a 2-hexadecyloctadecyl group, a 2-tetradecyleicosyl group, and a 2-hexadecyleicosyl group.
• linear or branched alkyl groups such as a hexacosyl group, an octacosyl group, a triaconty
• Examples of the alkenyl group having 26 to 40 carbon atoms represented by R 1 in the above general formula (1) include linear or branched alkenyl groups such as a hexacosenyl group, an octacosenyl group, a triacontenyl group, a dotriacontenyl group, a hexatriacontenyl group, a tetracontenyl group, a 2-dodecylhexadecenyl group, and a 2-dodecyloctadecenyl group.
• the position of the double bond may be the ⁇ -position, an internal group, or a ⁇ -position.
• R 1 in general formula (1) is preferably an alkyl group having 26 to 40 carbon atoms or a group represented by general formula (2), more preferably a group represented by general formula (2), which allows the compound to exhibit better heat resistance.
• R 1 in general formula (1) is an alkyl group having 26 to 40 carbon atoms
• the alkyl group is preferably an alkyl group having 28 to 36 carbon atoms, more preferably an alkyl group having 30 to 34 carbon atoms, and particularly preferably an alkyl group having 31 to 33 carbon atoms. This further improves the heat resistance and resin stabilization performance of the resin additive of the present invention.
• alkyl group having 1 to 18 carbon atoms represented by R 2 in the above general formula (2) examples include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, tert-hexyl, heptyl, isoheptyl, tert-heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, 2-propylheptyl, undecyl, isoundecyl, dodecyl, isododecyl, tridecyl, isotri
• R2 in the general formula (2) is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group. This further improves the heat resistance and resin stabilization performance of the resin additive of the present invention.
• m is an integer that gives the group represented by general formula (2) a number average molecular weight of 100 or more, preferably an integer that gives the group represented by general formula (2) a number average molecular weight of 400 or more, more preferably an integer that gives the group represented by general formula (2) a number average molecular weight of 800 or more, even more preferably an integer that gives the group represented by general formula (2) a number average molecular weight of 1,000 or more, and particularly preferably an integer that gives the group represented by general formula (2) a number average molecular weight of 1,500 or more.
• This provides the resin additive of the present invention with a better balance between heat resistance and resin stabilization performance.
• m in the above general formula (2) is an integer that results in the number average molecular weight of the group represented by general formula (2) being 10,000 or less, preferably an integer that results in the number average molecular weight of the group represented by general formula (2) being 5,000 or less, more preferably an integer that results in the number average molecular weight of the group represented by general formula (2) being 4,500 or less, even more preferably an integer that results in the number average molecular weight of the group represented by general formula (2) being 3,500 or less, and particularly preferably an integer that results in the number average molecular weight of the group represented by general formula (2) being 2,500 or less. This further improves the heat resistance and resin stabilization performance of the resin additive of the present invention.
• the resin additive of the present invention may be an acidic phosphoric acid monoester in which n in the general formula (1) is 1, or an acidic phosphoric acid diester in which n in the general formula (1) is 2, but from the viewpoint of heat resistance and resin stabilization performance, it is preferable to contain an acidic phosphoric acid monoester and an acidic phosphoric acid diester.
• the content ratio of the acidic phosphoric acid monoester and the acidic phosphoric acid diester is preferably 100:1 to 100:10,000 by mass ratio (acidic phosphoric acid monoester:acidic phosphoric acid diester), more preferably 100:3 to 100:500, and even more preferably 100:5 to 100:100. This further improves the heat resistance and resin stabilization performance of the resin additive of the present invention.
• the mass ratio of the acidic phosphate monoester to the acidic phosphate diester can be measured by analysis using a nuclear magnetic resonance (NMR) spectrometer.
• NMR nuclear magnetic resonance
• the two R 1s may be the same or different, but are preferably the same. This further improves the heat resistance and resin stabilization performance of the resin additive of the present invention.
• the compound represented by the general formula (1) can be produced by a conventionally known method, for example, a method of reacting an alcohol corresponding to R 1 in the general formula (1) with diphosphorus pentoxide.
• examples of the resin additive of the present invention include compounds represented by the following formulas (3) and (4).
• the compound represented by the following formula (3) can be produced by reacting methoxypolyethylene glycol (polyethylene glycol monomethyl ether) having a specified molecular weight with diphosphorus pentoxide.
• the compound represented by the following formula (4) can be produced by reacting 2-tetradecyl octadecanol with diphosphorus pentoxide.
• the present invention is not limited to the following compounds.
• n represents an integer of 1 or 2.
• m represents an integer such that the number average molecular weight of the structural portion in the brackets is 100 to 10,000.
• the resin additive of the present invention preferably contains one or more compounds selected from the group consisting of compounds represented by the above formulas (3) and (4). Of these, it is more preferable that it contains one or more compounds selected from the group consisting of compounds represented by the above formula (3), and it is even more preferable that m in the above formula (3) represents an integer such that the number average molecular weight of the structural portion in the brackets is 400 to 5,000. This further improves the heat resistance and resin stabilization performance of the resin additive of the present invention.
• the resin additive of the present invention may be a single compound or a mixture of two or more compounds.
• composition of the present invention contains the above-mentioned resin additive and a thermoplastic resin.
• the lower limit of the content of the resin additive is preferably 0.01 parts by mass, more preferably 0.02 parts by mass, even more preferably 0.05 parts by mass, and particularly preferably 0.1 parts by mass, relative to 100 parts by mass of the composition of the present invention.
• the upper limit of the content of the resin additive is preferably 10 parts by mass, more preferably 7 parts by mass, even more preferably 5 parts by mass, and particularly preferably 3 parts by mass, relative to 100 parts by mass of the composition of the present invention. This allows the composition of the present invention to more effectively exhibit the effects of excellent heat resistance and stability performance.
• the lower limit of the content of the resin additive is preferably 0.01 parts by mass, more preferably 0.02 parts by mass, even more preferably 0.05 parts by mass, and particularly preferably 0.1 parts by mass, per 100 parts by mass of the thermoplastic resin.
• the upper limit of the content of the resin additive is preferably 10 parts by mass, more preferably 7 parts by mass, even more preferably 5 parts by mass, and particularly preferably 3 parts by mass, per 100 parts by mass of the composition of the present invention. This allows the composition of the present invention to more effectively exhibit the effects of excellent heat resistance and stability.
• thermoplastic resins include synthetic resins such as polyolefin resins, styrene-based resins, polyester resins, polycarbonate resins, polysulfide resins, polyamide resins, polyether resins, and halogen-containing resins. These may be used alone or in combination of two or more.
• thermoplastic resins include petroleum resins, coumarone resins, polyvinyl acetate, acrylic resins, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyurethane, cellulose resins, polyimide resins, polysulfones, liquid crystal polymers, and other thermoplastic resins, as well as blends of these.
• the thermoplastic resin may be a thermoplastic elastomer such as isoprene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, olefin-based elastomer, styrene-based elastomer, polyester-based elastomer, nitrile-based elastomer, vinyl chloride-based elastomer, polyamide-based elastomer, or polyurethane-based elastomer, or may be used in combination with the above synthetic resins, etc.
• a thermoplastic elastomer such as isoprene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copoly
• polystyrene-based resin examples include syndiotactic polystyrene and acrylonitrile-butadiene-styrene terpolymers.
• the polysulfide resin includes polyphenylene sulfide.
• the polyamide resin may, for example, be polyhexamethylene adipamide.
• thermoplastic resins polyester resins and polycarbonate resins are preferred because they can more effectively exhibit the resin stabilization performance of the resin additive of the present invention, and it is also preferred to use them in combination with thermoplastic elastomers.
• polyester resins examples include polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, and polycyclohexanedimethylene terephthalate; polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate; and degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, and poly(2-oxetanone).
• the polycarbonate resin is a resin having a carbonate bond, and is obtained, for example, by a polymerization reaction between a divalent hydroxy aromatic compound and a carbonate precursor.
• the above divalent hydroxy aromatic compounds include dihydroxybenzenes such as resorcinol and hydroquinone; bishydroxyaryls such as 4,4'-dihydroxydiphenyl; bis(hydroxyaryl)alkanes such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenoxy)ethane, and 2,2-bis(4-hydroxyphenyl)propane; dihydroxyaryl ketones such as bis(4-hydroxyphenyl)ketone and bis(4-hydroxy-3-methylphenyl)ketone; 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, and the like.
• dihydroxybenzenes such as resorcinol and hydroquinone
• bishydroxyaryls such as 4,4'-dihydroxydiphenyl
• bis(hydroxyaryl)alkanes such as bis(4-hydroxyphen
• dihydroxyaryl ethers such as 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether; dihydroxyaryl sulfur compounds such as 4,4'-thiodiphenol, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 2,2-bis(4-hydroxyphenyl)sulfone, 4,4'-dihydroxydiphenyl sulfone, and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; phenolphthalein, etc.
• dihydroxyaryl ethers such as 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether
• dihydroxyaryl sulfur compounds such as 4,4'-thiodiphenol,
• suitable carbonate precursors include phosgene, carbonic acid diesters, diphenyl carbonate, dihaloformates of dihydric phenols, and mixtures thereof.
• thermoplastic resins are not limited in molecular weight, degree of polymerization, polymerization method, density, softening point, proportion of insoluble matter in a solvent, degree of stereoregularity, presence or absence of catalyst residue, types and blending ratio of raw monomers, type of polymerization catalyst, etc., and any thermoplastic resin can be used. These thermoplastic resins may be used alone or in combination of two or more thereof. The thermoplastic resin may be alloyed.
• the lower limit of the content of the thermoplastic resin is preferably 90 parts by mass, more preferably 93 parts by mass, even more preferably 95 parts by mass, and particularly preferably 97 parts by mass, relative to 100 parts by mass of the composition of the present invention.
• the upper limit of the content of the thermoplastic resin is preferably 99.99 parts by mass, more preferably 99.98 parts by mass, even more preferably 99.95 parts by mass, and particularly preferably 99.9 parts by mass, relative to 100 parts by mass of the composition of the present invention. This allows the composition of the present invention to more effectively exhibit the effects of excellent heat resistance and stability performance.
• the composition of the present invention may contain other optional components together with the resin additive.
• the timing of mixing the resin additive and other optional components with the thermoplastic resin is not particularly limited.
• two or more selected from the blending components other than the thermoplastic resin may be mixed in advance and then blended with the thermoplastic resin, or each component other than the thermoplastic resin may be blended sequentially with the thermoplastic resin.
• each component may be crushed and then mixed, or mixed and then crushed.
• the thermoplastic resin is an alloy
• each component other than the thermoplastic resin may be added to a compound that is already alloyed, or may be added during the alloying process.
• the resin additive and the thermoplastic resin may be mixed by mixing the resin additive with the entire amount of the thermoplastic resin to be mixed, or by pre-mixing the resin additive with a portion of the thermoplastic resin to prepare a master batch, and then mixing the master batch with the remaining thermoplastic resin.
• the master batch may also contain the other optional components described above.
• the content of the resin additive in the master batch may be 1 part by mass or more, and may be 10 parts by mass or more and 90 parts by mass or less, per 100 parts by mass of the master batch.
• a stabilizer such as a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, an ultraviolet absorber, or a hindered amine-based light stabilizer to the composition of the present invention, as necessary, to stabilize the composition.
• phenol-based antioxidants examples include 2,6-di-tert-butyl p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl -m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-
• phenolic antioxidants may be used alone or in combination of two or more.
• the content of the phenolic antioxidant is preferably 0.001 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, relative to 100 parts by weight of the thermoplastic resin, from the viewpoint of antioxidant effect.
• the phosphorus-based antioxidants include, for example, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, didecyl monophenyl phosphite, bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, thritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl
• phosphorus-based antioxidants may be used alone or in combination of two or more.
• the content of the phosphorus-based antioxidant is preferably 0.001 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, relative to 100 parts by weight of the thermoplastic resin.
• the thioether-based antioxidants include, for example, dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; pentaerythritol tetrakis( ⁇ -alkyl mercaptopropionates; etc. These thioether-based antioxidants may be used alone or in combination of two or more. From the viewpoint of antioxidant effect, the content of the thioether-based antioxidant is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the thermoplastic resin.
• the ultraviolet absorber may, for example, be 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3' 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-
• the ultraviolet absorbers may be used alone or in combination of two or more.
• the content of the ultraviolet absorber is preferably 0.001 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, relative to 100 parts by weight of the thermoplastic resin, from the viewpoint of ultraviolet absorbing effect.
• hindered amine-based light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, and tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarbo xylates, bis(2,2,6,6-tetramethyl-4-piperidyl)bis(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6,
• the content of the hindered amine light stabilizer is preferably 0.001 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass, per 100 parts by mass of the thermoplastic resin.
• composition of the present invention may further contain additives that are normally used in synthetic resins, such as crosslinking agents, antistatic agents, anti-fogging agents, anti-plate-out agents, surface treatment agents, plasticizers, lubricants, reinforcing agents, nucleating agents, flame retardants, flame retardant assistants, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, release agents, silicone oils, silane coupling agents, fillers, hydrotalcites, metal soaps, pigments, and dyes, within the range that does not impair the effects of the present invention.
• additives that are normally used in synthetic resins, such as crosslinking agents, antistatic agents, anti-fogging agents, anti-plate-out agents, surface treatment agents, plasticizers, lubricants, reinforcing agents, nucleating agents, flame retardants, flame retardant assistants, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, release agents, silicone oils, silane coupling agents,
• the form of the composition of the present invention is not particularly limited, but from the viewpoint of the handleability of the composition, it is preferably in the form of pellets, powder, granules or flakes, and more preferably in the form of pellets.
• composition of the present invention can be used for molding, etc., either alone or in combination with compositions other than the present invention, additive components, or mixtures thereof.
• the composition of the present invention can also be used as a masterbatch.
• the molded article of the present invention can be obtained by molding the composition of the present invention by a known method.
• the molding method is not particularly limited, and examples of the molding method include extrusion molding, calendar molding, injection molding, roll molding, compression molding, and blow molding.By using these molding methods, molded articles of various shapes such as resin plates, sheets, films, pellets, and irregular shapes can be produced.
• composition of the present invention and its molded products can be used in a wide range of industrial fields, including electricity, electronics, communications, agriculture, forestry, fisheries, mining, construction, food, textiles, clothing, medicine, coal, petroleum, rubber, leather, automobiles, precision instruments, wood, building materials, civil engineering, furniture, printing and musical instruments.
• office equipment such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic organizers, cards, holders and stationery; home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game consoles, irons and kotatsu; AV equipment such as TVs, VTRs, video cameras, radio cassette players, tape recorders, minidiscs, CD players, speakers and liquid crystal displays; electrical and electronic parts such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers, deflection yokes, distribution boards and clocks; and communication equipment.
• office equipment such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic
• composition of the present invention and its molded article can also be used for optical materials such as optical disks, CD disks, DVD disks, and lenses, and as a replacement for glass.
• composition of the present invention and its molded articles can be used in a wide range of applications, including seats (padding, covering material, etc.), belts, ceiling coverings, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulation materials, handrails, handrail straps, wire covering materials, electrical insulation materials, paints, coating materials, upholstery materials, flooring materials, bulkheads, carpets, wallpaper, wall covering materials, exterior materials, interior materials, roofing materials, deck materials, wall materials, Used for a variety of purposes, including materials for automobiles, vehicles, ships, aircraft, buildings, homes and construction, such as pillars, flooring, fence materials, frameworks and moldings, window and door shapes, shingles, paneling, terraces, balconies, soundproofing boards, heat-insulating boards, and window materials; civil engineering materials; and daily necessities and sports goods, such as clothing, curtains, sheets, plywood, synthetic fiber boards, carpets, entrance mats, sheets, buckets,
• R 1 represents an alkyl group having 26 to 40 carbon atoms, an alkenyl group having 26 to 40 carbon atoms, or a group represented by the following general formula (2), and n represents an integer of 1 or 2. When n is 2, multiple R 1s may be the same or different.
• R2 represents hydrogen or an alkyl group having 1 to 18 carbon atoms
• m represents an integer such that the number average molecular weight of the group represented by general formula (2) is 100 to 10,000
• * represents a bond.
• the compound of the present invention has the above-mentioned specific structure, and thus can exhibit excellent heat resistance and excellent resin stabilization performance. Note that the compound of the present invention is similar to the content described in the above ⁇ Resin Additives> section, so a detailed description is omitted here.
• the present invention includes the following aspects.
• a resin additive comprising a compound represented by the following general formula (1):
• R 1 represents an alkyl group having 26 to 40 carbon atoms, an alkenyl group having 26 to 40 carbon atoms, or a group represented by the following general formula (2), and n represents an integer of 1 or 2. When n is 2, multiple R 1s may be the same or different.
• R2 represents hydrogen or an alkyl group having 1 to 18 carbon atoms
• m represents an integer such that the number average molecular weight of the group represented by general formula (2) is 100 to 10,000
• * represents a bond.
• a resin additive, wherein R 1 in the general formula (1) is an alkyl group having 28 to 36 carbon atoms.
• the resin additive according to any one of [1] to [5], The resin additive comprises an acidic phosphoric acid monoester in which n in the general formula (1) is 1 and an acidic phosphoric acid diester in which n in the general formula (1) is 2.
• the resin additive according to [6] The resin additive, wherein the content ratio of the acidic phosphoric acid monoester to the acidic phosphoric acid diester is in the range of 100:1 to 100:10,000 in terms of mass ratio (acidic phosphoric acid monoester:acidic phosphoric acid diester).
• thermoplastic resin is at least one selected from a polyester resin and a polycarbonate resin.
• R 1 represents an alkyl group having 26 to 40 carbon atoms, an alkenyl group having 26 to 40 carbon atoms, or a group represented by the following general formula (2), and n represents an integer of 1 or 2. When n is 2, multiple R 1s may be the same or different.
• R2 represents hydrogen or an alkyl group having 1 to 18 carbon atoms
• m represents an integer such that the number average molecular weight of the group represented by general formula (2) is 100 to 10,000
• * represents a bond.
• Resin additives (A)-1 to (A)-6 and comparative resin additive (B)-2 were obtained according to the following Production Examples 1 to 7.
• the mass ratio of the acidic phosphoric acid monoester to the acidic phosphoric acid diester was measured by 31 P-NMR under the following measurement conditions. The mass ratio was calculated from the integral ratio of the peak (1.7 ppm to 2.5 ppm) derived from the acidic phosphoric acid monoester to the peak (0.4 ppm to 1.2 ppm) derived from the acidic phosphoric acid diester in the obtained 31 P-NMP spectrum, and the substance amount of each phosphate.
• Apparatus Ascend 400 (manufactured by Bruker Corporation)
• Solvent deuterated chloroform Number of times: 256
• resin additive (A)-1 acidic phosphate ester of methoxypolyethylene glycol (number average molecular weight: 400).
• the content ratio of acidic phosphate monoester and acidic phosphate diester in resin additive (A)-1 was 55:45 by mass ratio.
• resin additive (A)-2 acidic phosphate ester of methoxypolyethylene glycol (number average molecular weight: 1,000).
• the content ratio of acidic phosphate monoester and acidic phosphate diester in resin additive (A)-2 was 57:43 by mass ratio.
• resin additive (A)-3 acidic phosphate ester of methoxypolyethylene glycol (number average molecular weight: 2,000).
• the content ratio of acidic phosphate monoester and acidic phosphate diester in resin additive (A)-3 was 59:41 by mass ratio.
• resin additive (A)-4 acidic phosphate ester of methoxypolyethylene glycol (number average molecular weight: 4,000).
• the content ratio of acidic phosphate monoester and acidic phosphate diester in resin additive (A)-4 was 63:37 by mass ratio.
• resin additive (A)-5 acidic phosphate ester of methoxypolyethylene glycol (number average molecular weight: 5,000).
• the content ratio of acidic phosphate monoester and acidic phosphate diester in resin additive (A)-5 was 63:37 by mass ratio.
• the composition obtained above was molded using an injection molding machine (machine name: NEX80, manufactured by Nissei Plastic Industrial Co., Ltd.) under conditions of a cylinder temperature of 260°C and a mold temperature of 80°C to obtain plate-shaped test pieces (60 mm x 60 mm x 2 mm).
• the weight loss rate (mass%) was measured when the temperature was raised from 30°C to 400°C at a heating rate of 10°C/min in a nitrogen atmosphere using a thermogravimetric/differential thermal analyzer (device name: Thermo plus EVO, manufactured by Rigaku Corporation), and the temperatures (°C) at which the weight loss rate was -5%, -10%, and -20% were determined.
• the results are shown in Table 1.
• ⁇ Method 1 for evaluating resin stabilization performance Colorability> The resin stabilizing performance of the resin additive was evaluated based on the colorability of the composition.
• the test pieces obtained above were measured for yellowness (YI) using a spectrophotometer (device name: ColorEye 7000A, manufactured by X-RITE) in accordance with JIS K7105 to evaluate colorability.
• YI yellowness
• a spectrophotometer device name: ColorEye 7000A, manufactured by X-RITE
• JIS K7105 JIS K7105
• the crystallization temperature of the composition obtained above was measured using a differential scanning calorimeter (Diamond DSC, manufactured by PerkinElmer).
• the sample was prepared by cutting the pellet-like composition obtained above into small pieces and weighing 8 ⁇ 1 mg into an aluminum pan.
• the crystallization temperature was measured by the following procedure. Under a nitrogen atmosphere, the temperature was raised from 30° C. to the holding temperature shown below at a rate of 20° C./min, and after holding for 5 minutes, it was cooled to 30° C. at a rate of ⁇ 20° C./min.
• resin additives (A)-1 to (A)-6 have high weight loss temperatures and excellent heat resistance.
• comparative resin additives (B)-1 and (B)-2 have lower weight loss temperatures than resin additives (A)-1 to (A)-6 and are inferior in heat resistance.
• the compositions of Examples 2-1 to 2-19 did not have any processing problems such as smoke generation and eye jerk during processing.
• the compositions of Comparative Examples 2-2 to 2-4 had processing problems such as smoke generation and eye jerk during processing. From this, it was found that the resin additive of the present invention has excellent heat resistance.
• Tables 3 to 5 show the evaluation results for compositions using alloys of PC resin and PBT resin with different content ratios than those in Table 2.
• Table 6 shows the evaluation results for compositions using alloys of PC resin and PET resin.
• the compositions containing the resin additive of the present invention did not experience processing problems such as smoke generation and eye gunk during processing.
• the compositions containing the comparative resin additive experienced processing problems such as smoke generation and eye gunk during processing.
• the compositions containing the resin additive of the present invention had smaller YI and ⁇ Tc values than the compositions not containing the resin additive of the present invention.

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