WO2011129394A1 - 熱可塑性ポリマー組成物および安定剤組成物 - Google Patents
熱可塑性ポリマー組成物および安定剤組成物 Download PDFInfo
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- WO2011129394A1 WO2011129394A1 PCT/JP2011/059265 JP2011059265W WO2011129394A1 WO 2011129394 A1 WO2011129394 A1 WO 2011129394A1 JP 2011059265 W JP2011059265 W JP 2011059265W WO 2011129394 A1 WO2011129394 A1 WO 2011129394A1
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- 0 *C(c1cc(*)cc(*)c1O)c1cc(*)cc(*)c1OC(C(*)=C)=O Chemical compound *C(c1cc(*)cc(*)c1O)c1cc(*)cc(*)c1OC(C(*)=C)=O 0.000 description 1
Classifications
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- 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
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- 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
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
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- 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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
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- 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
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- 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
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Definitions
- thermoplastic polymer composition containing at least one compound selected from the group consisting of compounds represented by formula (8), trehalose, and a thermoplastic polymer exhibits excellent processing stability. . Based on such knowledge, the inventors have reached the following invention.
- Each R 11 and each R 12 independently represent a hydrogen atom, a C 1-9 alkyl group, a C 5-8 cycloalkyl group, a C 6-12 alkylcycloalkyl group, a C 7-12 aralkyl group or a phenyl group.
- Each L 2 independently represents a single bond, a sulfur atom or formula (6a):
- R 13 and R 14 each independently represent a hydrogen atom or a C 1-7 alkyl group on condition that the total number of carbon atoms is 7 or less.
- ⁇ represents a divalent group.
- Each L 3 independently represents a C 2-8 alkylene group.
- Each R 15 and each R 16 independently represents a hydrogen atom, a C 1-9 alkyl group, a C 5-8 cycloalkyl group, a C 6-12 alkylcycloalkyl group, a C 7-12 aralkyl group or a phenyl group.
- R 17 is a C 1-8 alkyl group, or at least one selected from the group consisting of a C 1-9 alkyl group, a C 5-8 cycloalkyl group, a C 6-12 alkylcycloalkyl group, and a C 7-12 aralkyl group.
- L 4 represents a single bond, a sulfur atom or the formula (7a):
- Each R 20 , each R 21 , R 23 and R 24 is independently a hydrogen atom, a C 1-8 alkyl group, a C 5-8 cycloalkyl group, a C 6-12 alkyl cycloalkyl group, a C 7-12 Represents an aralkyl group or a phenyl group.
- Each R 22 independently represents a hydrogen atom or a C 1-8 alkyl group.
- L 5 represents a single bond, a sulfur atom or the formula (8a):
- L 7 represents a single bond or a C 1-8 alkylene group. * Represents bonding to the oxygen atom side. ⁇ Represents a divalent group.
- One of Z 1 and Z 2 represents a hydroxy group, a C 1-8 alkyl group, a C 1-8 alkoxy group or a C 7-12 aralkyloxy group, and the other represents a hydrogen atom or a C 1-8 alkyl group Represents.
- a thermoplastic polymer composition comprising: a compound represented by the formula: trehalose; and a thermoplastic polymer.
- thermoplastic polymer composition according to the above [10], wherein the total amount of the compound represented by the formula (8) and trehalose is 0.001 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic polymer.
- a stabilizer composition comprising a compound represented by formula (8) and trehalose.
- the compound represented by the formula (8) is 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz.
- the stabilizer composition according to the above [12] which is [d, f] [1, 3, 2] dioxaphosphine.
- a method for producing a thermoplastic polymer composition comprising mixing the stabilizer composition according to any one of the above [12] to [16] and a thermoplastic polymer.
- thermoplastic polymer composition comprising a compound represented by formula (2), trehalose and a thermoplastic polymer.
- a stabilizer composition comprising a compound represented by formula (2) and trehalose.
- the compound represented by the formula (2) is octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,9-bis [2- ⁇ 3- (3-t- Butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and pentaerythritol tetrakis [3- (3
- a stabilizer composition comprising at least one selected from the group consisting of compounds represented by formulas (3) to (7) and trehalose.
- a method for producing a thermoplastic polymer composition comprising mixing the stabilizer composition according to any one of [30] to [33] above and a thermoplastic polymer.
- thermoplastic polymer composition When at least one selected from the group consisting of compound (1), compound (2), compound (3) to compound (7) or compound (8) and trehalose are used in combination, processing stability of the thermoplastic polymer composition Can be improved.
- thermoplastic polymer composition of the present invention and the stabilizer composition of the present invention containing compound (1) and trehalose as essential components are referred to as “first thermoplastic polymer composition” and “first May be referred to as a "stabilizer composition”.
- first thermoplastic polymer composition and “first May be referred to as a "stabilizer composition”.
- second thermoplastic polymer composition and “second stability”.
- agent composition sometimes referred to as “agent composition”.
- the first thermoplastic polymer composition contains compound (1), trehalose and a thermoplastic polymer. Only 1 type may be used for a compound (1) and it may use 2 or more types together.
- the compound (1) will be described in order.
- Each R 1 and each R 2 in Formula (1) each independently represents a C 1-8 alkyl group, a C 6-12 aryl group, or a C 7-18 aralkyl group. There are two R 1 s, but each R 1 may be the same as or different from each other, preferably the same. The same applies to each R 2 .
- R 3 in the formula (1) represents a hydrogen atom or a C 1-3 alkyl group.
- the C 1-3 alkyl group may be linear or branched. Examples of the C 1-3 alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
- R 3 is preferably a hydrogen atom or a methyl group.
- R 4 in formula (1) represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
- Examples of the compound (1) include 2,4-di-t-butyl-6- [1- (3,5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl (meth) acrylate, 2- t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl (meth) acrylate, 2,4-di-t-pentyl-6- [1- (3 5-Di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl (meth) acrylate, 2,4-di-t-butyl-6- (3,5-di-t-butyl-2-hydroxy-benzyl) Phenyl (meth) acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-ethylphenyl (meth) acrylate, 2-t-pentyl-6- (3 -T
- Compound (1-1) is commercially available as Sumilizer (registered trademark) GS (F) (manufactured by Sumitomo Chemical Co., Ltd.), and Compound (1-2) is commercially available as Sumilizer (registered trademark) GM (manufactured by Sumitomo Chemical Co., Ltd.).
- Compound (1) may be a commercially available product, or can be produced according to a known method (for example, the method described in JP-A No. 1-168643 or JP-A No. 58-84835).
- Trehalose may be an anhydride, a hydrate, or a mixture thereof. Trehalose is commercially available, and a commercially available product can be used as it is.
- thermoplastic polymer Only one type of thermoplastic polymer may be used, or two or more types may be used in combination.
- examples of the thermoplastic polymer include polyethylene resins (high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl alcohol copolymer (EVOH), ethylene-acrylic.
- HDPE high density polyethylene
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- EVOH ethylene-vinyl alcohol copolymer
- ethylene-acrylic ethylene-acrylic.
- Ethyl acetate copolymer Ethyl acetate copolymer
- Ethyl acetate copolymer Ethyl acetate copolymer
- EVA ethylene-vinyl acetate copolymer
- polypropylene resin crystalline propylene homopolymer, propylene-ethylene random copolymer, propylene- ⁇ -olefin random copolymer
- Propylene-ethylene- ⁇ -olefin copolymer propylene homopolymer or block of propylene-based copolymer
- Polypropylene block co-weight Methylpentene polymers, polystyrene resins (polystyrene (PS), poly (p-methylstyrene), poly ( ⁇ -methylstyrene) and other polystyrenes, acrylonitrile-styrene copolymer (
- polyethylene resins polypropylene resins, polystyrene resins and polybutadiene resins are preferable, polyethylene resins and polybutadiene resins are more preferable, and styrene-butadiene block copolymers (SBS). Is more preferable.
- SBS styrene-butadiene block copolymers
- the Mw of the thermoplastic polymer is generally 1000 or more and 300,000 or less. This Mw can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard.
- the total amount of compound (1) and trehalose in the first thermoplastic polymer composition is preferably 0.001 to 3 parts by weight, more preferably 0.02 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. Part, more preferably 0.02 to 1 part by weight.
- the weight ratio of compound (1) to trehalose in the first thermoplastic polymer composition is preferably 1000: 1 to 0.05: 1.
- Compound (1): Trehalose is more preferably 1000: 1 to 0.1: 1 from the viewpoint of processing stability of the thermoplastic polymer composition, and further from the viewpoint of suppressing discoloration of the thermoplastic polymer composition.
- the ratio is preferably 1000: 1 to 0.5: 1, particularly preferably 1000: 1 to 1: 1.
- Each R 5 and each R 6 in the formula (2) each independently represents a hydrogen atom or a C 1-6 alkyl group.
- n is 2 or more, each R 5 may be the same as or different from each other, preferably the same. The same applies to each R 6 .
- the C 1-6 alkyl group may be either chain or cyclic, and the chain may be either linear or branched.
- Examples of the C 1-6 alkyl group include a linear C 1-6 alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group), branched C 3-6 alkyl group (for example, , Isopropyl group, isobutyl group, t-butyl group, isopentyl group, t-pentyl group, t-hexyl group), cyclic C 3-6 alkyl group (ie C 3-6 cycloalkyl group such as cyclopentyl group, cyclohexyl group) ).
- a linear C 1-6 alkyl group methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group
- branched C 3-6 alkyl group for example, , Isopropyl group, isobutyl group, t-butyl group, isopentyl group
- Each R 5 and each R 6 are independently preferably a linear C 1-6 alkyl group or a branched C 3-6 alkyl group, more preferably a methyl group or a t-butyl group. More preferably, each R 5 and each R 6 are all t-butyl groups.
- L 1 in the formula (2) represents an n-valent C 1-24 alcohol residue which may contain a hetero atom, and n represents an integer of 1 to 4.
- the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom, and these hetero atoms may be replaced with carbon atoms in the n-valent C 1-24 alcohol residue. That is, the n-valent C 1-24 alcohol residue represents —O—, —S—, —NR— (wherein R represents a hydrogen atom or another substituent (eg, a C 1-6 alkyl group)). ) And the like.
- R represents a hydrogen atom or another substituent (eg, a C 1-6 alkyl group)).
- R represents a hydrogen atom or another substituent (eg, a C 1-6 alkyl group)
- a hetero atom an oxygen atom is preferable.
- the chain may be linear or branched.
- Examples of monovalent C 1-24 alcohol residues include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and the like. Residue.
- divalent C 1-24 alcohol residue examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, diethylene glycol, triethylene glycol, 3,9-bis ( And residues such as 1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane.
- Examples of the tetravalent C 1-24 alcohol residue include residues such as erythritol and pentaerythritol.
- Examples of the compound (2) include 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid and 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid. Or esters of 3- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols.
- Examples of the monohydric or polyhydric alcohol include methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9.
- neopentyl glycol diethylene glycol, thioethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3- Thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane, 3,9-bis (1,1- Dimethyl-2-hydroxy Ethyl) -2,4,8,10 such tetraoxaspiro [5.5] undecane and mixtures thereof.
- Compound (2-1) is “Irganox (registered trademark) 1076” (manufactured by BASF)
- compound (2-2) is “Smilizer (registered trademark) GA-80” (manufactured by Sumitomo Chemical)
- compound ( 2-3) is commercially available as “Irganox (registered trademark) 1010” (manufactured by BASF).
- Compound (2) may be a commercially available product, or may be produced according to a known method (for example, the method described in US Pat. No. 3,330,859, US Pat. No. 3,644,482 or JP-A-59-25826). Can do.
- the content of the compound (2) is preferably 0.001 to 3 weights with respect to 100 parts by weight of the first thermoplastic polymer composition. Part, more preferably 0.02 to 2 parts by weight.
- the first thermoplastic polymer composition may further contain at least one selected from the group consisting of compounds (3) to (7). Only one of compound (3) to compound (7) may be used, or two or more may be used in combination. Hereinafter, the compounds (3) to (7) will be described in order.
- each R 7 and each R 8 are each independently a hydrogen atom, a C 1-9 alkyl group, a C 5-8 cycloalkyl group, a C 6-12 alkylcycloalkyl group, a C 7-12 Represents an aralkyl group or a phenyl group.
- There are three R 7 s and each R 7 may be the same as or different from each other, preferably the same. The same applies to each R 8 .
- the positions of R 7 and R 8 are preferably the 2nd and 4th positions.
- Examples of the C 5-8 cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
- Examples of the C 6-12 alkylcycloalkyl group include 1-methylcyclopentyl group, 2-methylcyclopentyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 1-methyl-4-isopropylcyclohexyl group and the like. .
- Examples of the C 7-12 aralkyl group include a benzyl group, ⁇ -methylbenzyl group (also referred to as 1-phenylethyl group), ⁇ , ⁇ -dimethylbenzyl group (1-methyl-1-phenylethyl group or cumyl group). For example).
- Each R 7 and each R 8 are independently preferably a hydrogen atom or a C 1-9 alkyl group, more preferably a hydrogen atom, a t-butyl group or a nonyl group, and still more preferably a t-butyl group.
- Examples of the compound (3) include tris (2,4-di-t-butylphenyl) phosphite (hereinafter sometimes abbreviated as “compound (3-1)”), triphenyl phosphite, tris (4 -Nonylphenyl) phosphite, tris (2,4-dinonylphenyl) phosphite and the like. Of these, the compound (3-1) is preferable.
- the compound (3-1) is commercially available as “Irgaphos (registered trademark) 168” (manufactured by BASF).
- Each R 9 in formula (4) is independently a hydrogen atom, a C 1-9 alkyl group, a C 5-8 cycloalkyl group, a C 6-12 alkylcycloalkyl group, a C 7-12 aralkyl group or phenyl. Represents a group. There are four R 9 s , and each R 9 may be the same as or different from each other, preferably the same. Examples of the C 1-9 alkyl group, the C 5-8 cycloalkyl group, the C 6-12 alkylcycloalkyl group, and the C 7-12 aralkyl group represented by R 9 include those described above. Each R 9 is independently preferably a hydrogen atom or a C 1-9 alkyl group, more preferably a hydrogen atom.
- Examples of the compound (4) include tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonite (hereinafter sometimes abbreviated as “compound (4-1)”), tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4-biphenylenediphosphonite (hereinafter sometimes abbreviated as “compound (4-2)”). Of these, the compound (4-1) is preferable.
- Compound (4-1) is “Sandstub (registered trademark) P-EPQ” (manufactured by Clariant), and Compound (4-2) is “Yosinox (registered trademark) GSY-P101” (manufactured by API). It is commercially available.
- Each R 10 in the formula (5) independently represents a C 1-18 alkyl group or a phenyl group.
- the phenyl group of R 10 is at least one selected from the group consisting of a C 1-9 alkyl group, a C 5-8 cycloalkyl group, a C 6-12 alkylcycloalkyl group, and a C 7-12 aralkyl group as a substituent. You may have. In addition, the above-mentioned thing is mentioned as a substituent of these phenyl groups.
- Two R 10 exist, and each R 10 may be the same as or different from each other, preferably the same.
- the C 1-18 alkyl group may be linear or branched.
- the carbon number of the C 1-18 alkyl group is preferably 12 or more and 18 or less.
- Examples of the C 1-18 alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group. Group, octadecyl group and the like.
- Examples of the phenyl group substituted with a C 1-9 alkyl group include a 2-methylphenyl group, a 4-methylphenyl group, a 2-t-butylphenyl group, a 4-t-butylphenyl group, a 2-nonylphenyl group, 4-nonylphenyl group, 2,4-di-t-butylphenyl group, 2,4-di-nonylphenyl group, 2,6-di-t-butylphenyl group, 2-t-butyl-4-methylphenyl Group, 2-t-butyl-4-ethylphenyl group, 2,5-di-t-butylphenyl group, 2,6-di-t-butyl-4-methylphenyl group and the like.
- Examples of the phenyl group substituted with a C 5-8 cycloalkyl group include a 2-cyclopentylphenyl group, a 2-cyclohexylphenyl group, a 4-cyclohexylphenyl group, and a 2,4-dicyclohexylphenyl group.
- Examples of the phenyl group substituted with a C 6-12 alkylcycloalkyl group include 2- (2-methylcyclohexyl) phenyl group, 4- (2-methylcyclohexyl) phenyl group, 2,4-di- (2-methyl). (Cyclohexyl) phenyl group and the like.
- Examples of the phenyl group substituted with a C 7-12 aralkyl group include a 2-benzylphenyl group, a 2-cumylphenyl group, a 4-cumylphenyl group, and a 2,4-dicumylphenyl group.
- Each R 10 is preferably independently an octadecyl group (also referred to as a stearyl group), a 2,6-di-t-butyl-4-methylphenyl group, a 2,4-di-t-butylphenyl group, or 2 , 4-Dicumylphenyl group.
- octadecyl group also referred to as a stearyl group
- 2,6-di-t-butyl-4-methylphenyl group a 2,4-di-t-butylphenyl group
- 2 4-Dicumylphenyl group.
- Examples of the compound (5) include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (hereinafter sometimes referred to as “compound (5-1)”), bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (hereinafter sometimes abbreviated as “compound (5-2)”), bis (2,4-dicumylphenyl) pentaerythritol diphosphite (Hereinafter sometimes abbreviated as “compound (5-3)”), distearyl pentaerythritol diphosphite (hereinafter sometimes abbreviated as “compound (5-4)”), diisodecyl pentaerythritol diphosphite, Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-buty
- the compound (5-1), the compound (5-2) and the compound (5-3) are preferable.
- Compound (5-1) is “ADK STAB (registered trademark) PEP-36” (manufactured by Adeka)
- compound (5-2) is “Ultranox (registered trademark) 626” (manufactured by GE Plastics)
- compound ( 5-3) is commercially available as “Doverphos S9228T” (manufactured by Dover Chemical)
- compound (5-4) is commercially available as “Adekastab (registered trademark) PEP-8” (manufactured by Adeka).
- each R 11 and each R 12 are independently a hydrogen atom, a C 1-9 alkyl group, a C 5-8 cycloalkyl group, a C 6-12 alkylcycloalkyl group, a C 7-12 Represents an aralkyl group or a phenyl group.
- Examples of the C 1-9 alkyl group, C 5-8 cycloalkyl group, C 6-12 alkylcycloalkyl group and C 7-12 aralkyl group of R 11 and R 12 include those described above.
- each R 11 may be the same as or different from each other, preferably the same. The same applies to each R 12 .
- R 11 and R 12 are preferably the 3rd and 5th positions when the position of the carbon atom of the benzene ring to which L 2 is bonded is the 1st position, respectively.
- Each R 11 and each R 12 are independently preferably a C 1-9 alkyl group, more preferably a t-butyl group.
- Each L 2 in the formula (6) independently represents a single bond, a sulfur atom or a divalent group represented by the formula (6a).
- R 13 and R 14 in the formula (6a) Each independently represents a hydrogen atom or a C 1-7 alkyl group, provided that the total number of carbon atoms is 7 or less.
- There are three L 2 s and each L 2 may be the same or different from each other, and is preferably the same.
- the C 1-7 alkyl group may be linear or branched.
- the carbon number of the C 1-7 alkyl group is preferably 1 or more and 3 or less.
- the total number of carbon atoms of R 13 and R 14 is preferably 3 or less.
- Examples of the C 1-7 alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, t- A pentyl group, a hexyl group, a heptyl group, etc. are mentioned.
- Examples of the divalent group (6a) include —CH 2 —, —CH (CH 3 ) —, —CH (C 2 H 5 ) —, —C (CH 3 ) 2 —, —CH (n—C). 3 H 7 ) — and the like.
- Each L 2 is preferably —CH 2 — or a single bond, more preferably a single bond.
- Each L ⁇ 3 > in Formula (6) represents a C2-8 alkylene group each independently.
- Examples of the C 2-8 alkylene group include ethylene, propylene (—CH (CH 3 ) CH 2 —, —CH 2 CH (CH 3 ) —), trimethylene, tetramethylene, pentamethylene, hexa
- Examples include a methylene group, an octamethylene group, and a 2,2-dimethyl-1,3-propylene group.
- Each L 3 is independently preferably an ethylene group or a trimethylene group, more preferably an ethylene group.
- compound (6-1) As the compound (6), 6,6 ′, 6 ′′-[nitrilotris (ethyleneoxy)] tris (2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] Dioxaphosphepine) (hereinafter sometimes abbreviated as “compound (6-1)”).
- Compound (6-1) is commercially available as “Irgaphos (registered trademark) 12” (manufactured by BASF).
- each R 15 and each R 16 independently represent a hydrogen atom, a C 1-9 alkyl group, a C 5-8 cycloalkyl group, a C 6-12 alkylcycloalkyl group, a C 7-12 Represents an aralkyl group or a phenyl group.
- Examples of the C 1-9 alkyl group, the C 5-8 cycloalkyl group, the C 6-12 alkylcycloalkyl group, and the C 7-12 aralkyl group of R 15 and R 16 include those described above.
- each R 15 may be the same as or different from each other, preferably the same. The same applies to each R 16 .
- the positions of R 15 and R 16 are the 3rd and 5th positions when the position of the carbon atom of the benzene ring to which L 4 is bonded is the 1st position, that is, the benzene ring to which O is bonded. When the position of each carbon atom is the 1st position, the 2nd and 4th positions are preferred.
- Each R 15 and each R 16 are independently preferably a C 1-9 alkyl group, more preferably a t-butyl group.
- R 17 in the formula (7) represents a C 1-8 alkyl group or a phenyl group.
- the phenyl group of R 17 is at least one selected from the group consisting of a C 1-9 alkyl group, a C 5-8 cycloalkyl group, a C 6-12 alkylcycloalkyl group, and a C 7-12 aralkyl group as a substituent. You may have. Examples of the phenyl group having a C 1-8 alkyl group and a substituent for R 17 include those described above. However, the carbon number of the C 1-8 alkyl group of R 17 is preferably 4 or more and 8 or less. R 17 is preferably a C 1-8 alkyl group, more preferably an octyl group.
- L 4 in the formula (7) represents a single bond, a sulfur atom or a divalent group represented by the formula (7a), and R 18 and R 19 in the formula (7a) have a total carbon number of 7 or less.
- Examples of the C 1-7 alkyl group for R 18 and R 19 include those described above.
- the total number of carbon atoms of R 18 and R 19 is preferably 3 or less.
- Specific examples of the divalent group (7a) include the same as the divalent group (6a).
- L 4 is preferably —CH 2 — or a single bond, more preferably —CH 2 —.
- Examples of the compound (7) include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (hereinafter sometimes abbreviated as “compound (7-1)”) and 2,2 Examples include '-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite. Of these, the compound (7-1) is preferable.
- Compound (7-1) is commercially available as “Adekastab (registered trademark) HP-10” (manufactured by Adeka).
- the compound (3) is preferable, and the compound (3-1) is more preferable.
- the first thermoplastic polymer composition contains at least one selected from the group consisting of compounds (3) to (7), the total of compounds selected from the group consisting of compounds (3) to (7) The amount is preferably 0.001 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, based on 100 parts by weight of the first thermoplastic polymer composition.
- the second thermoplastic polymer composition contains compound (8), trehalose and a thermoplastic polymer. Only one type of compound (8) may be used, or two or more types may be used in combination. The description of trehalose and thermoplastic polymer in the second thermoplastic polymer composition is the same as described above. Hereinafter, the compound (8) will be described in order.
- each R 20 , each R 21 , R 23 and R 24 is independently a hydrogen atom, a C 1-8 alkyl group, a C 5-8 cycloalkyl group, a C 6-12 alkyl cycloalkyl. Represents a group, a C 7-12 aralkyl group or a phenyl group.
- each R 20 may be the same as or different from each other, preferably the same. The same applies to each R 21 .
- the C 1-8 alkyl group may be linear or branched.
- the carbon number of the C 1-8 alkyl group is preferably 1 or more and 5 or less.
- Examples of the C 1-8 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a t-pentyl group, and an isooctyl group (6-methyl).
- a heptyl group), a t-octyl group also referred to as a 1,1,3,3-tetramethylbutyl group
- 2-ethylhexyl group and the like.
- Examples of the C 5-8 cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
- Examples of the C 6-12 alkylcycloalkyl group include 1-methylcyclopentyl group, 2-methylcyclopentyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 1-methyl-4-isopropylcyclohexyl group and the like. .
- Examples of the C 7-12 aralkyl group include a benzyl group, ⁇ -methylbenzyl group (also referred to as 1-phenylethyl group), ⁇ , ⁇ -dimethylbenzyl group (1-methyl-1-phenylethyl group or cumyl group). For example).
- Each R 20 and R 23 is preferably independently a C 1-8 alkyl group (more preferably a C 4-8 alkyl group having a tertiary carbon atom) or a C 5-8 cycloalkyl group (more preferably A cyclohexyl group) or a C 6-12 alkylcycloalkyl group (more preferably a 1-methylcyclohexyl group).
- the C 4-8 alkyl group having a tertiary carbon atom is more preferably a t-butyl group, a t-pentyl group or a t-octyl group.
- Each R 21 is independently preferably a C 1-8 alkyl group, a C 5-8 cycloalkyl group or a C 6-12 alkylcycloalkyl group, and more preferably a C 1-5 alkyl group.
- the C 1-5 alkyl group may be linear or branched. Examples of the C 1-5 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, and a t-pentyl group. More preferably, each R 21 independently represents a methyl group, a t-butyl group or a t-pentyl group.
- R 24 is preferably a hydrogen atom or a C 1-5 alkyl group, more preferably a hydrogen atom or a methyl group.
- Examples of the C 1-5 alkyl group for R 24 include those described above.
- Each R 22 in Formula (8) independently represents a hydrogen atom or a C 1-8 alkyl group. There are two R 22 s , and each R 22 may be the same as or different from each other, preferably the same. Each R 22 is preferably a hydrogen atom or a C 1-5 alkyl group, more preferably a methyl group or a hydrogen atom. Examples of the C 1-8 alkyl group and the C 1-5 alkyl group for R 22 include those described above.
- L 5 in the formula (8) represents a single bond, a sulfur atom or a divalent group represented by the formula (8a), and R 25 in the formula (8a) represents a hydrogen atom, a C 1-8 alkyl group or C 5-8 represents a cycloalkyl group.
- R 25 is preferably a hydrogen atom or a C 1-5 alkyl group. Examples of the C 1-8 alkyl group, C 1-5 alkyl group, and C 5-8 cycloalkyl group represented by R 25 include those described above.
- L 5 is preferably a single bond or a divalent group (8a), and more preferably a single bond.
- L 6 in the formula (8) represents a C 2-8 alkylene group or a divalent group represented by the formula (8b), and L 7 in the formula (8b) represents a single bond or a C 1-8 alkylene group.
- Both the C 2-8 alkylene group and the C 1-8 alkylene group may be linear or branched.
- Examples of the C 2-8 alkylene group include ethylene, propylene (—CH (CH 3 ) CH 2 —, —CH 2 CH (CH 3 ) —), trimethylene, tetramethylene, pentamethylene, hexa
- Examples include a methylene group, an octamethylene group, and a 2,2-dimethyl-1,3-propylene group.
- Examples of the C 1-8 alkylene group include a methylene group and the aforementioned C 2-8 alkylene group.
- L 6 is preferably a C 2-8 alkylene group, a divalent group (8b) in which L 7 is a single bond (ie, a carbonyl group), or a divalent group (8b) in which L 7 is an ethylene group. Yes ; more preferably a C 2-8 alkylene group; still more preferably a trimethylene group.
- any one of Z 1 and Z 2 represents a hydroxy group, a C 1-8 alkyl group, a C 1-8 alkoxy group or a C 7-12 aralkyloxy group, and the other represents a hydrogen atom or C 1-8 represents an alkyl group.
- Examples of the C 1-8 alkyl group for Z 1 and Z 2 include those described above.
- the C 1-8 alkoxy group may be linear or branched.
- Examples of the C 1-8 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a t-pentyloxy group, and an isooctyloxy group.
- t-octyloxy group also referred to as 1,1,3,3-tetramethylbutyloxy group
- 2-ethylhexyloxy group and the like are examples of the C 1-8 alkoxy group.
- Examples of the C 7-12 aralkyloxy group include benzyloxy group, ⁇ -methylbenzyloxy group, ⁇ , ⁇ -dimethylbenzyloxy group and the like.
- one of Z 1 and Z 2 is a hydroxy group and the other is a hydrogen atom.
- each R 20 and R 23 is each independently a C 4-8 alkyl group, cyclohexyl or 1-methylcyclohexyl group having a tertiary carbon atom, and each R 21 is independently Are each a C 1-5 alkyl group, each R 22 is independently a hydrogen atom or a C 1-5 alkyl group, R 24 is a hydrogen atom or a C 1-5 alkyl group, and L 5 is a single bond And a combination in which L 6 is a C 2-8 alkylene group, one of Z 1 and Z 2 is a hydroxy group, and the other is a hydrogen atom.
- each R 20 is more preferably the same as each other.
- each R 20 , each R 22 and R 23 is more preferably a t-butyl group or a t-pentyl group (particularly a t-butyl group) in common.
- Examples of the compound (8) include 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f ] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-) t-butyl-4-hydroxyphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propoxy]
- compound (8-1) 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [ 1,3,2] dioxaphosphepine (hereinafter sometimes abbreviated as “compound (8-1)”) is preferred.
- Compound (8-1) is commercially available as “Sumilyzer (registered trademark) GP” (manufactured by Sumitomo Chemical Co., Ltd.).
- Compound (8) may be a commercially available product, or can be produced according to a known method (for example, the method described in JP-A-10-273494).
- the total amount of compound (8) and trehalose in the second thermoplastic polymer composition is preferably 0.001 to 3 parts by weight, more preferably 0.02 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. Part, more preferably 0.02 to 1 part by weight.
- the weight ratio of compound (8) to trehalose in the second thermoplastic polymer composition is preferably 1000: 1 to 0.05: 1.
- Compound (8): Trehalose is more preferably 1000: 1 to 0.1: 1 from the viewpoint of processing stability of the thermoplastic polymer composition, and further from the viewpoint of suppressing discoloration of the thermoplastic polymer composition.
- the ratio is preferably 1000: 1 to 0.5: 1, particularly preferably 1000: 1 to 1: 1.
- the second thermoplastic polymer composition may further contain a compound (2). Only one type of compound (2) may be used, or two or more types may be used in combination. The description of compound (2) is the same as described above.
- the content of the compound (2) is preferably 0.001 to 3 weights with respect to 100 parts by weight of the second thermoplastic polymer composition. Part, more preferably 0.02 to 2 parts by weight.
- the second thermoplastic polymer composition may further contain at least one selected from the group consisting of compounds (3) to (7). Only one of compound (3) to compound (7) may be used, or two or more may be used in combination. The description of the compounds (3) to (7) is the same as described above.
- the second thermoplastic polymer composition contains at least one selected from the group consisting of compounds (3) to (7), the total of compounds selected from the group consisting of compounds (3) to (7) The amount is preferably 0.001 to 3 parts by weight, more preferably 0.02 to 2 parts by weight with respect to 100 parts by weight of the second thermoplastic polymer composition.
- the third thermoplastic polymer composition contains compound (2), trehalose and a thermoplastic polymer. Only one type of compound (2) may be used, or two or more types may be used in combination. The description of the compound (2), trehalose and the thermoplastic polymer in the third thermoplastic polymer composition is the same as described above.
- the total amount of compound (2) and trehalose in the third thermoplastic polymer composition is preferably 0.001 to 3 parts by weight, more preferably 0.02 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. Part, more preferably 0.02 to 1 part by weight.
- the weight ratio of compound (2) to trehalose in the third thermoplastic polymer composition is preferably 1000: 1 to 0.05: 1.
- Compound (2): Trehalose is more preferably 1000: 1 to 0.1: 1 from the viewpoint of processing stability of the thermoplastic polymer composition, and further from the viewpoint of suppressing discoloration of the thermoplastic polymer composition.
- the ratio is preferably 1000: 1 to 0.5: 1, particularly preferably 1000: 1 to 1: 1.
- the third thermoplastic polymer composition may further contain a compound (1). Only 1 type may be used for a compound (1) and it may use 2 or more types together. The description of compound (1) is the same as described above.
- the third thermoplastic polymer composition may further contain at least one selected from the group consisting of compounds (3) to (7). Only one of compound (3) to compound (7) may be used, or two or more may be used in combination. The description of the compounds (3) to (7) is the same as described above.
- the third thermoplastic polymer composition may further contain a compound (8). Only one type of compound (8) may be used, or two or more types may be used in combination. The description of compound (8) is the same as described above.
- compounds (1) and (3) to (8) that can be used in the third thermoplastic polymer composition compounds (1), (3) and (8) are preferred.
- each of compounds (1) and (3) to (8) contains at least one of compound (1) and compounds (3) to (8), each of compounds (1) and (3) to (8)
- the amount is preferably 0.001 to 3 parts by weight, more preferably 0.02 to 2 parts by weight with respect to 100 parts by weight of the third thermoplastic polymer composition.
- the fourth thermoplastic polymer composition contains at least one selected from the group consisting of compound (3) to compound (7) (that is, organophosphorus compound), trehalose and a thermoplastic polymer. Only one of compound (3) to compound (7) may be used, or two or more may be used in combination. The descriptions of the compounds (3) to (7) and the thermoplastic polymer in the fourth thermoplastic polymer composition are the same as those described above.
- the total amount of the compound selected from the group consisting of compounds (3) to (7) and trehalose in the fourth thermoplastic polymer composition is preferably 0.001 to 3 with respect to 100 parts by weight of the thermoplastic polymer. Parts by weight, more preferably 0.02 to 2 parts by weight, still more preferably 0.02 to 1 part by weight.
- the weight ratio of the compound selected from the group consisting of compound (3) to compound (7) and trehalose in the fourth thermoplastic polymer composition is preferably 1000: 1 to 0.05: 1.
- the compound selected from the group consisting of compounds (3) to (7): trehalose is more preferably 1000: 1 to 0.1: 1 from the viewpoint of processing stability of the thermoplastic polymer composition, From the viewpoint of suppressing discoloration of the plastic polymer composition, it is more preferably 1000: 1 to 0.5: 1, and particularly preferably 1000: 1 to 1: 1.
- the fourth thermoplastic polymer composition may further contain at least one selected from the group consisting of compound (1), compound (2) and compound (8).
- a compound (1), a compound (2), and a compound (8) all may use only 1 type and may use 2 or more types together.
- the explanation of compound (1), compound (2) and compound (8) is the same as described above.
- the fourth thermoplastic polymer composition contains at least one of the compound (1), the compound (2) and the compound (8), each of the compound (1), the compound (2) and the compound (8)
- the amount is preferably 0.001 to 3 parts by weight, more preferably 0.02 to 2 parts by weight with respect to 100 parts by weight of the fourth thermoplastic polymer composition.
- thermoplastic polymer composition of the present invention may contain additives other than the above components (hereinafter abbreviated as “other additives”). Only 1 type may be used for another additive and it may use 2 or more types together.
- Other additives include, for example, antioxidants, ultraviolet absorbers, light stabilizers, stabilizers, lubricants, metal deactivators, nucleating agents, antistatic agents, flame retardants, fillers, pigments, inorganic fillers Agents and the like.
- antioxidants examples include phenolic antioxidants (excluding compounds (1) and (2)), sulfur antioxidants, and phosphorus antioxidants (excluding compounds (3) to (8). ) And hydroquinone antioxidants.
- phenolic antioxidant examples include those described in the following [1] to [16].
- ⁇ - (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and a mono- or polyhydric alcohol for example, methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3 -Propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) Isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6 7 Trio key rust cycl
- ⁇ - (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and a mono- or polyhydric alcohol for example, methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N , N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- Riokisabishikuro
- Tocopherols such as ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, and ⁇ -tocopherol.
- sulfur antioxidants include dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'- Examples include thiodipropionate, lauryl stearyl, 3,3′-thiodipropionate, and neopentanetetrakis (3-lauryl thiopropionate).
- phosphorus antioxidants include trilauryl phosphite, trioctadecyl phosphite, tristearyl sorbitol triphosphite, 2,2′-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4-di-t-butyl-6-methylphenyl) methyl phosphite, 2- (2,4,6- And tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane.
- hydroquinone antioxidant examples include 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-pentylhydroquinone, 2,6 -Diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl steer And bis (3,5-di-t-butyl-4-hydroxyphenyl) adipate.
- ultraviolet absorber examples include those described in [1] to [3] below.
- Examples of the light stabilizer include those described in [1] to [5] below.
- [1] A hindered amine light stabilizer such as those described in the following [a] to [c].
- Examples of the stabilizer include N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, and N, N-ditetradecylhydroxyamine.
- Hydroxyamines such as N, N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine, and the like.
- the lubricant examples include aliphatic hydrocarbons such as paraffin and wax, C 8-22 higher fatty acids, C 8-22 higher fatty acid metal (Al, Ca, Mg, Zn) salts, C 8-22 aliphatic alcohols, Examples include polyglycols, esters of C 4-22 fatty acids and C 4-18 aliphatic monohydric alcohols, C 8-22 higher aliphatic amides, silicone oils, rosin derivatives, and the like.
- aliphatic hydrocarbons such as paraffin and wax
- C 8-22 higher fatty acids C 8-22 higher fatty acid metal (Al, Ca, Mg, Zn) salts
- C 8-22 aliphatic alcohols examples include polyglycols, esters of C 4-22 fatty acids and C 4-18 aliphatic monohydric alcohols, C 8-22 higher aliphatic amides, silicone oils, rosin derivatives, and the like.
- Particularly preferred phenolic antioxidants include the following: 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,4-bis ( Octylthiomethyl) -6-t-butylphenol, 2,2'-thiobis (6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis ( 4-ethyl-6-t-butylphenol), 2,2′-methylenebis [4-methyl-6- ( ⁇ -methylcyclohexyl) phenol], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4,6-di-t-butylphenol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), 4,4'-methylenebis (6-t-butyl-2-methylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,
- Particularly preferred phosphorus antioxidants include the following: 2,2′-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-) Butyl-6-methylphenyl) ethyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane.
- Particularly preferred ultraviolet absorbers include the following: phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4 ′ -Hydroxybenzoate, 4-t-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, Bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxypheny ) Benzotriazole, 2- (5′-t-butyl-2′-hydroxyphenyl) benzotriazole
- hindered amine light stabilizers include the following: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl- 4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) ) Sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3 5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2, -Bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate
- thermoplastic polymer composition of the present invention examples include, for example, (A) When kneading the thermoplastic polymer, compounds (1) to (8) and trehalose as essential components, and optional components (1) to (8) and other additions as necessary A method of separately blending the agent with the thermoplastic polymer; (B) First, the compounds (1) to (8) and trehalose, which are essential components, and optional components (1) to (8) and other additives are mixed and stabilized as necessary. A method of producing an agent composition and then mixing the resulting stabilizer composition into a thermoplastic polymer; Etc. From the viewpoint of dispersibility of the essential components of the compounds (1) to (8) and trehalose in the thermoplastic polymer, the method (b) is preferred.
- the method for producing the stabilizer composition in the method (b) is the same as the method exemplified in the method for producing the stabilizer composition described later.
- thermoplastic polymer composition pellets As a method of mixing the stabilizer composition and the thermoplastic polymer, for example, (C) A method in which a stabilizer composition and a thermoplastic polymer are dry-blended, and then melt-kneaded in a single-screw or multi-screw extruder, followed by extrusion to obtain thermoplastic polymer composition pellets; (D) A method in which the stabilizer composition is dissolved in a solvent such as cyclohexane to prepare a solution of the stabilizer composition, and this solution is added to the polymer solution after the completion of the polymerization of the thermoplastic polymer to remove the solvent; Etc.
- a solvent such as cyclohexane
- the obtained thermoplastic polymer composition may be molded by supplying it to a molding machine in a molten state without cooling.
- the molding method is not particularly limited, and for example, a molding method such as an injection molding method, an extrusion molding method, an extrusion blow molding method, an injection blow molding method, or a biaxial stretch blow molding method can be used.
- thermoplastic polymer molded article made of the thermoplastic polymer composition of the present invention is obtained.
- Applications of the thermoplastic polymer moldings obtained include, for example, electronic components (for example, coil bobbins, connectors, switches, resistor components, sockets, relays, capacitor cases, fuses, motors, microwave ovens, printed boards, IC manufacturing equipment, lamps.
- Automotive parts eg air outlet garnish, hood vent, distributor cap, exhaust gas control valve, etc.
- watch parts eg gears, cams and other mechanical parts, ground plates, etc.
- camera parts eg bottom lid, lens barrel, Lever, etc.
- leisure parts eg reels
- home appliance housing lighting and wiring equipment, film, bottle, textile, septic tank, toilet, bathtub, unit bath, water tank, ship, chemical tank, pipe, corrugated sheet , Flat plate, paint, decorative plate, sealing of electrical parts Wood, and the like resin concrete.
- the stabilizer composition of the present invention (that is, the first to fourth stabilizer compositions) will be described.
- the stabilizer composition of the present invention is used for improving the processing stability of a thermoplastic polymer composition.
- the processing stability of the thermoplastic polymer composition can be evaluated by the method described in Examples described later.
- the first stabilizer composition contains compound (1) and trehalose. Only 1 type may be used for a compound (1) and it may use 2 or more types together. The description of compound (1) and trehalose is the same as described above.
- the weight ratio of compound (1) to trehalose in the first stabilizer composition is preferably 1000: 1 to 0.05: 1.
- Compound (1): Trehalose is more preferably 1000: 1 to 0.1: 1 from the viewpoint of processing stability of the thermoplastic polymer composition, and further from the viewpoint of suppressing discoloration of the thermoplastic polymer composition.
- the ratio is preferably 1000: 1 to 0.5: 1, particularly preferably 1000: 1 to 1: 1.
- the first stabilizer composition may contain components other than the compound (1) and trehalose as long as the effects of the present invention are not impaired.
- the first stabilizer composition may further contain a compound (2).
- the first stabilizer composition may further contain at least one selected from the group consisting of compounds (3) to (7).
- the compounds (2) to (7) only one kind may be used, or two or more kinds may be used in combination.
- the description of the compounds (2) to (7) is the same as described above.
- the content of the compound (2) in the first stabilizer composition is preferably 0 to 90 parts by weight, more preferably 0.1 to 80 parts by weight with respect to 100 parts by weight of the first stabilizer composition. It is.
- the total amount of compounds selected from the group consisting of compounds (3) to (7) in the first stabilizer composition is preferably 0 to 10 weights per 100 parts by weight of the first stabilizer composition. Parts, more preferably 0.001 to 5 parts by weight.
- the first stabilizer composition may further contain other additives.
- the description of the other additives is the same as described above.
- the second stabilizer composition contains compound (8) and trehalose. Only one type of compound (8) may be used, or two or more types may be used in combination. The description of compound (8) and trehalose is the same as described above.
- the weight ratio of compound (8) to trehalose in the second stabilizer composition is preferably 1000: 1 to 0.05: 1.
- Compound (8): Trehalose is more preferably 1000: 1 to 0.1: 1 from the viewpoint of processing stability of the thermoplastic polymer composition, and further suppresses discoloration of the thermoplastic polymer composition.
- the ratio is preferably 1000: 1 to 0.5: 1, particularly preferably 1000: 1 to 1: 1.
- the second stabilizer composition may contain components other than compound (8) and trehalose as long as the effects of the present invention are not impaired.
- the second stabilizer composition may further contain a compound (2).
- the second stabilizer composition may further contain at least one selected from the group consisting of compounds (3) to (7).
- the compounds (2) to (7) only one kind may be used, or two or more kinds may be used in combination. The description of the compounds (2) to (7) is the same as described above.
- the content of the compound (2) in the second stabilizer composition is preferably 0 to 90 parts by weight, more preferably 0.1 to 80 parts by weight with respect to 100 parts by weight of the second stabilizer composition. It is.
- the total amount of compounds selected from the group consisting of compounds (3) to (7) in the second stabilizer composition is preferably 0 to 10 weights with respect to 100 parts by weight of the second stabilizer composition. Parts, more preferably 0.001 to 5 parts by weight.
- the second stabilizer composition may further contain other additives.
- the description of the other additives is the same as described above.
- the third stabilizer composition contains compound (2) and trehalose. Only one type of compound (2) may be used, or two or more types may be used in combination. The description of compound (2) and trehalose is the same as described above.
- the third stabilizer composition preferably comprises compound (2) and trehalose.
- “consisting of compound (2) and trehalose” means that the total amount of compound (2) and trehalose is 99% by weight or more in the third stabilizer composition.
- the weight ratio of compound (2) to trehalose in the third stabilizer composition is preferably 1000: 1 to 0.05: 1.
- Compound (2): Trehalose is more preferably 1000: 1 to 0.1: 1 from the viewpoint of processing stability of the thermoplastic polymer composition, and further suppresses discoloration of the thermoplastic polymer composition.
- the ratio is preferably 1000: 1 to 0.5: 1, and more preferably 1000: 1 to 1: 1.
- the third stabilizer composition may contain components other than the compound (2) and trehalose as long as the effects of the present invention are not impaired.
- the third stabilizer composition may further contain compound (1).
- the third stabilizer composition may further contain at least one selected from the group consisting of compounds (3) to (7).
- the third thermoplastic polymer composition may further contain a compound (8).
- the compound (1) and the compounds (3) to (8) only one kind may be used or two or more kinds may be used in combination. The description of the compound (1) and the compounds (3) to (8) is the same as described above.
- Each content of compound (1) and compounds (3) to (8) in the third stabilizer composition is preferably 0 to 90 parts by weight with respect to 100 parts by weight of the third stabilizer composition. More preferably, it is 0.1 to 80 parts by weight.
- the third stabilizer composition may further contain other additives.
- the description of the other additives is the same as described above.
- the fourth stabilizer composition contains at least one selected from the group consisting of compounds (3) to (7) and trehalose.
- compounds (3) to (7) only one kind may be used, or two or more kinds may be used in combination.
- the explanation of compound (3) to compound (7) and trehalose is the same as described above.
- the fourth stabilizer composition preferably comprises at least one selected from the group consisting of compounds (3) to (7) and trehalose.
- “consisting of at least one selected from the group consisting of compound (3) to compound (7) and trehalose” means the total of the compound selected from the group consisting of compound (3) to compound (7) and trehalose. The amount represents 99% by weight or more in the fourth stabilizer composition.
- the weight ratio of the compound selected from the group consisting of compound (3) to compound (7) and trehalose in the fourth stabilizer composition is preferably 1000: 1 to 0.05: 1.
- the compound selected from the group consisting of the compounds (3) to (7): trehalose is more preferably 1000: 1 to 0.1: 1 from the viewpoint of processing stability of the thermoplastic polymer composition. In order to suppress discoloration of the polymer composition, it is more preferably 1000: 1 to 0.5: 1, and still more preferably 1000: 1 to 1: 1.
- the fourth stabilizer composition may contain components other than the compounds (3) to (7) and trehalose as long as the effects of the present invention are not impaired.
- the fourth stabilizer composition may further contain at least one selected from the group consisting of compound (1), compound (2) and compound (8).
- a compound (1), a compound (2), and a compound (8) all may use only 1 type and may use 2 or more types together.
- the explanation of compound (1), compound (2) and compound (8) is the same as described above.
- Each content of the compound (1), the compound (2) and the compound (8) in the fourth stabilizer composition is preferably 0 to 90 parts by weight with respect to 100 parts by weight of the fourth stabilizer composition. More preferably, it is 0.1 to 80 parts by weight.
- the fourth stabilizer composition may further contain other additives.
- the description of other additives in the fourth stabilizer composition is the same as described above.
- Examples of the method for producing the stabilizer composition of the present invention include essential components of the first to fourth stabilizer compositions and optional components (that is, compounds (1) to (8), trehalose and Other additives) may be mixed with a mixer such as a Henschel mixer, a super mixer, or a high speed mixer.
- a mixer such as a Henschel mixer, a super mixer, or a high speed mixer.
- the mixture thus obtained (stabilizer composition) may be further subjected to extrusion molding or stirring granulation.
- melt flow rate is described as “MFR”.
- Example 1-1 to 1-253 the first stabilizer composition containing compound (1) and trehalose as essential components is used, and in Examples 2-1 to 2-208, the compound ( 8) and a second stabilizer composition containing trehalose as essential components, and in Examples 3-1 to 3-134, a third stabilizer composition comprising compound (2) and trehalose as essential components
- a fourth stabilizer composition containing at least one selected from the group consisting of compounds (3) to (7) and trehalose as essential components is used. To do.
- Example 1-1 (Production of Stabilizer Composition) A stabilizer composition was produced by mixing 0.4 part of compound (1-1) and 0.01 part of trehalose.
- Example 1-2 to Example 1-4 (Production of Stabilizer Composition) A stabilizer composition was produced in the same manner as in Example 1-1 except that the amount of trehalose used was 0.05 part, 0.1 part, and 0.2 part, respectively.
- Examples 1-5 to 1-8 (Production of Stabilizer Composition) A stabilizer composition was produced in the same manner as in Example 1-1 to Example 1-4, respectively, except that compound (1-2) was used instead of compound (1-1).
- Example 1-9 (Production of thermoplastic polymer composition) 100 parts of a styrene-butadiene block copolymer (Asahi Kasei Co., Ltd.) and the total amount of the stabilizer composition obtained in Example 1-1 were mixed to obtain a lab plast mill (“4C-150” manufactured by Toyo Seiki Co., Ltd.). Was used and kneaded in a nitrogen atmosphere under the conditions of a temperature of 250 ° C. and a rotation speed of 100 rpm to obtain pellets of a thermoplastic polymer composition.
- a lab plast mill (“4C-150” manufactured by Toyo Seiki Co., Ltd.
- thermoplastic polymer composition Similar to Example 1-9, except that the stabilizer composition obtained in Example 1-2 to Example 1-4 was used in place of the stabilizer composition obtained in Example 1-1. Thus, pellets of the thermoplastic polymer composition were obtained.
- Comparative Example 1-1 Pellet of thermoplastic polymer composition in the same manner as in Example 1-9 except that 0.4 part of compound (1-1) was used instead of the stabilizer composition obtained in Example 1-1. Got.
- Examples 1-13 to 1-16 (Production of thermoplastic polymer composition) The same procedure as in Example 1-9 except that the stabilizer composition obtained in Example 1-5 to Example 1-8 was used in place of the stabilizer composition obtained in Example 1-1. Thus, pellets of the thermoplastic polymer composition were obtained.
- Comparative Example 1-2 Pellet of thermoplastic polymer composition in the same manner as in Example 1-13, except that 0.4 part of compound (1-2) was used in place of the stabilizer composition obtained in Example 1-5. Got.
- Test Example 1-1 Evaluation of processing stability under dynamic conditions
- the time required for the Laboplast mill torque to reach the maximum value was measured as the build-up time. The longer the buildup time, the better the processing stability under dynamic conditions for the thermoplastic polymer composition.
- the improvement rate of processing stability was calculated.
- the value of the buildup time of Comparative Example 1-1 is used in Examples 1-9 to 1-12, and Examples 1-13 to 1-16 are used.
- the build-up value of Comparative Example 1-2 was used.
- compositions of the stabilizer compositions of Examples 1-1 to 1-8 are shown in Table 1, and the thermoplastic polymers of Examples 1-9 to 1-16, Comparative Example 1-1, and Comparative Example 1-2
- the composition, build-up time and processing stability of the composition are shown in Table 2.
- Example 1-17 (Production of thermoplastic polymer composition) After dry blending 100 parts of an ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd.), 0.3 part of compound (1-1) and 0.2 part of trehalose, the resulting mixture was a single screw extruder having a screw diameter of 30 mm.
- a thermoplastic polymer composition is obtained by kneading and extruding using a (VS30-28 type extruder manufactured by Tanabe Plastics Co., Ltd.) at a temperature of 230 ° C. and a screw rotation speed of 50 rpm, and cutting the strand with a pelletizer. A product pellet was obtained.
- thermoplastic polymer composition A pellet of a thermoplastic polymer composition was obtained in the same manner as in Example 1-17, except that 0.1 part of compound (1-1) and 0.4 part of trehalose were used as the stabilizer composition.
- Comparative Example 1-3 A pellet of a thermoplastic polymer composition was obtained in the same manner as in Example 1-17, except that only 0.5 part of compound (1-1) was used as a stabilizer.
- Test Example 1-2 Evaluation of processing stability under static conditions
- the test is based on JIS K 7210, using a melt indexer (L217-E14011, manufactured by Techno Seven Co., Ltd.) under the conditions of a temperature in a cylinder of 270 ° C. and a load of 2.16 kg (MFR before residence) (g / 10 min. ) And post-retention MFR (g / 10 min).
- MFR fluctuation rate (%) Absolute value of (MFR after residence-MFR before residence) x 100 / (MFR before residence) Based on the above, the MFR fluctuation rate was calculated. The smaller the MFR variation rate, the better the processing stability of the thermoplastic polymer composition. The results are shown in Table 3.
- Examples 1-19 to 1-22 (Production of Stabilizer Composition) Compound (1-1), trehalose, compound (2-1) and compound (3-1) were mixed in the amounts shown in Table 4 to obtain a stabilizer composition.
- Example 1-23 (Production of thermoplastic polymer composition) After dry blending 100 parts of a styrene-butadiene block copolymer (manufactured by Denki Kagaku) and 0.31 part of the stabilizer composition obtained in Example 1-19, the resulting mixture was mixed with a screw having a screw diameter of 30 mm. A strand is obtained by kneading and extruding at a temperature of 230 ° C. and a screw rotation speed of 50 rpm using a single screw extruder (“VS30-28 type extruder” manufactured by Tanabe Plastics Co., Ltd.), and the strand is cut with a pelletizer to be thermoplastic. Polymer composition pellets were obtained.
- a single screw extruder (“VS30-28 type extruder” manufactured by Tanabe Plastics Co., Ltd.
- Example 1-24 (Production of thermoplastic polymer composition) In the same manner as in Example 1-23, except that 0.51 part of the stabilizer composition obtained in Example 1-20 was used instead of the stabilizer composition obtained in Example 1-19, A pellet of thermoplastic polymer composition was obtained.
- Example 1-25 (Production of thermoplastic polymer composition) In the same manner as in Example 1-23, except that 0.51 part of the stabilizer composition obtained in Example 1-21 was used instead of the stabilizer composition obtained in Example 1-19, A pellet of thermoplastic polymer composition was obtained.
- Example 1-26 (Production of thermoplastic polymer composition) In the same manner as in Example 1-23, except that 0.71 part of the stabilizer composition obtained in Example 1-22 was used instead of the stabilizer composition obtained in Example 1-19, A pellet of thermoplastic polymer composition was obtained.
- Comparative Example 1-4 Pellet of thermoplastic polymer composition in the same manner as in Example 1-23, except that 0.3 part of compound (1-1) was used in place of the stabilizer composition obtained in Example 1-19. Got.
- Test Example 1-3 Evaluation of processing stability under static conditions
- thermoplastic polymer composition pellets obtained in Examples 1-23 to 1-26 and Comparative Example 1-4 were used, respectively.
- a residence MFR test was conducted in the same manner as in Test Example 1-2.
- the results are shown in Table 5.
- Examples 1-27 to 1-31 (Production of Stabilizer Composition) Compound (1-1) and trehalose were mixed in the amounts shown in Table 6 to obtain a stabilizer composition.
- Examples 1-32 to 1-36 (Production of Thermoplastic Polymer Composition) Example except that 0.21 part of the stabilizer composition obtained in each of Examples 1-27 to 31 was used instead of 0.31 part of the stabilizer composition obtained in Example 1-19. In the same manner as in 1-23, pellets of a thermoplastic polymer composition were obtained.
- Test Example 1-4 Evaluation of processing stability under static conditions
- thermoplastic polymer composition pellets obtained in Examples 1-32 to 1-36 Using the thermoplastic polymer composition pellets obtained in Examples 1-32 to 1-36, a residence MFR test was conducted in the same manner as in Test Example 1-2. The results are shown in Table 7.
- a stabilizer composition can be obtained by mixing the components listed in Tables 8-1 to 8-3.
- Thermoplastic polymer compositions containing these stabilizer compositions are expected to be excellent in processing stability.
- Example 1-124 to Example 1-253 (Production of Thermoplastic Polymer Composition) Example 1-4, except that 100 parts of the thermoplastic polymer described in Tables 9-1 to 9-4 and the stabilizer composition of the type and amount described in Tables 9-1 to 9-4 were used. In the same manner, pellets of the thermoplastic polymer composition are obtained. The resulting thermoplastic polymer composition is expected to be excellent in processing stability.
- thermoplastic polymers listed in Tables 9-1 to 9-4 are as follows.
- the MFR described below is the MFR before residence of the thermoplastic polymer measured under the conditions of Test Example 1-2.
- P1-1 High density polyethylene (HDPE) (excluding P1-45 to P1-50)
- P1-2 Low density polyethylene (LDPE) (excluding P1-51 to P1-57)
- P1-3 Linear low density polyethylene (LLDPE) (excluding P1-58 to P1-64)
- EAA Ethylene-ethyl acrylate copolymer
- EVA Ethylene-vinyl acetate copolymer
- P1-6 Polypropylene (PP) (excluding P1-65 to P1-71)
- P1-7 Propylene-ethylene random copolymer
- P1-8 Propylene- ⁇ -olefin random copolymer
- P1-9 Propylene-ethylene- ⁇ -olefin copolymer
- P1-10 Polystyrene (PS)
- Example 2-1 (Production of Stabilizer Composition) A stabilizer composition was prepared by mixing 0.2 part of Compound (8-1) and 0.05 part of trehalose.
- Example 2-2 (Production of Stabilizer Composition) A stabilizer composition was produced by mixing 0.1 part of Compound (8-1) and 0.01 part of trehalose.
- Example 2-3 (Production of thermoplastic polymer composition) After dry blending 100 parts of an ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd.) and the total amount of the stabilizer composition obtained in Example 2-1, the resulting mixture was converted into a single screw A thermoplastic polymer composition is obtained by kneading and extruding at a temperature of 230 ° C. and a screw rotation speed of 50 rpm using an extruder (“VS30-28 type extruder” manufactured by Tanabe Plastics), and cutting the strand with a pelletizer. A product pellet was obtained.
- Example 2-4 (Production of thermoplastic polymer composition) A thermoplastic polymer composition was obtained in the same manner as in Example 2-3 except that the stabilizer composition obtained in Example 2-2 was used instead of the stabilizer composition obtained in Example 2-1. A product pellet was obtained.
- Comparative Example 2-1 Pellet of thermoplastic polymer composition in the same manner as in Example 2-3 except that 0.1 part of compound (8-1) was used instead of the stabilizer composition obtained in Example 2-1. Got.
- Test Example 2-1 Evaluation of processing stability
- a residence MFR test was conducted using the pellets of the thermoplastic polymer composition obtained in Example 2-34 and Comparative Example 2-1, respectively.
- the test is based on JIS K 7210, using a melt indexer (L217-E14011, manufactured by Techno Seven Co., Ltd.) under the conditions of a temperature in a cylinder of 270 ° C. and a load of 2.16 kg (MFR before residence) (g / 10 min. ) And post-retention MFR (g / 10 min).
- MFR before residence was measured after filling the cylinder with pellets of the thermoplastic polymer composition and taking a preheating time of 5 minutes.
- MFR fluctuation rate (%) Absolute value of (MFR after residence-MFR before residence) x 100 / (MFR before residence) Based on the above, the MFR fluctuation rate was calculated. The smaller the MFR variation rate, the better the processing stability of the thermoplastic polymer composition.
- Table 10 shows the composition of the stabilizer composition of Example 2-1 and Example 2-2. The composition and residence of the thermoplastic polymer compositions of Example 2-3, Example 2-4, and Comparative Example 2-1.
- Table 11 shows the pre-MFR, post-retention MFR, and MFR fluctuation rate.
- a stabilizer composition can be obtained by mixing the components listed in Tables 12-1 to 12-3. Thermoplastic polymer compositions containing these stabilizer compositions are expected to be excellent in processing stability.
- Example 2-92 to Example 2-208 (Production of thermoplastic polymer composition) Example 2-2 except that 100 parts of the thermoplastic polymer described in Table 13-1 to Table 13-4 and the stabilizer composition of the type and amount described in Table 13-1 to Table 13-4 were used. In the same manner, pellets of the thermoplastic polymer composition are obtained. The resulting thermoplastic polymer composition is expected to be excellent in processing stability.
- thermoplastic polymers described in Table 13-1 to Table 13-4 are as follows.
- the MFR described below is the MFR before residence of the thermoplastic polymer measured under the conditions of Test Example 2-1.
- P2-1 High density polyethylene (HDPE) (excluding P2-45 to P2-50)
- P2-2 Low density polyethylene (LDPE) (excluding P2-51 to P2-57)
- P2-3 Linear low density polyethylene (LLDPE) (excluding P2-58 to P2-64)
- EVA Ethylene-ethyl acrylate copolymer
- P2-5 Ethylene-vinyl acetate copolymer (EVA)
- P2-6 Polypropylene (PP) (excluding P2-65 to P2-71)
- P2-7 Propylene-ethylene random copolymer
- P2-8 Propylene- ⁇ -olefin random copolymer
- P2-9 Propylene-ethylene- ⁇ -olef
- Example 3-1 (Production of Stabilizer Composition) A stabilizer composition was prepared by mixing 0.2 part of compound (2-1), 0.01 part of trehalose and 0.3 part of compound (1-1).
- Reference Example 3-1 A stabilizer composition was produced by mixing 0.2 part of compound (2-1) and 0.3 part of compound (1-1).
- Example 3-2 Production of thermoplastic polymer composition
- a styrene-butadiene block copolymer manufactured by Asahi Kasei Co., Ltd.
- the resulting mixture was passed through a screw having a screw diameter of 30 mm.
- a strand is obtained by kneading and extruding at a temperature of 230 ° C. and a screw rotation speed of 50 rpm using a single-screw extruder (“VS30-28 type extruder” manufactured by Tanabe Plastics), and the strand is cut with a pelletizer to obtain thermoplasticity.
- Polymer composition pellets were obtained.
- thermoplastic polymer was prepared in the same manner as in Example 3-2 except that 0.5 part of the composition obtained in Reference Example 3-1 was used instead of the stabilizer composition obtained in Example 3-1. A pellet of the composition was obtained.
- Test Example 3-1 Evaluation of processing stability
- a residence MFR test was conducted using the pellets of the thermoplastic polymer composition obtained in Example 3-2 and Reference Example 3-2, respectively.
- the test is based on JIS K 7210, using a melt indexer (L217-E14011, manufactured by Techno Seven Co., Ltd.) under the conditions of a temperature in a cylinder of 270 ° C. and a load of 2.16 kg (MFR before residence) (g / 10 min. ) And post-retention MFR (g / 10 min).
- MFR before residence was measured after filling the cylinder with pellets of the thermoplastic polymer composition and taking a preheating time of 5 minutes.
- MFR fluctuation rate (%) Absolute value of (MFR after residence-MFR before residence) x 100 / (MFR before residence) Based on the above, the MFR fluctuation rate was calculated.
- the composition of the stabilizer composition of Example 3-1 and Reference Example 3-1 is shown in Table 14, the composition of the thermoplastic polymer composition of Example 3-2 and Reference Example 3-2, the MFR before residence, and the MFR after residence.
- Table 15 shows the MFR fluctuation rate.
- the smaller the MFR variation rate the better the processing stability.
- Example 3-3 (Production of Stabilizer Composition) A stabilizer composition was prepared by mixing 0.1 part of compound (2-2) and 0.1 part of trehalose.
- Example 3-4 Production of thermoplastic polymer composition
- a single-screw extruder having a screw diameter of 30 mm A strand is obtained by kneading and extruding using a “VS30-28 type extruder” manufactured by Tanabe Plastic Co., Ltd. at a temperature of 230 ° C. and a screw rotation speed of 50 rpm, and cutting the strand with a pelletizer, thereby pelletizing the thermoplastic polymer composition Got.
- Comparative Example 3-1 Pellet of thermoplastic polymer composition in the same manner as in Example 3-4 except that 0.1 part of compound (2-2) was used instead of the stabilizer composition obtained in Example 3-3. Got.
- Test Example 3-2 Evaluation of processing stability
- a residence MFR test was conducted using the pellets of the thermoplastic polymer composition obtained in Example 3-4 and Comparative Example 3-1, respectively.
- the test is based on JIS K 7210, using a melt indexer (L217-E14011, manufactured by Techno Seven Co., Ltd.) under the conditions of a temperature in a cylinder of 270 ° C. and a load of 2.16 kg, and MFR (g / 10 minutes after residence) ) Was measured.
- the post-retention MFR was measured after the thermoplastic polymer composition pellets were retained in the cylinder for a total of 30 minutes including the preheating time.
- Table 16 shows the composition of the stabilizer composition of Example 3-3
- Table 17 shows the composition and MFR after residence of the thermoplastic polymer compositions of Example 3-4 and Comparative Example 3-1.
- Examples 3-5 to 3-7 (Production of Stabilizer Composition) Compound (2-1), trehalose, compound (1-1) and compound (3-1) were mixed in the amounts shown in Table 18 to prepare stabilizer compositions.
- Example 3-8 (Production of thermoplastic polymer composition) After dry blending 100 parts of a styrene-butadiene block copolymer (manufactured by Denki Kagaku Co., Ltd.) and 0.21 part of the stabilizer composition obtained in Example 3-5, the resulting mixture was mixed with a screw diameter of 30 mm. Using a single screw extruder (“VS30-28 type extruder” manufactured by Tanabe Plastics Co., Ltd.) to obtain a strand by kneading and extrusion at a temperature of 230 ° C. and a screw rotation speed of 50 rpm, and cutting this strand with a pelletizer, A pellet of the plastic polymer composition was obtained.
- VS30-28 type extruder manufactured by Tanabe Plastics Co., Ltd.
- Example 3-9 (Production of thermoplastic polymer composition) In the same manner as in Example 3-8, except that 0.41 part of the stabilizer composition obtained in Example 3-6 was used instead of the stabilizer composition obtained in Example 3-5, A pellet of thermoplastic polymer composition was obtained.
- Examples 3-10 (Production of thermoplastic polymer composition) In the same manner as in Example 3-8 except that 0.71 part of the stabilizer composition obtained in Example 3-7 was used instead of the stabilizer composition obtained in Example 3-5, A pellet of thermoplastic polymer composition was obtained.
- Comparative Example 3-2 Pellet of thermoplastic polymer composition in the same manner as in Example 3-8, except that 0.2 part of compound (2-1) was used in place of the stabilizer composition obtained in Example 3-5. Got.
- Test Example 3-3 Evaluation of processing stability
- MFR before residence g / 10 minutes
- post-retention MFR g / 10 min
- a stabilizer composition can be obtained by mixing the components described in Table 20-1 and Table 20-2.
- Thermoplastic polymer compositions containing these stabilizer compositions are expected to be excellent in processing stability.
- Example 3-79 to Example 3-134 (Production of thermoplastic polymer composition) Example 3-4 except that 100 parts of the thermoplastic polymer described in Table 21-1 and Table 21-2 and the stabilizer composition of the type and amount described in Table 21-1 and Table 21-2 were used. In the same manner, pellets of the thermoplastic polymer composition are obtained. The resulting thermoplastic polymer composition is expected to be excellent in processing stability.
- thermoplastic polymers described in Table 21-1 and Table 21-2 are as follows.
- P3-1 High density polyethylene (HDPE)
- LDPE Low density polyethylene
- P3-3 Linear low density polyethylene (LLDPE)
- P3-4 Ethylene-vinyl alcohol copolymer (EVOH)
- EAA Ethylene-ethyl acrylate copolymer
- EVA Ethylene-vinyl acetate copolymer
- P3-7 Propylene-ethylene random copolymer
- P3-8 Propylene- ⁇ -olefin random copolymer
- P3-9 Propylene-ethylene- ⁇ -olefin copolymer
- P3-10 Polystyrene (PS)
- P3-11 Acrylonitrile-styrene copolymer (SAN)
- P3-12 Acrylonitrile-butadiene-styrene copolymer (ABS)
- P3-13 Special acrylic rubber
- Example 4-1 (Production of Stabilizer Composition) A stabilizer composition was produced by mixing 0.1 part of compound (3-1) and 0.01 part of trehalose.
- Example 4-2 (Production of thermoplastic polymer composition) After dry blending 100 parts of polypropylene (manufactured by Sumitomo Chemical Co., Ltd.) and the stabilizer composition obtained in Example 4-1, the resulting mixture was mixed with a single screw extruder (manufactured by Tanabe Plastics Co., Ltd.) having a screw diameter of 30 mm. Using a “VS30-28 type extruder”), a strand was obtained by kneading and extrusion at a temperature of 230 ° C. and a screw rotation speed of 50 rpm, and the strand was cut with a pelletizer to obtain a pellet of a thermoplastic polymer composition.
- a single screw extruder manufactured by Tanabe Plastics Co., Ltd.
- thermoplastic polymer composition was Pellets were obtained.
- Test Example 4-1 Evaluation of processing stability
- a residence MFR test was conducted using the pellets of the thermoplastic polymer composition obtained in Example 4-2 and Comparative Example 4-1, respectively.
- the test is based on JIS K 7210, using a melt indexer (L217-E14011, manufactured by Techno Seven Co., Ltd.) under the conditions of a temperature in a cylinder of 270 ° C. and a load of 2.16 kg, and MFR (g / 10 minutes after residence) ) Was measured.
- the post-retention MFR was measured after the thermoplastic polymer composition pellets were retained in the cylinder for a total of 30 minutes including the preheating time.
- Polypropylene is decomposed by heat during processing. Therefore, in a thermoplastic polymer composition containing polypropylene, the smaller the MFR after residence, the better the processing stability.
- Table 22 shows the composition of the stabilizer composition of Example 4-1
- Example 4-3 to Example 4-6 (Production of Stabilizer Composition)
- Compound (3-1), trehalose, compound (1-1) and compound (2-1) were mixed in the amounts shown in Table 24 to prepare stabilizer compositions.
- Example 4-7 (Production of thermoplastic polymer composition) After dry blending 100 parts of a styrene-butadiene block copolymer (manufactured by Denki Kagaku) and 0.21 part of the stabilizer composition obtained in Example 4-3, the resulting mixture was mixed with a screw diameter of 30 mm. Using a single screw extruder (“VS30-28 type extruder” manufactured by Tanabe Plastics Co., Ltd.) to obtain a strand by kneading and extrusion at a temperature of 230 ° C. and a screw rotation speed of 50 rpm, and cutting this strand with a pelletizer A pellet of the plastic polymer composition was obtained.
- VS30-28 type extruder manufactured by Tanabe Plastics Co., Ltd.
- Example 4-8 (Production of thermoplastic polymer composition) In the same manner as in Example 4-7, except that 0.51 part of the stabilizer composition obtained in Example 4-4 was used instead of the stabilizer composition obtained in Example 4-3, A pellet of thermoplastic polymer composition was obtained.
- Example 4-9 (Production of thermoplastic polymer composition) In the same manner as in Example 4-7, except that 0.41 part of the stabilizer composition obtained in Example 4-5 was used instead of the stabilizer composition obtained in Example 4-3, A pellet of thermoplastic polymer composition was obtained.
- Example 4-10 (Production of thermoplastic polymer composition) In the same manner as in Example 4-7 except that 0.71 part of the stabilizer composition obtained in Example 4-6 was used instead of the stabilizer composition obtained in Example 4-3, A pellet of thermoplastic polymer composition was obtained.
- thermoplastic polymer composition was Pellets were obtained.
- Test Example 4-2 Evaluation of processing stability
- the residence MFR test was performed using the pellets of the thermoplastic polymer composition obtained in Examples 4-7 to 4-10 and Comparative Example 4-2, respectively. Carried out.
- the test is based on JIS K 7210, using a melt indexer (L217-E14011, manufactured by Techno Seven Co., Ltd.) under the conditions of a temperature in a cylinder of 270 ° C. and a load of 2.16 kg (MFR before residence) (g / 10 min. ) And post-retention MFR (g / 10 min).
- MFR before residence was measured after filling the cylinder with pellets of the thermoplastic polymer composition and taking a preheating time of 5 minutes.
- MFR fluctuation rate (%) Absolute value of (MFR after residence-MFR before residence) x 100 / (MFR before residence) Based on the above, the MFR fluctuation rate was calculated.
- the composition of the stabilizer composition of Example 4-3 to Example 4-6 is shown in Table 24.
- the composition and residence of the thermoplastic polymer compositions of Example 4-7 to Example 4-10 and Comparative Example 4-2 Table 25 shows the pre-MFR, post-retention MFR, and MFR fluctuation rate.
- a stabilizer composition can be obtained by mixing the components described in Table 26-1 to Table 26-4.
- Thermoplastic polymer compositions containing these stabilizer compositions are expected to be excellent in processing stability.
- Example 4-140 to Example 4-199 (Production of thermoplastic polymer composition) Example 4-2 except that 100 parts of the thermoplastic polymer described in Table 27-1 and Table 27-2 and the stabilizer composition of the type and amount described in Table 27-1 and Table 27-2 were used. In the same manner, pellets of the thermoplastic polymer composition are obtained. The resulting thermoplastic polymer composition is expected to be excellent in processing stability.
- thermoplastic polymers described in Table 27-1 and Table 27-2 are as follows.
- P4-1 High density polyethylene (HDPE)
- P4-2 Low density polyethylene (LDPE)
- P4-3 Linear low density polyethylene (LLDPE)
- P4-4 Ethylene-vinyl alcohol copolymer (EVOH)
- EAA Ethylene-ethyl acrylate copolymer
- EVA Ethylene-vinyl acetate copolymer
- P4-7 Propylene-ethylene random copolymer
- P4-8 Propylene- ⁇ -olefin random copolymer
- P4-9 Propylene-ethylene- ⁇ -olefin copolymer
- P4-10 Polystyrene (PS)
- P4-11 Acrylonitrile-styrene copolymer (SAN)
- P4-12 Acrylonitrile-butadiene-styrene copolymer (ABS)
- P4-13 Special acrylic
- thermoplastic polymer composition of the present invention comprising at least one selected from the group consisting of compound (1), compound (2), compound (3) to compound (7) or compound (8) and trehalose is excellent. Shows processing stability.
- the thermoplastic polymer composition of the present invention can be used, for example, in the production of electronic parts, automobile parts, watch parts, camera parts, leisure parts and the like.
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Abstract
Description
各R1および各R2は、それぞれ独立に、C1-8アルキル基、C6-12アリール基またはC7-18アラルキル基を表す。
R3は、水素原子またはC1-3アルキル基を表す。
R4は、水素原子またはメチル基を表す。]
で示される化合物、トレハロースおよび熱可塑性ポリマーを含有することを特徴とする熱可塑性ポリマー組成物。
[2] 式(1)で示される化合物およびトレハロースの合計量が、熱可塑性ポリマー100重量部に対して0.001~3重量部である上記[1]に記載の熱可塑性ポリマー組成物。
[3] 式(1)で示される化合物およびトレハロースを含有することを特徴とする安定剤組成物。
[4] 式(1)で示される化合物が、2,4-ジ-t-ペンチル-6-[1-(3,5-ジ-t-ペンチル-2-ヒドロキシフェニル)エチル]フェニル アクリレートおよび2-t-ブチル-6-(3-t-ブチル-2-ヒドロキシ-5-メチルベンジル)-4-メチルフェニル アクリレートからなる群から選ばれる少なくとも一つである上記[3]に記載の安定剤組成物。
[5] さらに、式(2):
各R5および各R6は、それぞれ独立に、水素原子またはC1-6アルキル基を表す。
L1は、ヘテロ原子を含んでいてもよいn価のC1-24アルコール残基を表し、nは1~4の整数を表す。ここでアルコール残基とは、アルコールのヒドロキシ基から水素原子を除いた残りの基を表す。]
で示される化合物を含有する上記[3]または[4]に記載の安定剤組成物。
[6] さらに、式(3)~式(7):
各R11および各R12は、それぞれ独立に、水素原子、C1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
各L2は、それぞれ独立に、単結合、硫黄原子または式(6a):
各L3は、それぞれ独立に、C2-8アルキレン基を表す。]
各R15および各R16は、それぞれ独立に、水素原子、C1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
R17は、C1-8アルキル基、またはC1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基およびC7-12アラルキル基からなる群から選ばれる少なくとも一つで置換されていてもよいフェニル基を表す。
L4は、単結合、硫黄原子または式(7a):
で示される化合物からなる群から選ばれる少なくとも一つを含有する上記[3]~[5]のいずれか一つに記載の安定剤組成物。
[7] 式(3)~式(7)で示される化合物からなる群から選ばれる少なくとも一つが、式(3)で示される化合物である上記[6]に記載の安定剤組成物。
[8] 上記[3]~[7]のいずれか一つに記載の安定剤組成物および熱可塑性ポリマーを混合することを特徴とする熱可塑性ポリマー組成物の製造方法。
[9] 熱可塑性ポリマー組成物の加工安定性を向上させるための、上記[3]~[7]のいずれか一つに記載の安定剤組成物の使用。
各R20、各R21、R23およびR24は、それぞれ独立に、水素原子、C1-8アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
各R22は、それぞれ独立に、水素原子またはC1-8アルキル基を表す。
L5は、単結合、硫黄原子または式(8a):
L6は、C2-8アルキレン基または式(8b):
Z1およびZ2のいずれか一方は、ヒドロキシ基、C1-8アルキル基、C1-8アルコキシ基またはC7-12アラルキルオキシ基を表し、他方は、水素原子またはC1-8アルキル基を表す。]
で示される化合物、トレハロースおよび熱可塑性ポリマーを含有することを特徴とする熱可塑性ポリマー組成物。
[11] 式(8)で示される化合物およびトレハロースの合計量が、熱可塑性ポリマー100重量部に対して0.001~3重量部である上記[10]に記載の熱可塑性ポリマー組成物。
[12] 式(8)で示される化合物およびトレハロースを含有することを特徴とする安定剤組成物。
[13] 式(8)で示される化合物が、6-[3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-2,4,8,10-テトラ-t-ブチルジベンズ[d,f][1,3,2]ジオキサホスフェピンである上記[12]に記載の安定剤組成物。
[14] さらに、式(2)で示される化合物を含有する上記[12]または[13]に記載の安定剤組成物。
[15] さらに、式(3)~式(7)で示される化合物からなる群から選ばれる少なくとも一つを含有する上記[12]~[14]のいずれか一つに記載の安定剤組成物。
[16] 式(3)~式(7)で示される化合物からなる群から選ばれる少なくとも一つが、式(3)で示される化合物である上記[15]に記載の安定剤組成物。
[17] 上記[12]~[16]のいずれか一つに記載の安定剤組成物および熱可塑性ポリマーを混合することを特徴とする熱可塑性ポリマー組成物の製造方法。
[18] 熱可塑性ポリマー組成物の加工安定性を向上させるための、上記[12]~[16]のいずれか一つに記載の安定剤組成物の使用。
[20] 式(2)で示される化合物およびトレハロースの合計量が、熱可塑性ポリマー100重量部に対して0.001~3重量部である上記[19]に記載の熱可塑性ポリマー組成物。
[21] 熱可塑性ポリマーが、スチレン-ブタジエンブロック共重合体である上記[19]または[20]に記載の熱可塑性ポリマー組成物。
[22] 式(2)で示される化合物およびトレハロースを含有することを特徴とする安定剤組成物。
[23] 式(2)で示される化合物およびトレハロースからなることを特徴とする安定剤組成物。
[24] 式(2)で示される化合物が、オクタデシル 3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、3,9-ビス[2-{3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ}-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカンおよびペンタエリスリトール テトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]からなる群から選ばれる少なくとも一つである上記[22]または[23]に記載の安定剤組成物。
[25] 上記[22]~[24]のいずれか一つに記載の安定剤組成物および熱可塑性ポリマーを混合することを特徴とする熱可塑性ポリマー組成物の製造方法。
[26] 熱可塑性ポリマー組成物の加工安定性を向上させるための、上記[22]~[24]のいずれか一つに記載の安定剤組成物の使用。
[28] 式(3)~式(7)で示される化合物からなる群から選ばれる化合物およびトレハロースの合計量が、熱可塑性ポリマー100重量部に対して0.001~3重量部である上記[27]に記載の熱可塑性ポリマー組成物。
[29] 熱可塑性ポリマーが、スチレン-ブタジエンブロック共重合体である上記[27]または[28]に記載の熱可塑性ポリマー組成物。
[30] 式(3)~式(7)で示される化合物からなる群から選ばれる少なくとも一つおよびトレハロースを含有することを特徴とする安定剤組成物。
[31] 式(3)~式(7)で示される化合物からなる群から選ばれる少なくとも一つおよびトレハロースからなることを特徴とする安定剤組成物。
[32] 式(3)~式(7)で示される化合物からなる群から選ばれる少なくとも一つが、式(3)で示される化合物である上記[30]または[31]に記載の安定剤組成物。
[33] 式(3)で示される化合物が、トリス(2,4-ジ-t-ブチルフェニル)ホスファイトである上記[32]に記載の安定剤組成物。
[34] 上記[30]~[33]のいずれか一つに記載の安定剤組成物および熱可塑性ポリマーを混合することを特徴とする熱可塑性ポリマー組成物の製造方法。
[35] 熱可塑性ポリマー組成物の加工安定性を向上させるための、上記[30]~[33]のいずれか一つに記載の安定剤組成物の使用。
また、化合物(8)およびトレハロースを必須成分として含有する本発明の熱可塑性ポリマー組成物および本発明の安定剤組成物を、それぞれ、「第2の熱可塑性ポリマー組成物」および「第2の安定剤組成物」と呼ぶことがある。
また、化合物(2)およびトレハロースを必須成分として含有する本発明の熱可塑性ポリマー組成物および本発明の安定剤組成物を、それぞれ、「第3の熱可塑性ポリマー組成物」および「第3の安定剤組成物」と呼ぶことがある。
また、化合物(3)~化合物(7)からなる群から選ばれる少なくとも一つおよびトレハロースを必須成分として含有する本発明の熱可塑性ポリマー組成物および本発明の安定剤組成物を、それぞれ、「第4の熱可塑性ポリマー組成物」および「第4の安定剤組成物」と呼ぶことがある。
[1]2,6-ジ-t-ブチル-4-メチルフェノール、2,4,6-トリ-t-ブチルフェノール、2,6-ジ-t-ブチルフェノール、2-t-ブチル-4,6-ジメチルフェノール、2,6-ジ-t-ブチル-4-エチルフェノール、2,6-ジ-t-ブチル-4-n-ブチルフェノール、2,6-ジ-t-ブチル-4-イソブチルフェノール、2,6-ジシクロペンチル-4-メチルフェノール、2-(α-メチルシクロヘキシル)-4,6-ジメチルフェノール、2,6-ジオクタデシル-4-メチルフェノール、2,4,6-トリシクロヘキシルフェノール、2,6-ジ-t-ブチル-4-メトキシメチルフェノール、2,6-ジ-ノニル-4-メチルフェノール、2,4-ジメチル-6-(1’-メチルウンデシル-1’-イル)フェノール、2,4-ジメチル-6-(1’-メチルヘプタデシル-1’-イル)フェノール、2,4-ジメチル-6-(1’-メチルトリデシル-1’-イル)フェノールなどのアルキル化モノフェノール。
[1]ヒンダードアミン系光安定剤、例えば、以下の[a]~[c]に記載する物。
[a]ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス(2,2,6,6-テトラメチル-4-ピペリジル)スクシネート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケート、ビス(N-オクトキシ-2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス(N-ベンジルオキシ-2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス(N-シクロヘキシルオキシ-2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)2-(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-2-ブチルマロネート、ビス(1-アクロイル-2,2,6,6-テトラメチル-4-ピペリジル)2,2-ビス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)マロネート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)デカンジオエート、2,2,6,6-テトラメチル-4-ピペリジル メタクリレート、4-[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ]-1-[2-(3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ)エチル]-2,2,6,6-テトラメチルピペリジン、2-メチル-2-(2,2,6,6-テトラメチル-4-ピペリジル)アミノ-N-(2,2,6,6-テトラメチル-4-ピペリジル)プロピオンアミド、テトラキス(2,2,6,6-テトラメチル-4-ピペリジル)1,2,3,4-ブタンテトラカルボキシレート、テトラキス(1,2,2,6,6-ペンタメチル-4-ピペリジル)1,2,3,4-ブタンテトラカルボキシレート。
(a)熱可塑性ポリマーを混練する際に、必須成分である化合物(1)~化合物(8)およびトレハロース、並びに必要に応じて任意成分である化合物(1)~化合物(8)および他の添加剤を、熱可塑性ポリマーに別々に配合する方法;
(b)まず、必須成分である化合物(1)~化合物(8)およびトレハロース、並びに必要に応じて、任意成分である化合物(1)~化合物(8)および他の添加剤を混合して安定剤組成物を製造し、次いで得られた安定剤組成物を熱可塑性ポリマーに混合する方法;
などが挙げられる。必須成分である化合物(1)~化合物(8)およびトレハロースの熱可塑性ポリマーへの分散性の観点から、前記(b)の方法が好ましい。
(c)安定剤組成物と熱可塑性ポリマーとをドライブレンドし、次いで一軸または多軸押出し機で溶融混練した後、押出しを行って熱可塑性ポリマー組成物のペレットを得る方法;
(d)シクロへキサンなどの溶剤に安定剤組成物を溶解させて、安定剤組成物の溶液を調製し、この溶液を熱可塑性ポリマー重合終了後のポリマー溶液に添加し、脱溶媒する方法;
などが挙げられる。
化合物(1-1):2,4-ジ-t-ペンチル-6-[1-(3,5-ジ-t-ペンチル-2-ヒドロキシフェニル)エチル]フェニル アクリレート(住友化学社製「スミライザー(登録商標)GS(F)」)
化合物(1-2):2-t-ブチル-6-(3-t-ブチル-2-ヒドロキシ-5-メチルベンジル)-4-メチルフェニル アクリレート(住友化学社製「スミライザー(登録商標)GM」)
化合物(2-1):オクタデシル 3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート(BASF社製「イルガノックス(登録商標)1076」)
化合物(2-2):3,9-ビス[2-{3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ}-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン(住友化学社製「スミライザー(登録商標)GA-80」)
化合物(2-3):ペンタエリスリトール テトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製「イルガノックス(登録商標)1010」)
化合物(3-1):トリス(2,4-ジ-t-ブチルフェニル)ホスファイト(BASF社製「イルガフォス(登録商標)168」)
化合物(4-1):テトラキス(2,4-ジ-t-ブチルフェニル)-4,4-ビフェニレンジホスホナイト(クラリアント社製「サンドスタブ(登録商標)P-EPQ」)
化合物(5-1):ビス(2,6-ジ-t-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト(アデカ社製「アデカスタブ(登録商標)PEP-36」)
化合物(5-2):ビス(2,4-ジ-t-ブチルフェニル)ペンタエリスリトールジホスファイト(GEプラスチック社製「ウルトラノックス(登録商標)626」)
化合物(5-3):ビス(2,4-ジクミルフェニル)ペンタエリスリトールジホスファイト(ドーヴァーケミカル社製「ドーヴァーフォスS9228T」)
化合物(6-1):6,6’,6”-[ニトリロトリス(エチレンオキシ)]トリス(2,4,8,10-テトラ-t-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン)(BASF社製「イルガフォス(登録商標)12」)
化合物(7-1):2,2-メチレンビス(4,6-ジ-t-ブチルフェニル)オクチルホスファイト(アデカ社製「アデカスタブ(登録商標)HP-10」)
化合物(8-1):6-[3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-2,4,8,10-テトラ-t-ブチルジベンズ[d,f][1,3,2]ジオキサホスフェピン(住友化学社製「スミライザー(登録商標)GP」)
トレハロース(林原社製)
化合物(1-1)0.4部およびトレハロース0.01部を混合して、安定剤組成物を製造した。
トレハロースの使用量を、それぞれ0.05部、0.1部および0.2部としたこと以外は実施例1-1と同様にして、安定剤組成物を製造した。
化合物(1-1)に替えて化合物(1-2)を用いたこと以外は、それぞれ、実施例1-1~実施例1-4と同様にして、安定剤組成物を製造した。
スチレン-ブタジエンブロック共重合体(旭化成社製)100部と、実施例1-1で得られた安定剤組成物の全量とを混合し、ラボプラストミル(東洋精機社製「4C-150」)を用いて、窒素雰囲気にて温度250℃および回転数100rpmの条件で混練し、熱可塑性ポリマー組成物のペレットを得た。
実施例1-1で得られた安定剤組成物に替えて、実施例1-2~実施例1-4でそれぞれ得られた安定剤組成物を用いたこと以外は実施例1-9と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例1-1で得られた安定剤組成物に替えて、化合物(1-1)0.4部を用いたこと以外は実施例1-9と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例1-1で得られた安定剤組成物に替えて、実施例1-5~実施例1-8でそれぞれ得られた安定剤組成物を用いたこと以外は実施例1-9と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例1-5で得られた安定剤組成物に替えて、化合物(1-2)0.4部を用いたこと以外は実施例1-13と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例1-9~実施例1-13並びに比較例1-1および比較例1-2において、ラボプラストミルのトルクが最大値に到達するまでの時間を、ビルドアップタイムとして測定した。ビルドアップタイムが長いほど、熱可塑性ポリマー組成物は、動的条件下での加工安定性に優れる。
加工安定性の向上率(%)
=実施例のビルドアップタイム(分)×100/比較例のビルドアップタイム(分)
に基づき、加工安定性の向上率を計算した。なお、加工安定性の向上率の計算には、実施例1-9~実施例1-12では比較例1-1のビルドアップタイムの値を用い、実施例1-13~実施例1-16では比較例1-2のビルドアップの値を用いた。
エチレン-ビニルアルコール共重合体(クラレ社製)100部、化合物(1-1)0.3部およびトレハロース0.2部をドライブレンドした後、得られた混合物をスクリュー径30mmの単軸押出機(田辺プラスチック社製「VS30-28型押出機」)を用いて温度230℃およびスクリュー回転数50rpmの条件で混練押出してストランドを得て、このストランドをペレタイザーで切断することによって、熱可塑性ポリマー組成物のペレットを得た。
安定剤組成物として化合物(1-1)0.1部およびトレハロース0.4部を使用したこと以外は実施例1-17と同様にして、熱可塑性ポリマー組成物のペレットを得た。
安定剤として化合物(1-1)0.5部のみを使用したこと以外は実施例1-17と同様にして、熱可塑性ポリマー組成物のペレットを得た。
押出加工の運転時の(即ち、静的条件下における)加工安定性を評価するために、実施例1-17、実施例1-18および比較例1-3でそれぞれ得られた熱可塑性ポリマー組成物のペレットを用いて、滞留MFR試験を実施した。該試験はJIS K 7210に準拠し、メルトインデクサ(L217-E14011、テクノ・セブン社製)を、シリンダー内の温度270℃および荷重2.16kgの条件で用いて、滞留前MFR(g/10分)と滞留後MFR(g/10分)とを測定した。滞留前MFRは、該シリンダー内に熱可塑性ポリマー組成物のペレットを充填して5分間の予熱時間を取った後に測定した。滞留後MFRは、熱可塑性ポリマー組成物のペレットを該シリンダー内で予熱時間を含めて合計30分間滞留させた後に測定した。このようにして測定された滞留前MFRと滞留後MFRとから、下記式:
MFR変動率(%)
=(滞留後MFR-滞留前MFR)の絶対値×100/(滞留前MFR)
に基づき、MFR変動率を計算した。MFR変動率が小さいほど、熱可塑性ポリマー組成物の加工安定性は良好である。結果を表3に示す。
表4に記載の量で化合物(1-1)、トレハロース、化合物(2-1)および化合物(3-1)を混合して、安定剤組成物を得た。
スチレン-ブタジエンブロック共重合体(電気化学社製)100部と、実施例1-19で得られた安定剤組成物0.31部とをドライブレンドした後、得られた混合物をスクリュー径30mmの単軸押出機(田辺プラスチック社製「VS30-28型押出機」)を用いて温度230℃およびスクリュー回転数50rpmで混練押出してストランドを得て、このストランドをペレタイザーで切断することによって、熱可塑性ポリマー組成物のペレットを得た。
実施例1-19で得られた安定剤組成物に替えて、実施例1-20で得られた安定剤組成物0.51部を使用したこと以外は実施例1-23と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例1-19で得られた安定剤組成物に替えて、実施例1-21で得られた安定剤組成物0.51部を使用したこと以外は実施例1-23と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例1-19で得られた安定剤組成物に替えて、実施例1-22で得られた安定剤組成物0.71部を使用したこと以外は実施例1-23と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例1-19で得られた安定剤組成物に替えて、化合物(1-1)0.3部を使用したこと以外は実施例1-23と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例1-23~実施例1-26および比較例1-4でそれぞれ得られた熱可塑性ポリマー組成物のペレットを用いて、試験例1-2と同様にして、滞留MFR試験を実施した。結果を表5に示す。
表6に記載の量で化合物(1-1)およびトレハロースを混合して、安定剤組成物を得た。
実施例1-19で得られた安定剤組成物0.31部に替えて、実施例1-27~31のそれぞれで得られた安定剤組成物0.2部を使用したこと以外は実施例1-23と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例1-32~実施例1-36でそれぞれ得られた熱可塑性ポリマー組成物のペレットを用いて、試験例1-2と同様にして、滞留MFR試験を実施した。結果を表7に示す。
表8-1~表8-3に記載の成分を混合することによって、安定剤組成物が得られる。これらの安定剤組成物を含む熱可塑性ポリマー組成物は、加工安定性に優れることが予測される。
表9-1~表9-4に記載の熱可塑性ポリマー100部と、表9-1~表9-4に記載の種類および量の安定剤組成物とを用いること以外は実施例1-4と同様にして、熱可塑性ポリマー組成物のペレットが得られる。得られる熱可塑性ポリマー組成物は、加工安定性に優れることが予測される。
P1-1:高密度ポリエチレン(HDPE)(P1-45~P1-50を除く)
P1-2:低密度ポリエチレン(LDPE)(P1-51~P1-57を除く)
P1-3:直鎖状低密度ポリエチレン(LLDPE)(P1-58~P1-64を除く)
P1-4:エチレン-アクリル酸エチル共重合体(EEA)
P1-5:エチレン-酢酸ビニル共重合体(EVA)
P1-6:ポリプロピレン(PP)(P1-65~P1-71を除く)
P1-7:プロピレン-エチレンランダム共重合体
P1-8:プロピレン-α-オレフィンランダム共重合体
P1-9:プロピレン-エチレン-α-オレフィン共重合体
P1-10:ポリスチレン(PS)
P1-11:アクリロニトリル-スチレン共重合体(SAN)
P1-12:アクリロニトリル-ブタジエン-スチレン共重合体(ABS)
P1-13:特殊アクリルゴム-アクリロニトリル-スチレン共重合体
P1-14:アクリロニトリル-塩素化ポリエチレン-スチレン共重合体(ACS)
P1-15:ポリブタジエンゴム(BR)
P1-16:スチレン-ブタジエン共重合体(SB)
P1-17:スチレン-ブタジエンブロック共重合体(SBS)
P1-18:塩素化ポリエチレン(CPE)
P1-19:ポリクロロプレン
P1-20:塩素化ゴム
P1-21:ポリ塩化ビニル(PVC)
P1-22:ポリ塩化ビニリデン(PVDC)
P1-23:メタクリル樹脂
P1-24:フッ素樹脂
P1-25:ポリアセタール(POM)
P1-26:グラフト化ポリフェニレンエーテル樹脂
P1-27:ポリフェニレンサルファイド樹脂(PPS)
P1-28:ポリウレタン(PU)(P1-75~P1-77を除く)
P1-29:ポリアミド(PA)(P1-78~P1-86を除く)
P1-30:ポリエチレンテレフタレート(PET)
P1-31:ポリブチレンテレフタレート(PBT)
P1-32:ポリ乳酸(PLA)
P1-33:ポリカーボネート(PC)
P1-34:ポリアクリレート
P1-35:ポリスルホン(PPSU)
P1-36:ポリエーテルエーテルケトン(PEEK)
P1-37:ポリエーテルスルホン(PES)
P1-38:芳香族ポリエステル
P1-39:ジアリルフタレートプレポリマー
P1-40:シリコーン樹脂(SI)
P1-41:1,2-ポリブタジエン
P1-42:ポリイソプレン
P1-43:ブタジエン-アクリロニトリル共重合体(NBR)
P1-44:エチレン-メチルメタクリレート共重合体(EMMA)
P1-45:MFRが40g/10分である高密度ポリエチレン(HDPE)
P1-46:MFRが20g/10分である高密度ポリエチレン(HDPE)
P1-47:MFRが10g/10分である高密度ポリエチレン(HDPE)
P1-48:MFRが5g/10分である高密度ポリエチレン(HDPE)
P1-49:MFRが1g/10分である高密度ポリエチレン(HDPE)
P1-50:MFRが0.1g/10分である高密度ポリエチレン(HDPE)
P1-51:MFRが75g/10分である低密度ポリエチレン(LDPE)
P1-52:MFRが50g/10分である低密度ポリエチレン(LDPE)
P1-53:MFRが25g/10分である低密度ポリエチレン(LDPE)
P1-54:MFRが10g/10分である低密度ポリエチレン(LDPE)
P1-55:MFRが5g/10分である低密度ポリエチレン(LDPE)
P1-56:MFRが2g/10分である低密度ポリエチレン(LDPE)
P1-57:MFRが1g/10分である低密度ポリエチレン(LDPE)
P1-58:MFRが0.1g/10分である低密度ポリエチレン(LDPE)
P1-59:MFRが100g/10分である直鎖状低密度ポリエチレン(LLDPE)
P1-60:MFRが50g/10分である直鎖状低密度ポリエチレン(LLDPE)
P1-61:MFRが25g/10分である直鎖状低密度ポリエチレン(LLDPE)
P1-62:MFRが10g/10分である直鎖状低密度ポリエチレン(LLDPE)
P1-63:MFRが5g/10分である直鎖状低密度ポリエチレン(LLDPE)
P1-64:MFRが1g/10分である直鎖状低密度ポリエチレン(LLDPE)
P1-65:MFRが0.1g/10分である直鎖状低密度ポリエチレン(LLDPE)
P1-66:MFRが100g/10分であるポリプロピレン(PP)
P1-67:MFRが50g/10分であるポリプロピレン(PP)
P1-68:MFRが25g/10分であるポリプロピレン(PP)
P1-69:MFRが10g/10分であるポリプロピレン(PP)
P1-70:MFRが5g/10分であるポリプロピレン(PP)
P1-71:MFRが1g/10分であるポリプロピレン(PP)
P1-72:MFRが0.1g/10分であるポリプロピレン(PP)
P1-73:スチレン-ブタジエン系熱可塑性エラストマー
P1-74:スチレン-エチレン-ブチレン-スチレンブロック共重合体(SEBS)
P1-75:スチレン-イソプレン-スチレンブロック共重合体(SIS)
P1-76:重量平均分子量が1000であるポリウレタン(PU)
P1-77:重量平均分子量が2000であるポリウレタン(PU)
P1-78:重量平均分子量が5000であるポリウレタン(PU)
P1-79:数平均分子量が5000であるナイロン6(Ny6)
P1-80:数平均分子量が10000であるナイロン6(Ny6)
P1-81:数平均分子量が50000であるナイロン6(Ny6)
P1-82:数平均分子量が100000であるナイロン6(Ny6)
P1-83:ナイロン610(Ny610)
P1-84:ナイロン612(Ny612)
P1-85:ナイロン11(Ny11)
P1-86:ナイロン12(Ny12)
P1-87:ナイロンMXD6(NyMXD6)
化合物(8-1)0.2部およびトレハロース0.05部を混合して、安定剤組成物を製造した。
化合物(8-1)0.1部およびトレハロース0.01部を混合して、安定剤組成物を製造した。
エチレン-ビニルアルコール共重合体(クラレ社製)100部と、実施例2-1で得られた安定剤組成物の全量とをドライブレンドした後、得られた混合物を、スクリュー径30mmの単軸押出機(田辺プラスチック社製「VS30-28型押出機」)を用いて温度230℃およびスクリュー回転数50rpmで混練押出してストランドを得て、このストランドをペレタイザーで切断することによって、熱可塑性ポリマー組成物のペレットを得た。
実施例2-1で得られた安定剤組成物に替えて、実施例2-2で得られた安定剤組成物を用いたこと以外は実施例2-3と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例2-1で得られた安定剤組成物に替えて、化合物(8-1)0.1部を用いたこと以外は実施例2-3と同様にして、熱可塑性ポリマー組成物のペレットを得た。
押出加工の運転時の加工安定性を評価するために、実実施例2-34および比較例2-1でそれぞれ得られた熱可塑性ポリマー組成物のペレットを用いて、滞留MFR試験を実施した。該試験はJIS K 7210に準拠し、メルトインデクサ(L217-E14011、テクノ・セブン社製)を、シリンダー内の温度270℃および荷重2.16kgの条件で用いて、滞留前MFR(g/10分)と滞留後MFR(g/10分)とを測定した。滞留前MFRは、該シリンダー内に熱可塑性ポリマー組成物のペレットを充填して5分間の予熱時間を取った後に測定した。滞留後MFRは、熱可塑性ポリマー組成物のペレットを該シリンダー内で予熱時間を含めて合計30分間滞留させた後に測定した。このようにして測定された滞留前MFRと滞留後MFRとから、下記式:
MFR変動率(%)
=(滞留後MFR-滞留前MFR)の絶対値×100/(滞留前MFR)
に基づき、MFR変動率を計算した。MFR変動率が小さいほど、熱可塑性ポリマー組成物の加工安定性は良好である。
表12-1~表12-3に記載の成分を混合することによって、安定剤組成物が得られる。これらの安定剤組成物を含む熱可塑性ポリマー組成物は、加工安定性に優れることが予測される。
表13-1~表13-4に記載の熱可塑性ポリマー100部と、表13-1~表13-4に記載の種類および量の安定剤組成物とを用いること以外は実施例2-2と同様にして、熱可塑性ポリマー組成物のペレットが得られる。得られる熱可塑性ポリマー組成物は、加工安定性に優れることが予測される。
P2-1:高密度ポリエチレン(HDPE)(P2-45~P2-50を除く)
P2-2:低密度ポリエチレン(LDPE)(P2-51~P2-57を除く)
P2-3:直鎖状低密度ポリエチレン(LLDPE)(P2-58~P2-64を除く)
P2-4:エチレン-アクリル酸エチル共重合体(EEA)
P2-5:エチレン-酢酸ビニル共重合体(EVA)
P2-6:ポリプロピレン(PP)(P2-65~P2-71を除く)
P2-7:プロピレン-エチレンランダム共重合体
P2-8:プロピレン-α-オレフィンランダム共重合体
P2-9:プロピレン-エチレン-α-オレフィン共重合体
P2-10:ポリスチレン(PS)
P2-11:アクリロニトリル-スチレン共重合体(SAN)
P2-12:アクリロニトリル-ブタジエン-スチレン共重合体(ABS)
P2-13:特殊アクリルゴム-アクリロニトリル-スチレン共重合体
P2-14:アクリロニトリル-塩素化ポリエチレン-スチレン共重合体(ACS)
P2-15:ポリブタジエンゴム(BR)
P2-16:スチレン-ブタジエン共重合体(SB)
P2-17:スチレン-ブタジエンブロック共重合体(SBS)
P2-18:塩素化ポリエチレン(CPE)
P2-19:ポリクロロプレン
P2-20:塩素化ゴム
P2-21:ポリ塩化ビニル(PVC)
P2-22:ポリ塩化ビニリデン(PVDC)
P2-23:メタクリル樹脂
P2-24:フッ素樹脂
P2-25:ポリアセタール(POM)
P2-26:グラフト化ポリフェニレンエーテル樹脂
P2-27:ポリフェニレンサルファイド樹脂(PPS)
P2-28:ポリウレタン(PU)(P2-75~P2-77を除く)
P2-29:ポリアミド(PA)(P2-78~P2-86を除く)
P2-30:ポリエチレンテレフタレート(PET)
P2-31:ポリブチレンテレフタレート(PBT)
P2-32:ポリ乳酸(PLA)
P2-33:ポリカーボネート(PC)
P2-34:ポリアクリレート
P2-35:ポリスルホン(PPSU)
P2-36:ポリエーテルエーテルケトン(PEEK)
P2-37:ポリエーテルスルホン(PES)
P2-38:芳香族ポリエステル
P2-39:ジアリルフタレートプレポリマー
P2-40:シリコーン樹脂(SI)
P2-41:1,2-ポリブタジエン
P2-42:ポリイソプレン
P2-43:ブタジエン-アクリロニトリル共重合体(NBR)
P2-44:エチレン-メチルメタクリレート共重合体(EMMA)
P2-45:MFRが40g/10分である高密度ポリエチレン(HDPE)
P2-46:MFRが20g/10分である高密度ポリエチレン(HDPE)
P2-47:MFRが10g/10分である高密度ポリエチレン(HDPE)
P2-48:MFRが5g/10分である高密度ポリエチレン(HDPE)
P2-49:MFRが1g/10分である高密度ポリエチレン(HDPE)
P2-50:MFRが0.1g/10分である高密度ポリエチレン(HDPE)
P2-51:MFRが75g/10分である低密度ポリエチレン(LDPE)
P2-52:MFRが50g/10分である低密度ポリエチレン(LDPE)
P2-53:MFRが25g/10分である低密度ポリエチレン(LDPE)
P2-54:MFRが10g/10分である低密度ポリエチレン(LDPE)
P2-55:MFRが5g/10分である低密度ポリエチレン(LDPE)
P2-56:MFRが2g/10分である低密度ポリエチレン(LDPE)
P2-57:MFRが1g/10分である低密度ポリエチレン(LDPE)
P2-58:MFRが0.1g/10分である低密度ポリエチレン(LDPE)
P2-59:MFRが100g/10分である直鎖状低密度ポリエチレン(LLDPE)
P2-60:MFRが50g/10分である直鎖状低密度ポリエチレン(LLDPE)
P2-61:MFRが25g/10分である直鎖状低密度ポリエチレン(LLDPE)
P2-62:MFRが10g/10分である直鎖状低密度ポリエチレン(LLDPE)
P2-63:MFRが5g/10分である直鎖状低密度ポリエチレン(LLDPE)
P2-64:MFRが1g/10分である直鎖状低密度ポリエチレン(LLDPE)
P2-65:MFRが0.1g/10分である直鎖状低密度ポリエチレン(LLDPE)
P2-66:MFRが100g/10分であるポリプロピレン(PP)
P2-67:MFRが50g/10分であるポリプロピレン(PP)
P2-68:MFRが25g/10分であるポリプロピレン(PP)
P2-69:MFRが10g/10分であるポリプロピレン(PP)
P2-70:MFRが5g/10分であるポリプロピレン(PP)
P2-71:MFRが1g/10分であるポリプロピレン(PP)
P2-72:MFRが0.1g/10分であるポリプロピレン(PP)
P2-73:スチレン-ブタジエン系熱可塑性エラストマー
P2-74:スチレン-エチレン-ブチレン-スチレンブロック共重合体(SEBS)
P2-75:スチレン-イソプレン-スチレンブロック共重合体(SIS)
P2-76:重量平均分子量が1000であるポリウレタン(PU)
P2-77:重量平均分子量が2000であるポリウレタン(PU)
P2-78:重量平均分子量が5000であるポリウレタン(PU)
P2-79:数平均分子量が5000であるナイロン6(Ny6)
P2-80:数平均分子量が10000であるナイロン6(Ny6)
P2-81:数平均分子量が50000であるナイロン6(Ny6)
P2-82:数平均分子量が100000であるナイロン6(Ny6)
P2-83:ナイロン610(Ny610)
P2-84:ナイロン612(Ny612)
P2-85:ナイロン11(Ny11)
P2-86:ナイロン12(Ny12)
P2-87:ナイロンMXD6(NyMXD6)
化合物(2-1)0.2部、トレハロース0.01部および化合物(1-1)0.3部を混合して、安定剤組成物を製造した。
化合物(2-1)0.2部および化合物(1-1)0.3部を混合して、安定剤組成物を製造した。
スチレン-ブタジエンブロック共重合体(旭化成社製)100部と、実施例3-1で得られた安定剤組成物0.51部とをドライブレンドした後、得られた混合物を、スクリュー径30mmの単軸押出機(田辺プラスチック社製「VS30-28型押出機」)を用いて温度230℃およびスクリュー回転数50rpmで混練押出してストランドを得て、このストランドをペレタイザーで切断することによって、熱可塑性ポリマー組成物のペレットを得た。
実施例3-1で得られた安定剤組成物に替えて参考例3-1で得られた組成物0.5部を用いたこと以外は実施例3-2と同様にして、熱可塑性ポリマー組成物のペレットを得た。
押出加工の運転時の加工安定性を評価するために、実施例3-2および参考例3-2でそれぞれ得た熱可塑性ポリマー組成物のペレットを用いて、滞留MFR試験を実施した。該試験はJIS K 7210に準拠し、メルトインデクサ(L217-E14011、テクノ・セブン社製)を、シリンダー内の温度270℃および荷重2.16kgの条件で用いて、滞留前MFR(g/10分)と滞留後MFR(g/10分)とを測定した。滞留前MFRは、該シリンダー内に熱可塑性ポリマー組成物のペレットを充填して5分間の予熱時間を取った後に測定した。滞留後MFRは、熱可塑性ポリマー組成物のペレットを該シリンダー内で予熱時間を含めて合計30分間滞留させた後に測定した。このようにして測定された滞留前MFRと滞留後MFRとから、下記式:
MFR変動率(%)
=(滞留後MFR-滞留前MFR)の絶対値×100/(滞留前MFR)
に基づき、MFR変動率を計算した。
化合物(2-2)0.1部およびトレハロース0.1部を混合して、安定剤組成物を製造した。
ポリプロピレン100部(住友化学社製)と、実施例3-3で得られた安定剤組成物0.2部とをドライブレンドした後、得られた混合物を、スクリュー径30mmの単軸押出機(田辺プラスチック社製「VS30-28型押出機」)を用いて温度230℃およびスクリュー回転数50rpmで混練押出してストランドを得て、このストランドをペレタイザーで切断することによって、熱可塑性ポリマー組成物のペレットを得た。
実施例3-3で得られた安定剤組成物に替えて、化合物(2-2)0.1部を用いたこと以外は実施例3-4と同様にして、熱可塑性ポリマー組成物のペレットを得た。
押出加工の運転時の加工安定性を評価するために、実施例3-4および比較例3-1でそれぞれ得た熱可塑性ポリマー組成物のペレットを用いて、滞留MFR試験を実施した。該試験はJIS K 7210に準拠し、メルトインデクサ(L217-E14011、テクノ・セブン社製)を、シリンダー内の温度270℃および荷重2.16kgの条件で用いて、滞留後MFR(g/10分)を測定した。この滞留後MFRは、熱可塑性ポリマー組成物のペレットを該シリンダー内で予熱時間を含めて合計30分間滞留させた後に測定した。
表18に記載の量で化合物(2-1)、トレハロース、化合物(1-1)および化合物(3-1)混合して、それぞれ、安定剤組成物を製造した。
スチレン-ブタジエンブロック共重合体(電気化学社製)100部と、実施例3-5で得られた安定剤組成物0.21部とをドライブレンドした後、得られた混合物を、スクリュー径30mmの単軸押出機(田辺プラスチック社製「VS30-28型押出機」)を用いて温度230℃およびスクリュー回転数50rpmで混練押出してストランドを得て、このストランドをペレタイザーで切断することによって、熱可塑性ポリマー組成物のペレットを得た。
実施例3-5で得られた安定剤組成物に替えて、実施例3-6で得られた安定剤組成物0.41部を使用したこと以外は実施例3-8と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例3-5で得られた安定剤組成物に替えて、実施例3-7で得られた安定剤組成物0.71部を使用したこと以外は実施例3-8と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例3-5で得られた安定剤組成物に替えて、化合物(2-1)0.2部を使用したこと以外は実施例3-8と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例3-8~実施例3-10および比較例3-2で得られた熱可塑性ポリマー組成物のペレットを用いて、試験例3-1と同様にして、滞留前MFR(g/10分)および滞留後MFR(g/10分)を測定し、MFR変動率(%)を計算した。これらの結果を表19に示す。
表20-1および表20-2に記載の成分を混合することによって、安定剤組成物が得られる。これらの安定剤組成物を含む熱可塑性ポリマー組成物は、加工安定性に優れることが予測される。
表21-1および表21-2に記載の熱可塑性ポリマー100部と、表21-1および表21-2に記載の種類および量の安定剤組成物とを用いること以外は実施例3-4と同様にして、熱可塑性ポリマー組成物のペレットが得られる。得られる熱可塑性ポリマー組成物は、加工安定性に優れることが予測される。
P3-1:高密度ポリエチレン(HDPE)
P3-2:低密度ポリエチレン(LDPE)
P3-3:直鎖状低密度ポリエチレン(LLDPE)
P3-4:エチレン-ビニルアルコール共重合体(EVOH)
P3-5:エチレン-アクリル酸エチル共重合体(EEA)
P3-6:エチレン-酢酸ビニル共重合体(EVA)
P3-7:プロピレン-エチレンランダム共重合体
P3-8:プロピレン-α-オレフィンランダム共重合体
P3-9:プロピレン-エチレン-α-オレフィン共重合体
P3-10:ポリスチレン(PS)
P3-11:アクリロニトリル-スチレン共重合体(SAN)
P3-12:アクリロニトリル-ブタジエン-スチレン共重合体(ABS)
P3-13:特殊アクリルゴム-アクリロニトリル-スチレン共重合体
P3-14:アクリロニトリル-塩素化ポリエチレン-スチレン共重合体(ACS)
P3-15:ポリブタジエンゴム(BR)
P3-16:スチレン-ブタジエン共重合体(SB)
P3-17:スチレン-ブタジエンブロック共重合体(SBS)
P3-18:塩素化ポリエチレン(CPE)
P3-19:ポリクロロプレン
P3-20:塩素化ゴム
P3-21:ポリ塩化ビニル(PVC)
P3-22:ポリ塩化ビニリデン(PVDC)
P3-23:メタクリル樹脂
P3-24:フッ素樹脂
P3-25:ポリアセタール(POM)
P3-26:グラフト化ポリフェニレンエーテル樹脂
P3-27:ポリフェニレンサルファイド樹脂(PPS)
P3-28:ポリウレタン(PU)
P3-29:ポリアミド(PA)
P3-30:ポリエチレンテレフタレート(PET)
P3-31:ポリブチレンテレフタレート(PBT)
P3-32:ポリ乳酸(PLA)
P3-33:ポリカーボネート(PC)
P3-34:ポリアクリレート
P3-35:ポリスルホン(PPSU)
P3-36:ポリエーテルエーテルケトン(PEEK)
P3-37:ポリエーテルスルホン(PES)
P3-38:芳香族ポリエステル
P3-39:ジアリルフタレートプレポリマー
P3-40:シリコーン樹脂(SI)
P3-41:1,2-ポリブタジエン
P3-42:ポリイソプレン
P3-43:ブタジエン-アクリロニトリル共重合体(NBR)
P3-44:エチレン-メチルメタクリレート共重合体(EMMA)
化合物(3-1)0.1部およびトレハロース0.01部を混合して、安定剤組成物を製造した。
ポリプロピレン(住友化学社製)100部と、実施例4-1で得られた安定剤組成物とをドライブレンドした後、得られた混合物を、スクリュー径30mmの単軸押出機(田辺プラスチック社製「VS30-28型押出機」)を用いて温度230℃およびスクリュー回転数50rpmで混練押出してストランドを得て、このストランドをペレタイザーで切断することによって、熱可塑性ポリマー組成物のペレットを得た。
実施例4-1で得られた安定剤組成物に替えて、化合物(3-1)0.1部のみを用いたこと以外は実施例4-2と同様にして、熱可塑性ポリマー組成物のペレットを得た。
押出加工の運転時の加工安定性を評価するために、実施例4-2および比較例4-1でそれぞれ得た熱可塑性ポリマー組成物のペレットを用いて、滞留MFR試験を実施した。該試験はJIS K 7210に準拠し、メルトインデクサ(L217-E14011、テクノ・セブン社製)を、シリンダー内の温度270℃および荷重2.16kgの条件で用いて、滞留後MFR(g/10分)を測定した。この滞留後MFRは、熱可塑性ポリマー組成物のペレットを該シリンダー内で予熱時間を含めて合計30分間滞留させた後に測定した。ポリプロピレンは加工時の熱によって分解が進むので、ポリプロピレンを含む熱可塑性ポリマー組成物では、滞留後MFRが小さいほど、その加工安定性が良好である。
MFR上昇抑制率(%)
=[(比較例4-1の滞留後MFR)-(実施例4-2の滞留後MFR)]×100/(比較例4-1の滞留後MFR)
に基づきMFR上昇抑制率を計算した。この結果も表23に示す。
表24に記載の量で化合物(3-1)、トレハロース、化合物(1-1)および化合物(2-1)を混合して、それぞれ、安定剤組成物を製造した。
スチレン-ブタジエンブロック共重合体(電気化学社製)100部と、実施例4-3で得られた安定剤組成物0.21部とをドライブレンドした後、得られた混合物を、スクリュー径30mmの単軸押出機(田辺プラスチック社製「VS30-28型押出機」)を用いて温度230℃およびスクリュー回転数50rpmで混練押出してストランドを得て、このストランドをペレタイザーで切断することによって、熱可塑性ポリマー組成物のペレットを得た。
実施例4-3で得られた安定剤組成物に替えて、実施例4-4で得られた安定剤組成物0.51部を使用したこと以外は実施例4-7と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例4-3で得られた安定剤組成物に替えて、実施例4-5で得られた安定剤組成物0.41部を使用したこと以外は実施例4-7と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例4-3で得られた安定剤組成物に替えて、実施例4-6で得られた安定剤組成物0.71部を使用したこと以外は実施例4-7と同様にして、熱可塑性ポリマー組成物のペレットを得た。
実施例4-3で得られた安定剤組成物に替えて、化合物(3-1)0.2部のみを使用したこと以外は実施例4-7と同様にして、熱可塑性ポリマー組成物のペレットを得た。
押出加工の運転時の加工安定性を評価するために、実施例4-7~実施例4-10および比較例4-2でそれぞれ得た熱可塑性ポリマー組成物のペレットを用いて、滞留MFR試験を実施した。該試験はJIS K 7210に準拠し、メルトインデクサ(L217-E14011、テクノ・セブン社製)を、シリンダー内の温度270℃および荷重2.16kgの条件で用いて、滞留前MFR(g/10分)と滞留後MFR(g/10分)とを測定した。滞留前MFRは、該シリンダー内に熱可塑性ポリマー組成物のペレットを充填して5分間の予熱時間を取った後に測定した。滞留後MFRは、熱可塑性ポリマー組成物のペレットを該シリンダー内で予熱時間を含めて合計30分間滞留させた後に測定した。このようにして測定された滞留前MFRと滞留後MFRとから、下記式:
MFR変動率(%)
=(滞留後MFR-滞留前MFR)の絶対値×100/(滞留前MFR)
に基づき、MFR変動率を計算した。
表26-1~表26-4に記載の成分を混合することによって、安定剤組成物が得られる。これらの安定剤組成物を含む熱可塑性ポリマー組成物は、加工安定性に優れることが予測される。
表27-1および表27-2に記載の熱可塑性ポリマー100部と、表27-1および表27-2に記載の種類および量の安定剤組成物とを用いること以外は実施例4-2と同様にして、熱可塑性ポリマー組成物のペレットが得られる。得られる熱可塑性ポリマー組成物は、加工安定性に優れることが予測される。
P4-1:高密度ポリエチレン(HDPE)
P4-2:低密度ポリエチレン(LDPE)
P4-3:直鎖状低密度ポリエチレン(LLDPE)
P4-4:エチレン-ビニルアルコール共重合体(EVOH)
P4-5:エチレン-アクリル酸エチル共重合体(EEA)
P4-6:エチレン-酢酸ビニル共重合体(EVA)
P4-7:プロピレン-エチレンランダム共重合体
P4-8:プロピレン-α-オレフィンランダム共重合体
P4-9:プロピレン-エチレン-α-オレフィン共重合体
P4-10:ポリスチレン(PS)
P4-11:アクリロニトリル-スチレン共重合体(SAN)
P4-12:アクリロニトリル-ブタジエン-スチレン共重合体(ABS)
P4-13:特殊アクリルゴム-アクリロニトリル-スチレン共重合体
P4-14:アクリロニトリル-塩素化ポリエチレン-スチレン共重合体(ACS)
P4-15:ポリブタジエンゴム(BR)
P4-16:スチレン-ブタジエン共重合体(SB)
P4-17:スチレン-ブタジエンブロック共重合体(SBS)
P4-18:塩素化ポリエチレン(CPE)
P4-19:ポリクロロプレン
P4-20:塩素化ゴム
P4-21:ポリ塩化ビニル(PVC)
P4-22:ポリ塩化ビニリデン(PVDC)
P4-23:メタクリル樹脂
P4-24:フッ素樹脂
P4-25:ポリアセタール(POM)
P4-26:グラフト化ポリフェニレンエーテル樹脂
P4-27:ポリフェニレンサルファイド樹脂(PPS)
P4-28:ポリウレタン(PU)
P4-29:ポリアミド(PA)
P4-30:ポリエチレンテレフタレート(PET)
P4-31:ポリブチレンテレフタレート(PBT)
P4-32:ポリ乳酸(PLA)
P4-33:ポリカーボネート(PC)
P4-34:ポリアクリレート
P4-35:ポリスルホン(PPSU)
P4-36:ポリエーテルエーテルケトン(PEEK)
P4-37:ポリエーテルスルホン(PES)
P4-38:芳香族ポリエステル
P4-39:ジアリルフタレートプレポリマー
P4-40:シリコーン樹脂(SI)
P4-41:1,2-ポリブタジエン
P4-42:ポリイソプレン
P4-43:ブタジエン-アクリロニトリル共重合体(NBR)
P4-44:エチレン-メチルメタクリレート共重合体(EMMA)
Claims (25)
- 式(1)で示される化合物およびトレハロースの合計量が、熱可塑性ポリマー100重量部に対して0.001~3重量部である請求項1に記載の熱可塑性ポリマー組成物。
- 式(1)で示される化合物が、2,4-ジ-t-ペンチル-6-[1-(3,5-ジ-t-ペンチル-2-ヒドロキシフェニル)エチル]フェニル アクリレートおよび2-t-ブチル-6-(3-t-ブチル-2-ヒドロキシ-5-メチルベンジル)-4-メチルフェニル アクリレートからなる群から選ばれる少なくとも一つである請求項3に記載の安定剤組成物。
- さらに、式(3)~式(7):
各R11および各R12は、それぞれ独立に、水素原子、C1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
各L2は、それぞれ独立に、単結合、硫黄原子または式(6a):
各L3は、それぞれ独立に、C2-8アルキレン基を表す。]
各R15および各R16は、それぞれ独立に、水素原子、C1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
R17は、C1-8アルキル基、またはC1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基およびC7-12アラルキル基からなる群から選ばれる少なくとも一つで置換されていてもよいフェニル基を表す。
L4は、単結合、硫黄原子または式(7a):
で示される化合物からなる群から選ばれる少なくとも一つを含有する請求項3~5のいずれか一項に記載の安定剤組成物。 - 式(3)~式(7)で示される化合物からなる群から選ばれる少なくとも一つが、式(3)で示される化合物である請求項6に記載の安定剤組成物。
- 式(8):
各R20、各R21、R23およびR24は、それぞれ独立に、水素原子、C1-8アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
各R22は、それぞれ独立に、水素原子またはC1-8アルキル基を表す。
L5は、単結合、硫黄原子または式(8a):
L6は、C2-8アルキレン基または式(8b):
Z1およびZ2のいずれか一方は、ヒドロキシ基、C1-8アルキル基、C1-8アルコキシ基またはC7-12アラルキルオキシ基を表し、他方は、水素原子またはC1-8アルキル基を表す。]
で示される化合物、トレハロースおよび熱可塑性ポリマーを含有することを特徴とする熱可塑性ポリマー組成物。 - 式(8)で示される化合物およびトレハロースの合計量が、熱可塑性ポリマー100重量部に対して0.001~3重量部である請求項8に記載の熱可塑性ポリマー組成物。
- 式(8):
各R20、各R21、R23およびR24は、それぞれ独立に、水素原子、C1-8アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
各R22は、それぞれ独立に、水素原子またはC1-8アルキル基を表す。
L5は、単結合、硫黄原子または式(8a):
L6は、C2-8アルキレン基または式(8b):
Z1およびZ2のいずれか一方は、ヒドロキシ基、C1-8アルキル基、C1-8アルコキシ基またはC7-12アラルキルオキシ基を表し、他方は、水素原子またはC1-8アルキル基を表す。]
で示される化合物およびトレハロースを含有することを特徴とする安定剤組成物。 - 式(8)で示される化合物が、6-[3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-2,4,8,10-テトラ-t-ブチルジベンズ[d,f][1,3,2]ジオキサホスフェピンである請求項10に記載の安定剤組成物。
- さらに、式(3)~式(7):
各R13および各R14は、それぞれ独立に、水素原子、C1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
各L5は、それぞれ独立に、単結合、硫黄原子または式(6a):
各L6は、それぞれ独立に、C2-8アルキレン基を表す。]
各R17および各R18は、それぞれ独立に、水素原子、C1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
R19は、C1-8アルキル基、またはC1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基およびC7-12アラルキル基からなる群から選ばれる少なくとも一つで置換されていてもよいフェニル基を表す。
L7は、単結合、硫黄原子または式(7a):
で示される化合物からなる群から選ばれる少なくとも一つを含有する請求項10~12のいずれか一項に記載の安定剤組成物。 - 式(3)~式(7)で示される化合物からなる群から選ばれる少なくとも一つが、式(3)で示される化合物である請求項13に記載の安定剤組成物。
- 式(2)で示される化合物およびトレハロースの合計量が、熱可塑性ポリマー100重量部に対して0.001~3重量部である請求項15に記載の熱可塑性ポリマー組成物。
- 熱可塑性ポリマーが、スチレン-ブタジエンブロック共重合体である請求項15または16に記載の熱可塑性ポリマー組成物。
- 式(2)で示される化合物が、オクタデシル 3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、3,9-ビス[2-{3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ}-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカンおよびペンタエリスリトール テトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]からなる群から選ばれる少なくとも一つである請求項18に記載の安定剤組成物。
- 式(3)~式(7):
各R11および各R12は、それぞれ独立に、水素原子、C1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
各L2は、それぞれ独立に、単結合、硫黄原子または式(6a):
各L3は、それぞれ独立に、C2-8アルキレン基を表す。]
各R15および各R16は、それぞれ独立に、水素原子、C1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
R17は、C1-8アルキル基、またはC1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基およびC7-12アラルキル基からなる群から選ばれる少なくとも一つで置換されていてもよいフェニル基を表す。
L4は、単結合、硫黄原子または式(7a):
で示される化合物からなる群から選ばれる少なくとも一つ、トレハロースおよび熱可塑性ポリマーを含有することを特徴とする熱可塑性ポリマー組成物。 - 式(3)~式(7)で示される化合物からなる群から選ばれる化合物およびトレハロースの合計量が、熱可塑性ポリマー100重量部に対して0.001~3重量部である請求項20に記載の熱可塑性ポリマー組成物。
- 熱可塑性ポリマーが、スチレン-ブタジエンブロック共重合体である請求項20または21に記載の熱可塑性ポリマー組成物。
- 式(3)~式(7):
各R11および各R12は、それぞれ独立に、水素原子、C1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
各L2は、それぞれ独立に、単結合、硫黄原子または式(6a):
各L3は、それぞれ独立に、C2-8アルキレン基を表す。]
各R15および各R16は、それぞれ独立に、水素原子、C1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基、C7-12アラルキル基またはフェニル基を表す。
R17は、C1-8アルキル基、またはC1-9アルキル基、C5-8シクロアルキル基、C6-12アルキルシクロアルキル基およびC7-12アラルキル基からなる群から選ばれる少なくとも一つで置換されていてもよいフェニル基を表す。
L4は、単結合、硫黄原子または式(7a):
で示される化合物からなる群から選ばれる少なくとも一つおよびトレハロースを含有することを特徴とする安定剤組成物。 - 式(3)~式(7)で示される化合物からなる群から選ばれる少なくとも一つが、式(3)で示される化合物である請求項23に記載の安定剤組成物。
- 式(3)で示される化合物が、トリス(2,4-ジ-t-ブチルフェニル)ホスファイトである請求項24に記載の安定剤組成物。
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JP2012107184A (ja) * | 2010-06-29 | 2012-06-07 | Sumitomo Chemical Co Ltd | 熱可塑性ポリマー組成物 |
JP2012107182A (ja) * | 2010-05-12 | 2012-06-07 | Sumitomo Chemical Co Ltd | 熱可塑性ポリマー組成物 |
WO2013089280A1 (ja) * | 2011-12-16 | 2013-06-20 | 住友化学株式会社 | 繊維およびその製造方法 |
CN103214729A (zh) * | 2012-01-23 | 2013-07-24 | 住友化学株式会社 | 由聚丙烯树脂组合物构成的成形体 |
JP2013173924A (ja) * | 2012-01-23 | 2013-09-05 | Sumitomo Chemical Co Ltd | ポリプロピレン樹脂組成物およびそれを含む成形体 |
JP2013256671A (ja) * | 2011-11-17 | 2013-12-26 | Unitika Ltd | 半芳香族ポリアミド樹脂組成物 |
WO2014010137A1 (ja) * | 2012-07-13 | 2014-01-16 | 東洋スチレン株式会社 | 光学用スチレン系樹脂組成物、成形品および導光板 |
JP2023025808A (ja) * | 2021-08-11 | 2023-02-24 | ミュン ゴン キム | 射出成形靴底材料、それを含む靴底及びその製造方法並びに用途 |
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JP6433726B2 (ja) | 2014-08-27 | 2018-12-05 | 株式会社Adeka | 熱安定剤組成物およびこれを用いた合成樹脂組成物 |
EP3331945B1 (en) * | 2015-08-04 | 2020-10-07 | SABIC Global Technologies B.V. | Pipe for the transport of water having improved resistance to chlorinated disinfectants |
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