WO2007111059A1 - ポリエステル系樹脂組成物及び成形体 - Google Patents
ポリエステル系樹脂組成物及び成形体 Download PDFInfo
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- WO2007111059A1 WO2007111059A1 PCT/JP2007/053137 JP2007053137W WO2007111059A1 WO 2007111059 A1 WO2007111059 A1 WO 2007111059A1 JP 2007053137 W JP2007053137 W JP 2007053137W WO 2007111059 A1 WO2007111059 A1 WO 2007111059A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/126—Copolymers block
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention relates to a polyester-based resin composition excellent in properties such as heat cycle resistance and hydrolysis resistance, and a molded product thereof.
- Polyester block copolymers made from aromatic polyesters and latatones are excellent in rubber elasticity and weather resistance.
- a catalyst titanium compound, etc.
- crystalline aromatic A method of reacting aromatic polyesters with ratatones Japanese Patent Publication No. 48-4116 (Patent Document 1)
- Patent Document 2 Japanese Patent No. 49037
- Such a polyester block copolymer has insufficient hydrolysis resistance, and characteristics such as melt viscosity, tensile strength, and tensile elongation are significantly lowered when exposed to high humidity for a long time.
- Patent Document 3 discloses a polyester block copolymer, a compound having two or more functional groups capable of reacting with a polyester terminal (bisphenol A-glycidyl ether, polycarbodiimide). Polyester elastomer composition), and a stabilizer having a tertiary amine skeleton, wherein the weight loss at 150 ° C for 2 hours is 0.4% or less, 250 ° C, Disclosed are compositions having a gely degree of 50% or less at 4 hours. Japanese Patent Application Laid-Open No.
- Patent Document 4 describes a thermoplastic polyester in which a bifunctional or higher-functional epoxy compound is mixed in an amount of 0.01 to: LO part by weight with respect to 100 parts by weight of a polyester block copolymer.
- a flexible resin boot made of an elastomer is disclosed.
- JP-A-50-160362 discloses that a thermoplastic block copolymer polyester composed of an aromatic crystalline polyester segment and a polylatathone segment has at least two carpositimide groups per molecule.
- thermoplastic block copolymer polyester composition comprising a glass.
- Patent Document 6 a polyester-type block copolymer obtained by reacting a crystalline aromatic polyester with latatones is mixed with an epoxy compound having one or more functional groups and a heat-stable compound.
- a polyester type block copolymer composition containing an agent is disclosed.
- Patent Document 7 100 parts by weight of a polyester-polyester block copolymer having a crystalline aromatic polyester as a hard segment and polylatatone as a soft segment, (a) one or more functional groups
- Patent Document 1 Japanese Patent Publication No. 48-4116
- Patent Document 2 Japanese Patent Publication No. 52-49037
- Patent Document 3 Japanese Patent No. 3693152 (Claim 1)
- Patent Document 4 Japanese Patent Laid-Open No. 11 153226 (Claim 1)
- Patent Document 5 Japanese Patent Laid-Open No. 50-160362 (Claims)
- Patent Document 6 Japanese Patent Laid-Open No. 59-152951
- Patent Document 7 Japanese Patent Laid-Open No. 4-264156
- an object of the present invention is to provide a polyester-based resin composition and a molded product thereof that can suppress the melting point of the resin from being lowered even by repeated heating and melting, and are excellent in heat cycle resistance. There is.
- Another object of the present invention is to provide a polyester-based resin composition and a molded product thereof that can achieve both heat cycle resistance and hydrolysis resistance.
- Still another object of the present invention is to be used for applications such as being exposed to a high humidity atmosphere for a long time.
- Another object of the present invention is to provide a polyester-based rosin composition that is resistant to deterioration and has excellent recyclability, and a molded product thereof.
- the present inventor conducted a reaction of crystalline aromatic polyester (al) and latatones (a2) in the presence of acidic phosphate ester and tin compound.
- the polyester block copolymer (A) obtained in combination with the polyfunctional epoxy compound (B) and Z or the polycarpoimide compound (C) is combined, the melting point decreases even after repeated heating and melting. It was found that the heat cycle resistance can be suppressed and heat cycle resistance can be improved.
- the polyester-based resin composition of the present invention comprises a polyester block copolymer (A), at least one selected from a polyfunctional epoxy compound (B) and a polycarposimide compound (C).
- a polyester-based resin composition comprising the polyester block copolymer (A), a crystalline aromatic polyester (al) in the presence of an acidic phosphate ester and a tin compound, and ratatones.
- the polyester block copolymer (A) has a crystalline aromatic polyester (al), latatones (a2), and a hydroxyl group in the presence of an acidic phosphate ester and a tin compound.
- the acidic phosphate ester may be a mono- or dialkyl phosphate
- the tin compound may be at least one selected from tin halide, tin carboxylate and alkyltin oxide. ,.
- the ratio of the polyfunctional epoxy compound (B) is about 0.05 to 5 parts by weight with respect to 100 parts by weight of the polyester block copolymer (A).
- the proportion of the polycalcoid compound (C) may be 0.05 to 5 parts by weight.
- the proportion of the compound (a3) may be about 0.0005 to 2 parts by weight with respect to 100 parts by weight of the total amount of the crystalline aromatic polyester (al) and the latatones (a2).
- the ratio of acidic phosphoric acid ester may be 0.0001 to 0.03 parts by weight with respect to 100 parts by weight of the total amount of crystalline aromatic polyester (al) and latatones (a2).
- the ratio of the product may be about 1 to 10 parts by weight.
- the polyfunctional epoxy compound (B) may be at least one selected from the group of alicyclic epoxy compound and glycidyl ester type epoxy compound force.
- the compound which has a structural unit represented by a following formula may be sufficient.
- R represents a divalent hydrocarbon group which may have a substituent, and m represents an integer of 2 or more.
- a crystalline aromatic polyester (al) is reacted with latatones (a2) in the presence of an acidic phosphate ester and a tin compound to form a polyester block copolymer (A),
- This polyester block copolymer (A) can be mixed with at least one selected from the group consisting of a polyfunctional epoxy compound (B) and a polycarpoimide compound (C).
- the present invention includes a polyester-based resin composition obtained by such a method.
- the present invention also includes a molded body (such as a blow molded body) formed from the above-mentioned rosin composition.
- the resin composition of the present invention is a blow molding in which recycled resin is used. Suitable for molding process.
- the greave composition is useful as a molding material for boots for automobiles, particularly in applications where water resistance (hydrolysis resistance) is required.
- the polyester-based resin composition of the present invention comprises a specific polyester block copolymer (A), a polyfunctional epoxy compound (B), and a Z or polycarbodiimide compound (C). ing.
- the polyester block copolymer (A) is a block copolymer obtained by reacting the crystalline aromatic polyester (al) with the ratatanes (a2) in the presence of at least the acidic phosphate ester (a4).
- Such a polyester block copolymer (A) is composed of a block composed of a crystalline aromatic polyester (al) (node segment or rigid polyester block) and a ratatone (a2) as monomer components. It is composed at least of an aliphatic polyester block (soft segment or soft polyester block).
- Such a polyester block copolymer is generally sometimes referred to as a polyester elastomer.
- the above reaction may be performed using the acidic phosphate ester (a4) alone, but is usually performed in the presence of the acidic phosphate ester (a4) and the tin compound (a5).
- the polyester block copolymer (A) is a combination of the crystalline aromatic polyester (al) and the latatones (a2), and further includes polycarboxylic acids, polyols, and ester-forming derivatives thereof. It may be a block copolymer obtained by reaction with at least one selected compound (polyfunctional compound) (a3).
- Examples of the crystalline aromatic polyester constituting the hard polyester block include a dicarboxylic acid component essentially containing an aromatic dicarboxylic acid and a diol component (aliphatic diol, aromatic diol, and Z or alicyclic diol). Homopolyester or copolyester obtained by polycondensation with In addition, the crystalline aromatic polyester is added to the aromatic dicarboxylic acid, and if necessary, other monomer components such as other dicarboxylic acids (aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, etc.), oxycarbo- hydrate. Acids, ratatones and the like may be used in combination.
- the crystalline aromatic polyester may have a hydroxyl group at the molecular end.
- the aromatic dicarboxylic acid includes, for example, terephthalic acid, isophthalic acid, phthalic acid; alkyl-substituted phthalic acid such as methyl terephthalic acid; 4,4'-dipheninoresidue diphenyl dicarboxylic acid such as 4,4'-dipheninoresidue; 4,4'-diphenoxyalkane dicarboxylic acid such as diphenoxyethane dicarboxylic acid; diphenyl ether 4,4'-dicarboxylic acid Diphenyl ether dicarboxylic acid such as diphenylmethane dicarboxylic acid, etc.
- Alkane dicarboxylic acid such as diphenyl ketone dicarboxylic acid, aromatic dicarboxylic acid having about 8 to 20 carbon atoms (preferably 8 to 16), etc. Is mentioned.
- Aromatic dicarboxylic acids include derivatives capable of forming esters, such as C alkyl esters such as dimethyl esters.
- acid halides such as stealth, acid anhydrides and acid chlorides.
- aromatic dicarboxylic acids can be used alone or in combination of two or more.
- terephthalic acid is often used from the standpoint of crystallinity.
- an aromatic dicarboxylic acid and another dicarboxylic acid may be used in combination.
- examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexadecanedicarboxylic acid, and dimer acid.
- examples thereof include aliphatic dicarboxylic acids having about 2 to 40 carbon atoms (preferably 2 to 20 carbon atoms), such as 1,4-cyclohexanedicarboxylic acid and hexahydrophthalic acid.
- dicarboxylic acids having about 8 to 12 carbon atoms such as hexahydroisophthalic acid, hexahydroterephthalic acid, and hymic acid.
- dicarboxylic acids are derivatives capable of forming an ester such as C alkyl esters such as dimethyl ester, acid anhydrides, and acid chlorides.
- Any acid halide may be used. These other carboxylic acids can be used alone or in combination of two or more.
- examples of the aliphatic diol include ethylene glycol, propylene glycol, trimethylene glycol, 1,4 butanediol, 1,3 butanediol, 1,2 butanediol, and 1,5 pentanediol. , 3-methyl-1, 5 And aliphatic C diols such as (poly) C alkylene glycols such as tantalum diol, neopentyl glycol, 1,6 hexane diol, 1,9-nonane diol, polymethylene glycol, diethylene glycol, dipropylene glycol and the like. This
- aliphatic diols can be used alone or in combination of two or more.
- aromatic diol aromatic C diol such as resorcinol
- Bisphenols such as droquinone, naphthalenediol, 2,2 bis (4-hydroxyphenol) propane, bisphenol A, F, AD, etc., C alkyleneoxy of bisphenols
- the alicyclic diol includes an alicyclic C diol, for example
- Examples include hydrogenated bisphenols such as 1,4 cyclohexanediol, 1,4 cyclohexanedimethanol, 2,2 bis (4-hydroxyethoxycyclohexyl) propane, and C alkylene oxide adducts of these diols. Is mentioned.
- the diol components may be used alone or in combination of two or more.
- at least aliphatic diols which are often used at least, may be used in combination with aromatic diols and Z or alicyclic diols.
- aliphatic diols aliphatic C diols such as ethylene glycol, propylene glycol, 1,4 butanediol, and 1,3 butanediol are preferable! /.
- oxycarboxylic acid examples include aliphatic C oxycarboxylic acids such as glycolic acid, lactic acid, oxypropionic acid, oxybutyric acid, glyceric acid, and tartronic acid;
- aromatic oxycarboxylic acids such as benzoic acid and oxynaphthoic acid. These oxycarboxylic acids can be used alone or in combination of two or more.
- ratatones examples include propiolatatanes (/ 3 propiolatatanes, etc.), petit-mouthed ratatanes, valerolatatanes ( ⁇ -valerolatatanes, methylation ( ⁇ -valerolatatanes), etc.), cap-mouthed ratatanes ( ⁇ -one-protalataton, 2-methylone) C-latatones such as ⁇ -force prolatatones, 4-methyl- ⁇ -force prolatatanes, methylated force prolatatones such as 4, 4 'dimethyl- ⁇ one-strength prolatatanes (such as Methylou ⁇ ⁇ -force prolatatanes). These ratatons Can be used alone or in combination of two or more.
- copolyester in addition to the aromatic dicarboxylic acid and the aliphatic diol, a poly C alkylene glycol having an oxyalkylene unit having a repeating number of about 2 to 4 [J.
- Glycols containing poly (oxy-C alkylene) units such as tylene glycol
- the alicyclic diol e.g., alicyclic C diiodine such as cyclohexanedimethanol
- the aromatic diol aliphatic dicarboxylic acid (aliphatic dicarboxylic acid having about 6 to 12 carbon atoms such as adipic acid, pimelic acid, sebacic acid, etc.), the alicyclic dicarboxylic acid Often use!
- Examples of crystalline aromatic polyesters include polyalkylene acrylates (poly C alkylene acrylates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc.) and copolymer components (such as isophthalic acid).
- polyalkylene acrylates poly C alkylene acrylates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc.
- copolymer components such as isophthalic acid
- the crystalline aromatic polyester is crystalline, from the viewpoint of heat resistance or cost of raw materials, alkylene ⁇ Li rate units (e.g., Buchirentere phthalate units and ethylene terephthalate units) and 60 mol 0/0 or more (e.g., 60 to: LO 0 mole 0/0, preferably 70 to: L 00 about mole 0/0) to contain is preferred.
- alkylene ⁇ Li rate units e.g., Buchirentere phthalate units and ethylene terephthalate units
- 60 mol 0/0 or more e.g., 60 to: LO 0 mole 0/0, preferably 70 to: L 00 about mole 0/0
- the crystalline aromatic polyester constituting the hard polyester block preferably has a high degree of polymerization.
- the melting point of the crystalline aromatic polyester constituting the hard polyester block is 160 ° C or higher (for example, about 160 to 250 ° C), preferably 180 to 230 ° C, more preferably about 190 to 220 ° C. It is.
- the number average molecular weight of the crystalline aromatic polyester is 5,000 or more (for example, 5,000 to 1,000,000), and preferably ⁇ is 10,000 to 500,000. Further preferred ⁇ is about 15,000 to 30,000.
- the soft polyester block can be composed of an aliphatic polyester (homopolyester or copolyester) obtained by ring-opening polymerization of rataton.
- a aliphatic polyester homopolyester or copolyester
- the ratatones include the ratatones exemplified in the section of the hard polyester block (for example, C ratatones).
- ⁇ -force prolatatone For ring-opening polymerization of Rataton, a conventional initiator (a bifunctional or trifunctional initiator such as You can use active hydrogen compounds such as alcohol.
- the aliphatic polyester constituting the soft polyester block includes a poly-C alkylene alkylene having an oxyalkylene unit having about 2 to 4 repetitions.
- aliphatic dicarboxylic acids such as adipic acid, pimelic acid, sebacic acid, etc.
- oxystruconic acid such as oxycarboxylic acid exemplified in the above-mentioned hard polyester block
- Preferable aliphatic polyesters include, for example, Lataton homopolymers or copolymers using at least one selected from the above-mentioned Lataton's strength, particularly poly C-latatones such as poly- ⁇ -force prolatatone.
- the strain hardening property of the obtained resin composition can be further improved, and the thickness of the molded product can be made uniform even when molded (such as blow molding).
- the compound (a3) include dicarboxylic acids, diols, and ester-forming derivatives thereof exemplified in the hard polyester block section (ester-forming derivatives such as C alkyl esters, acid anhydrides, acid halides, etc. ) Etc., but usually force
- a compound (polycarboxylic acid and polyol (including oxypolycarboxylic acid, polyhydroxycarboxylic acid, etc.)) in which the total of lpoxyl group and hydroxyl group is 3 or more (for example, 3 to 5) in one molecule or These ester-forming derivatives are used.
- polycarboxylic acid examples include aliphatic polycarboxylic acids (aliphatic C tri or tetracarboxylic acids such as butanetetracarboxylic acid; glyceric acid, tartronic acid, malic acid, tartaric acid,
- Aromatic polycarboxylic acids for example, aromatic C such as trimesic acid, trimellitic acid, 1, 2, 3 benzenetriforce rubonic acid, pyromellitic acid, 1, 4, 5, 8 naphthalenetetracarboxylic acid
- Tri or tetracarboxylic acid 4 Hydroxyisophthalic acid, 3-hydroxyisophthalic acid, etc. Aromatic coxydi to tetracarboxylic acid).
- polyol examples include aliphatic polyols (for example, aliphatic C tri or glycerin, trimethylol ethane, trimethylol propane (TMP), pentaerythritol, etc.
- aliphatic polyols for example, aliphatic C tri or glycerin, trimethylol ethane, trimethylol propane (TMP), pentaerythritol, etc.
- Aliphatic c di such as dimethylolpropionic acid and dimethylolbutanoic acid
- alicyclic polyol alicyclic C tri or tetraol such as trihydroxycyclohexane
- aromatic polyol 1, 3, 5-trihydroxyben
- Aromatic C Tri or Tetraol such as Zen; 2, 3-Dihydroxybenzoic acid, 2, 4—
- Aromatic C dihydroxycals such as dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, protocatechuic acid, 2,4-dihydroxyphenol acetic acid
- These compounds (a3) may be used alone or in combination of two or more.
- multifunctional compounds (a3) aliphatic compounds (aliphatic polycarboxylic acids, aliphatic polyols or ester-forming derivatives thereof), aromatic compounds (aromatic polycarboxylic acids, aromatic polyols or esters thereof).
- aromatic compounds aromatic polycarboxylic acids, aromatic polyols or esters thereof.
- an aliphatic polycarboxylic acid or an ester-forming derivative thereof is preferable.
- the proportion of the polyfunctional compound (a3) is 0.0005 to 2 parts by weight with respect to the total amount of crystalline aromatic polyester (al) and latatones (a2) of 100 parts by weight, preferably ⁇
- the amount is about 1 part by weight, more preferably about 0.001 to 0.5 part by weight (for example, about 0.001 to 0.05 part by weight). If the proportion of the compound (a3) is too large, the transesterification reaction easily occurs, the melting point tends to decrease, and the effect of improving the heat resistance may be insufficient, or gelation may occur.
- the acidic phosphoric acid ester (a4) is orthophosphoric acid and Z or polyorthophosphoric acid (di-hexahexene) which should have at least one free hydroxyl group showing acidity bonded to a phosphorus atom in the molecule.
- Forces that include esters of alcohols (such as orthophosphoric acid) and alcohols (such as monools and Z or polyols) Orthophosphoric acid esters are usually used in many cases.
- the acidic phosphate ester may be a monoester or a polyester such as a diester or triester.
- acidic phosphate ester contains multiple ortho You may have an acid unit.
- monools include C aliphatic monools such as methanol, ethanol, t-butanol, nonanol, decanol, stearyl alcohol;
- C alicyclic monools such as clohexanol; phenol, benzyl alcohol, etc.
- c which c includes aromatic monools.
- polyol ethylene glycol
- C aliphatic polyols such as mononole, propylene glycolenole, glycerin, trimethylone propane, pentaerythritol, etc .
- C alicyclic polyols such as cyclohexanedimethanol
- C aromatic polyols such as hydroquinone.
- 6-14 may be diol or tetraol.
- the alcohols may be used alone or in combination of two or more to form orthophosphoric acid and an ester.
- acidic phosphate esters include monoalkyl phosphates such as methyl acid phosphate, butyl acid phosphate, monobutyl phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, and monoisodecyl phosphate.
- Sulfate mono C alkyl phosphate, etc.
- dibutyl phosphate bis (2-
- Dialkyl phosphates such as tilhexyl phosphate
- Mono- or di-phenol phosphate such as mono- or di-phenyl phosphate
- Ananolene bisphosphate such as ethylene bisphosphate (C
- C such as phenol-range phosphate, bi-range phosphate, etc.
- the acidic phosphate ester can be used alone or in combination of two or more.
- acidic phosphate esters mono or dialkyl phosphates (for example, mono C
- the ratio of the acidic phosphoric acid ester is 0.0001 to 0.05 parts by weight, preferably ⁇ 0.000 to 100 parts by weight of the total amount of the crystalline aromatic polyester (al) and the latatones (a2). ⁇ 0.03 parts by weight (for example, 0.0002 to 0.02 parts by weight), more preferably ⁇ 0.0005 to 0.01 parts by weight Degree. If the proportion of acidic phosphate is too small, the effect of inhibiting transesterification is insufficient, and the heat cycle resistance may not be greatly improved. Further, if the proportion of the acidic phosphate ester is too large, the hydrolysis resistance may be lowered, and the effect of compounding the epoxy compound or the polycarboimide compound may be lowered.
- Tin compounds include stannous halides (stannous fluoride, stannous chloride, stannous bromide, stannous iodide, etc.), tin salts of carboxylic acids [tin acetate, tin tetraacetate, 2-Carboxylic acid or partial ester (such as C alkyl ester) such as tin 2-ethylhexanoate, tin dioctanate, tin stearate, tin laurate, dibutyl tin laurate
- alkyl tin oxide (mono- or di-C such as dibutyltin oxide)
- the tin compounds can be used alone or in combination of two or more. As long as the tin compound has at least one tin atom in the molecule, it may have two or more. In the reaction between the crystalline aromatic polyester and the ratatones, the tin compound acts as a catalyst.
- tin compounds tin halide, tin carboxylate (C carboxylic acid or its
- Partial esters such as tin salts of C alkyl esters), alkyl tin oxides (mono
- Is 0.1 to 15 parts by weight for example, 0.5 to 10 parts by weight), preferably 1 to 100 parts by weight based on the total amount of crystalline aromatic polyester (al) and latatones (a2).
- the amount is about 10 parts by weight, more preferably about 1.5 to 7 parts by weight (for example, 2 to 5 parts by weight).
- the ratio of the tin compound (a5) is, for example, 1 to 20 parts by weight, preferably 1.5 to 15 parts by weight, more preferably 1 part by weight of the acidic phosphate ester (a4). 2 to: may be about L0 parts by weight. If the proportion of the tin compound is too small, the polymerization rate may be slowed and the reaction efficiency may be lowered. If the proportion is too large, the hydrolysis resistance is lowered, and the epoxy compound or polycarboimide compound is reduced. There is a possibility that the effect of blending is significantly suppressed.
- each component Prior to kneading, each component is preliminarily formed into a powder form with a freeze pulverizer or the like, or mixed with a tumbler, V-type blender, Henschel mixer, Nauta mixer, ribbon mixer, mechanochemical device, extrusion Premixing may also be performed with a mixer, a ball mill, or the like.
- the reaction temperature may be, for example, about 100 to 250 ° C, preferably 120 to 230 ° C, more preferably about 130 to 210 ° C.
- the reaction may be carried out in an atmosphere or flow of an inert gas (helium gas, nitrogen gas, argon gas, etc.) that may be carried out in air.
- the reaction may be carried out at atmospheric pressure or under pressure or reduced pressure as necessary.
- a conventional catalyst used for ring-opening polymerization of latatones (a catalyst other than the tin compound such as an aluminum catalyst or a titanium catalyst) and Z or an initiator (polyol) are used.
- a catalyst other than the tin compound such as an aluminum catalyst or a titanium catalyst
- Z or an initiator polyol
- the polyester block copolymer (A) may have a urethane bond, an amide bond or the like in addition to the ester bond.
- the polyester block copolymer (A) has a hydroxyl group at the molecular end.
- the polyfunctional epoxy compound (B) is not particularly limited as long as it has two or more epoxy groups in one molecule, and may be a monomer type epoxy compound or an oligomer or polymer type epoxy. It can be a compound (such as epoxy resin).
- Examples of such polyfunctional epoxy compounds include glycidyl ether type epoxy compounds [polyhydroxy compounds (bisphenols, polyhydric phenols, alicyclic polyhydric alcohols, aliphatic polyhydric alcohols].
- Glycidyl ethers e.g., (poly) C alkylene glycol diglycidyl such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, etc.
- epicchlorohydrin with Ethers
- resorcin hydroquinone, etc.
- Diglycidyl ethers of divalent phenols cyclohexanediol, cyclohexanedi Diglycidyl ether of alicyclic polyhydric alcohols such as methanol and hydrogenated bisphenols; Bisphenols such as bisphenols (4,4'-dihydroxybiphenol, bisphenol A) Etc.) or its C alkylene oxide adduct
- Diglycidyl ether novolac epoxy resin (phenol novolac type or cresol novolac epoxy resin, etc.), glycidyl ester type epoxy compound, alicyclic epoxy compound (or cycloaliphatic epoxy compound) Fats), heterocyclic epoxy resins (triglycidyl isocyanurate (TGIC), hydantoin type epoxy resins), glycidyl amine type epoxy compounds [reaction products of amines and epichlorohydrin, such as , N-glycidyl aromatic amine ⁇ tetraglycidyl diaminodiphenylmethane (TGDDM), triglycidylaminophenol (TGPAP, TGMAP, etc.), diglycidyl dilin (DGA), etc., N glycidyl alicyclic amine (tetra Glycidyl bisaminocyclohexane etc.) etc.].
- TGIC triglycidyl isocyanurate
- These polyfunctional epoxy compounds can be used alone or in combination of two or more.
- these epoxy compounds alicyclic epoxy compounds, glycidyl ester type epoxy compounds, and the like are preferred from the viewpoint of compounding and heat history of the resin accompanying Z or molding.
- the alicyclic epoxy compound has an epoxy cycloalkane (eg, 1,2-epoxy C cycloalkane) skeleton such as 1,2 epoxycyclohexane, for example.
- an epoxy cycloalkane eg, 1,2-epoxy C cycloalkane
- 1,2 epoxycyclohexane 1,2 epoxycyclohexane
- Such alicyclic epoxy compounds include compounds in which a plurality of epoxy cycloalkane skeletons are linked by an ester bond [for example, 3, 4-epoxycyclohexylmethyl-3 ′, 4 ′ epoxycyclohexane.
- An alcohol having an epoxycycloalkane skeleton such as carboxylate (epoxycycloalkanol such as 1,2 epoxy-4 hydroxycyclohexane; epoxycycloalkyl C such as 1,2 epoxy-4-hydroxymethylcyclohexane) or the like
- Tone adducts eg, latones such as epsilon prolataton or multimers of latatones (such as di- to tetramers)
- carboxylic acids having an epoxycycloalkane skeleton (1,2-epoxy 4 carboxycyclo Epoxycycloalkanecarboxylic acids such as xane; 1, 2 Epoxy 4 Esters with epoxy cycloalkyl such as carboxymethylcyclohexane C _ Alkane monolith rubonic acid, etc .
- Alicyclic diepoxy adipates bis
- Dicarboxylic acids such as (3,4-epoxycyclohexyl) adipate) (aliphatic dicarboxylic acids such as adipic acid, aromatic dicarboxylic acids such as terephthalic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid) or Rataton adducts (for example, diesters of latones such as ⁇ -force prolatatone or multimers of latatones (such as di to tetramers) and alcohols having the epoxycycloalkane skeleton), and a plurality of epoxy cyclo Compounds having an alkane skeleton linked by a heterocyclic ring (for example, a compound in which two epoxycycloalkanes such as alicyclic gepoxyacetal are linked by a cyclic acetal), epoxycycloalkanes having an epoxyalkyl group (for example, , Epoxies such as bull cyclohexened
- the raw material having no epoxy group which may be obtained by using a compound having an epoxy group as a raw material (for example, alcohol and ⁇ or carboxylic acid) is subjected to a reaction such as esterification, acetal, etc. It may be obtained by epoxidizing the product.
- a compound having an epoxy group as a raw material (for example, alcohol and ⁇ or carboxylic acid) is subjected to a reaction such as esterification, acetal, etc. It may be obtained by epoxidizing the product.
- an alcohol having an epoxycycloalkane skeleton such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate or a rataton adduct thereof (for example, a rataton or rataton such as ⁇ -strength prolataton)
- a rataton or rataton such as ⁇ -strength prolataton
- cycloalkene carboxylic acids such as tetrahydrophthalic anhydride
- cycloalkenyl alkanols such as tetrahydral benzyl alcohol.
- the carbon-carbon unsaturated bond can be obtained by epoxidizing the ester or the rataton-containing case with, for example, Daicel Chemical Industries, Ltd.
- Examples of the glycidyl ester-type epoxy compound include polyglycidyl esters of aromatic polycarboxylic acids; polyglycidyl esters of alicyclic polycarboxylic acids; Polyglycidyl ester of aromatic polycarboxylic acid and ester of z or alicyclic polycarboxylic acid and polyol (ester type polycarboxylic acid having at least two terminal carboxyl groups); dimer acid diglycidyl ester or modified product thereof Is mentioned.
- Polyglycidyl esters of aromatic polycarboxylic acids include aromatic C such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, trimellitic acid, and pyromellitic acid.
- aromatic C such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, trimellitic acid, and pyromellitic acid.
- Polyglycidyl esters of di- or tetracarboxylic acids include aromatic C such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, trimellitic acid, and pyromellitic acid.
- diglycidyl esters of dicarboxylic acids such as diglycidyl phthalate and diglycidyl terephthalate; di- or triglycidyl esters of tricarboxylic acids such as trimellitic acid di- or triglycidyl ester).
- Polyglycidyl esters of alicyclic polycarboxylic acids include polyglycidyl esters of alicyclic C di to tetracarboxylic acids such as tetrahydrophthalic acid, methyltetrahydrophthalic acid, and dimethylhexahydrophthalic acid.
- Steal eg polyglycidyl esters of alicyclic C di- or tricarboxylic acids such as methyltetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, etc.
- the dimer acid diglycidyl ester and its modified product are available from Japan Epoxy Resins Co., Ltd. under the trade names “Epicoat 871”, “Epicoat 87 2”, and the like.
- the ester-type polycarboxylic acid includes the aromatic polycarboxylic acid exemplified above and Z or alicyclic polycarboxylic acid.
- Acids and polyols aliphatic polyols such as mono- to tetra-c alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol; glycerin, trimethylolethane, trimethylo
- C Alkanetriols such as propane
- C Al forces such as pentaerythritol
- ester type polycarboxylic acid the number of repeating ester units is, for example, 1 to 10, preferably about 1 to 5.
- Z has an alkyl group such as a methyl group (C alkyl group etc.) as a substituent.
- the number of substituents in ring Z is not particularly limited, and may be, for example, about 14, preferably about 1 or 2. Further, n indicating the number of ester units is preferably an integer of 0 3, more preferably 1 or 2.
- the compound of I) is diglycidyl phthalate ester.
- the structure of the polycarbopositimide compound (C) is not particularly limited as long as it has two or more calpositimide groups in one molecule, and a monomeric polycarbopositimide compound (for example, Aromatic polycarpoimide compounds, alicyclic polycarpoimide compounds, etc.) may be used, but usually they are often oligomers (dimers or higher oligomers) or polymer-type polycarpoimide compounds. Polycarposimide compounds can be used alone or in combination of two or more.
- a monomeric polycarbopositimide compound for example, Aromatic polycarpoimide compounds, alicyclic polycarpoimide compounds, etc.
- Polycarposimide compounds can be used alone or in combination of two or more.
- Examples of the oligomer or polymer-type polycarposimide compound include compounds having a structural unit (repeating unit) represented by the following formula (II).
- R represents a divalent hydrocarbon group which may have a substituent, and m represents an integer of 2 or more.
- the divalent group R is, for example, an aliphatic hydrocarbon group [for example, an alkyl group] Xylene group or alkylidene group (C alkylene group such as methylene group, ethylene group, tetramethylene group, hexamethylene group etc. (eg C alkylene group etc.)), alicyclic carbon
- Hydrogen group e.g., cycloalkylene group (e.g., C
- C cycloalkenylene groups such as cyclohexenylene groups
- alkylcycloalkanes alkylcycloalkanes
- a divalent group corresponding to a methylcyclohexane, etc. eg, a C alkylene-C cycloalkylene group such as a methylene-cyclohexylene group, preferably a C
- diC cycloalkyl such as dicyclohexylmethane 4, 4 'diyl group
- C alkane diyl group preferably di C cycloalkyl C alkane diyl
- aromatic hydrocarbon groups [arylene groups such as C arylene groups such as phenylene and naphthylene groups (preferably C arylene groups etc.)], aromatic aliphatic carbons, etc.
- Hydrogenated groups for example, divalent groups corresponding to diarylalkanes (diphenylmethane-4,4, diyl groups, etc., di C aryl C alkane diyl groups, preferably diC
- di-C alkyl C-arylene diyl group such as ⁇ , ⁇ , monoxylylene group
- the group R may have a substituent (for example, an alkyl group such as a methyl group; an aryl group such as a phenyl group).
- a substituent for example, an alkyl group such as a methyl group; an aryl group such as a phenyl group.
- the groups R may be the same or different for each repeating unit.
- the polycarbopositimide compound may be a homopolymer or a copolymer made from a different monomer (for example, a polyisocyanate compound). .
- the number m of repeating units may be 2 or more (for example, about 2 to about L00), for example, 3 to 50, preferably 4 to 40, and more preferably 5 to 30. It may be about (for example, 8-20).
- the structure of the polycarbopositimides may be a chain (linear or branched), a network, or the like, and may be a chain.
- Representative polycarposimides include, for example, aliphatic polycarposimides, alicyclic polycarposimides, aromatic polycarposimides and the like. Aliphatic poly force
- Examples of rubodiimides include polyalkylene carbodiimides such as polyhexamethylene carbodiimide and poly (3-methylhexamethylene carbodiimide) (for example, poly (C
- Examples of the alicyclic polycarbopositimides include polydicycloalkylalkanecarbodiimides such as poly (4,4'-dicyclohexylmethancarbodiimide) (for example, poly (diCcycloalkyl-Calkanecarbodiimide)) ) And the like.
- the aromatic polycarbopositimides include, for example, polyarylene carbopositimides [for example, poly m-phenylene-carbodiimide, poly p-phenylene-carbodiimide, polytolylene carbodiimide, poly (diisopropylphenol-carbodiimide) , Poly (methyl diisopropylpropylene-carbodiimide), poly (triisopropylphenol-carbodiimide) and other poly (C arylenecarbodiimide)], polydiarylalkanecarbodiimide [Example, polyarylene carbopositimides [for example, poly m-phenylene-carbodiimide, poly p-phenylene-carbodiimide, polytolylene carbodiimide, poly (diisopropylphenol-carbodiimide) , Poly (methyl diisopropylpropylene-carbodiimide), poly (triisopropylphenol-carbodiimide
- Such a polycarposimide compound can also be synthesized by a conventional method using an organic polyisocyanate (such as an organic diisocyanate) or the like, which may be a commercially available product.
- the polycarbodiimide compound can be obtained, for example, by reacting (decarboxylating) an organic polyisocyanate (particularly, an organic diisocyanate) or a multimer thereof (such as a dimer or a trimer). The reaction of the organic polyisocyanate may be carried out in the absence of a catalyst.
- a carbodiimide-forming catalyst for example, phospholine, phosphoridine, phospholine oxide (1-methyl-1-oxophospholine, 1-ethyl-3-methyl-3phosphorin) 1-oxide, 3-methyl-1, 1-phenol, 2-phosphorine, 1-oxide, etc.), phosphorous catalysts such as phospholine sulfide, metal carbonyl, etc.
- a carbodiimide-forming catalyst for example, phospholine, phosphoridine, phospholine oxide (1-methyl-1-oxophospholine, 1-ethyl-3-methyl-3phosphorin) 1-oxide, 3-methyl-1, 1-phenol, 2-phosphorine, 1-oxide, etc.
- phosphorous catalysts such as phospholine sulfide, metal carbonyl, etc.
- an organic monoisocyanate may be used in combination as necessary.
- organic polyisocyanate examples include compounds corresponding to the polycarposimide compounds, such as aromatic polyisocyanates [for example, C
- C 1-4 arene diisocyanate (2,4,5 tris) having a substituent such as 1-4 kill group
- Isopropyl phenol 1,3 diisocyanate, 1,3,5-triisopropyl phenol — 2,4 diisocyanate, 1,3 diisopropyl phenol 2,4 diisocyanate, Tolylene-1,4-diisocyanate, tolylene-1,2,6-diisocyanate, etc.), and arene ring C may have substituents such as alkyl group C arene di C alkylene
- arylisocyanates eg, 4,4, -methylenebis (phenol isocyanate), etc., alkylene bis (C arylisocyanates, etc.)
- aliphatic polyisocyanates eg, 4,4, -methylenebis (phenol isocyanate), etc., alkylene bis (C arylisocyanates, etc.)
- Cyanate, etc. alicyclic polyisocyanates (hydrogenated products of the above-mentioned aromatic polyisocyanates, for example, 4,4-methylenebis (cyclohexyl isocyanate, etc.), multimers thereof (dimers (uretidione)) , Trimer (isocyanurate), etc.), etc.
- aromatic polyisocyanates for example, 4,4-methylenebis (cyclohexyl isocyanate, etc.), multimers thereof (dimers (uretidione)) , Trimer (isocyanurate), etc.
- These polyisocyanate compounds can be used alone or in combination of two or more.
- Examples of the monoisocyanate compounds include alkyl isocyanates such as methyl isocyanate; cycloalkyl isocyanates such as cyclohexyl isocyanate; phenylenoisocyanates; And arylenoisocyanates such as torinoleisocyanate. These monoisocyanate compounds can be used alone or in combination of two or more.
- the reaction of the isocyanate compound can be carried out by a conventional method. For example, see JP-B-52-16759, JP-A-6-298890, JP-A-7-165853, etc. it can.
- the proportion of the epoxy compound (B) is, for example, 0.05 to 5 parts by weight, preferably 0.03 to 3 parts by weight, more preferably 100 parts by weight of the polyester block copolymer (A). About 0.1 to 2 parts by weight. If the ratio of the epoxy compound (B) is too small, the heat resistance and Z or water resistance may be insufficient. If the ratio is too large, the ratio of the unreacted epoxy compound will increase. Workability and Z or appearance characteristics (such as the surface condition of the molded product) may be reduced.
- the proportion of the polycarposimide compound (C) is, for example, 0.05 to 5 parts by weight, preferably 0.07 to 3 parts per 100 parts by weight of the polyester block copolymer (A). Part by weight, even better Or about 0.1 to 2 parts by weight. If the proportion of the polycarpoimide compound is too small, the heat resistance and Z or water resistance may be insufficient, and even if the proportion is too large, it is difficult to obtain a remarkable addition effect. Or, the molded product tends to be colored or the surface condition of the molded product tends to be rough.
- the polyester-based resin composition of the present invention includes a polyester block copolymer (A), a polyfunctional epoxy compound (B), and Z or polycarpoimide compound (C). May have reacted.
- a resin composition is excellent in hydrolysis resistance while maintaining the elasticity and formability of the polyester block copolymer, and used for applications where it is exposed to a high humidity atmosphere for a long time. Even in this case, it is difficult to cause deterioration.
- the resin composition also has excellent heat resistance. In particular, even if heat history occurs in mixing (kneading, etc.) and Z or molding process, the melting point is suppressed, and high heat cycle resistance is achieved. Have. As described above, the resin composition is excellent in recyclability because degradation is suppressed and heat cycle resistance is high.
- the polyester-based resin composition of the present invention further includes various additives such as stabilizers (thermal stabilizers, antioxidants, ultraviolet absorbers, weathering (light) stabilizers, etc.), flame retardants (phosphorus).
- Inorganic fillers such as beads; organic fillers such as aramid fibers and cross-linked acrylic resin particles), release agents, lubricants, antistatic agents, colorants (such as inorganic or organic dyes) Good.
- additives can be used alone or in combination of two or more.
- the polyester-based resin composition contains at least the stabilizer (or antioxidant).
- stabilizers include Cinders such as hindered phenol compounds [for example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. Alkanetetraol tetrakis [3— (3,
- the ratio of the additive can be appropriately selected according to the type of additive and the use of the resin composition.
- the mixing of the additive is not particularly limited, and the constituents of the resin composition (polyester block copolymer (A), polyfunctional epoxy compound (B) and Z or polycarbodiimide compound (C), Alternatively, it may be added and mixed together with the mixing of the constituents that may be contained in advance in the constituents (polyester block, etc.) constituting these. Further, after mixing the constituent components, an additive may be mixed. For example, when using a stabilizer (such as a stabilizer having antioxidant and Z or photostabilizing effects), the stabilizer may be added to a polyester block copolymer or a polyester-based resin composition. You may mix
- a stabilizer such as a stabilizer having antioxidant and Z or photostabilizing effects
- the polyester-based resin composition of the present invention comprises a polyester block copolymer (A), a multifunctional epoxy compound (B), and a Z or polycarposimide compound (C), and other components as necessary. It can be produced by mixing (additive etc.). Mixing may be performed by a conventional method, for example, a mixing method (tumbler, V-type blender, Henschel mixer, Nauta mixer, ribbon mixer, mechanochemical device, extrusion mixer, etc.). Usually, the above components are often kneaded using a conventional kneading machine (for example, a single or twin screw extruder, a kneader, a calender roll, etc.).
- a conventional kneading machine for example, a single or twin screw extruder, a kneader, a calender roll, etc.
- the polyester block copolymer (A) By mixing (especially kneading), the polyester block copolymer (A) can be reacted with the polyfunctional epoxy compound (B) and Z or polycarposimide compound (C), and it is resistant to hydrolysis. Can be improved.
- each component Prior to kneading, each component may be preliminarily processed into a powder form with a freeze pulverizer or the like, or premixed with the mixer or the like. If necessary, the melted and kneaded rosin composition may be pelletized by a pelletizing means (such as a pelletizer).
- the resin composition of the present invention is excellent in properties such as elasticity and moldability, and is excellent in heat cycle resistance because it can suppress the melting point from being lowered even after repeated heating and melting.
- the resin composition is also excellent in hydrolysis resistance, and thus is useful for forming various resin moldings.
- the molded product (resin molded product) of the present invention is formed of the polyester-based resin composition.
- a molded body can be produced by molding the resin composition by a conventional molding method, for example, extrusion molding, injection molding, blow molding, calendar molding, press molding, vacuum molding or the like.
- the resin composition is highly recyclable because it suppresses a decrease in the melting point even after repeated heating and melting, has excellent heat cycle resistance, and is excellent in hydrolysis resistance.
- it is suitable for molding force used for recycling, for example, blow molding.
- the shape of the molded body is not particularly limited, and is 0-dimensional shape (granular, pellet-like, etc.), 1-dimensional shape (strand-like, rod-like, etc.), 2-dimensional shape (plate-like, sheet-like, film, etc.) Etc.) and three-dimensional shapes (tubular, bellows tubular, curved tubular, block shaped, etc.).
- the polyester-based resin composition and molded product of the present invention are excellent in characteristics such as heat resistance (particularly heat cycle resistance) and hydrolysis resistance, and thus in recyclability.
- Parts [Boots (rack pion boots, constant velocity joint boots, etc.), bushes (ball joint bushes, etc.), MacPherson strut covers, steering door covers, door latch strikers, safety belt stopper housings, window glass swing doors, Suitable for leaf springs, jacket springs, side trim moldings, grommets, etc.], machine parts (hydraulic hoses, coil tubes, flexible couplings, conveyor belts, etc.), electrical or electronic equipment parts (gear hubs, timing belts, etc.) ing.
- the resin composition is particularly suitable for blow molding, it is useful for blow molded articles, for example, automotive blow molded articles such as automobile boots, MacPherson strut covers, and steering rod covers.
- the melting point, heat cycle resistance, tensile breaking strength, tensile breaking elongation, hydrolysis resistance, Ml value, strain hardening, and drawdown properties are as follows.
- the melting point (unit: ° C) was measured according to JIS K 7121 using a differential scanning calorimeter (DSC). The melting peak temperature was taken as the melting point.
- DSC differential scanning calorimeter
- JIS No. 2 dumbbells were hydrolyzed with a pressure tacker at 120 ° C and 100% RH for 100 hours, then the tensile elongation at break was measured according to JIS K 7121, and the elongation before hydrolyzing was 100. Expressed as%.
- polyester block copolymer (al-2) was produced.
- the obtained polyester block copolymer (al-2) had a melting point of 206 ° C.
- a polyester block copolymer (referred to as a polyester block copolymer (al-3)) was produced in the same manner as in Production Example 1 except that AP-4 and stanostat were not added.
- the resulting polyester block copolymer (al-3) had a melting point of 203 ° C.
- polyester block copolymer (al-4) A polyester block copolymer (referred to as polyester block copolymer (al-4)) was produced in the same manner as in Production Example 1, except that 0.5 part of AP-4 and 1 part of stanotate were added. The melting point of the obtained polyester block copolymer (al-4) was 207 ° C.
- polyester block copolymer (al-5)) was produced in the same manner as in Production Example 2, except that AP-4 and stanotate were not added. Poly obtained The melting point of the ester block copolymer (al-5) was 204 ° C.
- polyfunctional epoxy compounds and polycarposimide compounds used in Examples and Comparative Examples are as follows.
- the heat cycle resistance is inferior in the comparative example without using the acidic phosphate ester and the tin compound, whereas in the examples, the heat cycle resistance is 98% or more, and the heat resistance. Excellent cycle performance.
- high hydrolysis resistance was also obtained.
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- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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JP2008507393A JPWO2007111059A1 (ja) | 2006-03-24 | 2007-02-21 | ポリエステル系樹脂組成物及び成形体 |
CA002647134A CA2647134A1 (en) | 2006-03-24 | 2007-02-21 | Polyester-series resin composition and molded article |
EP07714637A EP2011827A4 (en) | 2006-03-24 | 2007-02-21 | POLYESTER RESIN COMPOSITION AND FORM BODY |
MX2008012222A MX2008012222A (es) | 2006-03-24 | 2007-02-21 | Composicion de resina de poliester y cuerpo moldeado. |
US12/224,957 US20090198020A1 (en) | 2006-03-24 | 2007-02-21 | Polyester-Series Resin Composition and Molded Article |
Applications Claiming Priority (2)
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JP2006083956 | 2006-03-24 | ||
JP2006-083956 | 2006-03-24 |
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PCT/JP2007/053137 WO2007111059A1 (ja) | 2006-03-24 | 2007-02-21 | ポリエステル系樹脂組成物及び成形体 |
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US (1) | US20090198020A1 (ja) |
EP (1) | EP2011827A4 (ja) |
JP (1) | JPWO2007111059A1 (ja) |
KR (1) | KR20090005049A (ja) |
CN (1) | CN101410454A (ja) |
CA (1) | CA2647134A1 (ja) |
MX (1) | MX2008012222A (ja) |
WO (1) | WO2007111059A1 (ja) |
Cited By (5)
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JP2011084640A (ja) * | 2009-10-15 | 2011-04-28 | Toyobo Co Ltd | 熱可塑性ポリエステルエラストマー組成物およびその製造方法 |
WO2012128161A1 (ja) * | 2011-03-18 | 2012-09-27 | 東洋紡績株式会社 | フレキシブルブーツ用ポリエステルブロック共重合体組成物 |
WO2019163613A1 (ja) * | 2018-02-23 | 2019-08-29 | 日清紡ケミカル株式会社 | 樹脂組成物、樹脂材料及び樹脂架橋体 |
WO2021187474A1 (ja) * | 2020-03-18 | 2021-09-23 | 東洋紡株式会社 | ポリエステルエラストマー樹脂組成物 |
WO2024009906A1 (ja) * | 2022-07-08 | 2024-01-11 | Dic株式会社 | コポリエステル及びその製造方法 |
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US7420020B2 (en) * | 2004-05-14 | 2008-09-02 | Fuji Xerox Co., Ltd. | Resin particles and producing method thereof, toner for developing electrostatic latent image and producing method thereof, electrostatic latent image developer as well as image forming method |
CA2902145A1 (en) * | 2013-03-25 | 2014-10-02 | Teijin Limited | Resin composition |
WO2020133338A1 (zh) * | 2018-12-29 | 2020-07-02 | 广东生益科技股份有限公司 | 一种热固性树脂组合物及包含其的预浸料、层压板和高频电路基板 |
CN109694555B (zh) * | 2018-12-29 | 2021-07-30 | 广东生益科技股份有限公司 | 一种热固性树脂组合物及包含其的预浸料、层压板和高频电路基板 |
JP7312005B2 (ja) * | 2019-04-15 | 2023-07-20 | 日清紡ケミカル株式会社 | ポリエステル系樹脂組成物 |
TW202138424A (zh) * | 2020-02-17 | 2021-10-16 | 日商東洋紡股份有限公司 | 芳香族聚酯及其製造方法 |
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JP2011084640A (ja) * | 2009-10-15 | 2011-04-28 | Toyobo Co Ltd | 熱可塑性ポリエステルエラストマー組成物およびその製造方法 |
WO2012128161A1 (ja) * | 2011-03-18 | 2012-09-27 | 東洋紡績株式会社 | フレキシブルブーツ用ポリエステルブロック共重合体組成物 |
JP5146623B2 (ja) * | 2011-03-18 | 2013-02-20 | 東洋紡株式会社 | フレキシブルブーツ用ポリエステルブロック共重合体組成物 |
WO2019163613A1 (ja) * | 2018-02-23 | 2019-08-29 | 日清紡ケミカル株式会社 | 樹脂組成物、樹脂材料及び樹脂架橋体 |
JPWO2019163613A1 (ja) * | 2018-02-23 | 2021-02-04 | 日清紡ケミカル株式会社 | 樹脂組成物、樹脂材料及び樹脂架橋体 |
WO2021187474A1 (ja) * | 2020-03-18 | 2021-09-23 | 東洋紡株式会社 | ポリエステルエラストマー樹脂組成物 |
WO2024009906A1 (ja) * | 2022-07-08 | 2024-01-11 | Dic株式会社 | コポリエステル及びその製造方法 |
Also Published As
Publication number | Publication date |
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CN101410454A (zh) | 2009-04-15 |
JPWO2007111059A1 (ja) | 2009-08-06 |
MX2008012222A (es) | 2008-10-02 |
US20090198020A1 (en) | 2009-08-06 |
EP2011827A1 (en) | 2009-01-07 |
CA2647134A1 (en) | 2007-10-04 |
EP2011827A4 (en) | 2010-12-15 |
KR20090005049A (ko) | 2009-01-12 |
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