WO2005073315A1 - ポリエステルエラストマー組成物 - Google Patents
ポリエステルエラストマー組成物 Download PDFInfo
- Publication number
- WO2005073315A1 WO2005073315A1 PCT/JP2005/001315 JP2005001315W WO2005073315A1 WO 2005073315 A1 WO2005073315 A1 WO 2005073315A1 JP 2005001315 W JP2005001315 W JP 2005001315W WO 2005073315 A1 WO2005073315 A1 WO 2005073315A1
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- WIPO (PCT)
- Prior art keywords
- polyester elastomer
- weight
- compound
- elastomer composition
- group
- Prior art date
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- 229920000728 polyester Polymers 0.000 title claims abstract description 52
- 229920001971 elastomer Polymers 0.000 title claims abstract description 45
- 239000000806 elastomer Substances 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- 239000004593 Epoxy Substances 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 7
- 230000001603 reducing effect Effects 0.000 claims abstract description 6
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229920003232 aliphatic polyester Polymers 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 4
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 abstract description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- -1 polybutylene terephthalate Polymers 0.000 description 19
- 230000007062 hydrolysis Effects 0.000 description 16
- 238000006460 hydrolysis reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 229920006000 epoxidized styrene-butadiene-styrene block copolymer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- MCWUXNVMAKIFNN-UHFFFAOYSA-N butanedioic acid;decanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCCCCCC(O)=O MCWUXNVMAKIFNN-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical group [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical group [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—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
- C08K5/1515—Three-membered rings
-
- 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
-
- 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
Definitions
- the present invention relates to a polyester elastomer composition
- a polyester elastomer composition comprising a polyester elastomer, an epoxy compound and a polycarboimide compound, and a processed product obtained from the polyester elastomer composition has hydrolysis resistance, heat resistance, and oil resistance. Excellent in resistance, impact resistance and abrasion resistance. Background art
- Polyester elastomers have been preferably used for automobile parts and the like because of their excellent heat resistance, oil resistance, impact resistance and other physical properties.
- polyester elastomers have poor hydrolysis resistance, so they are prone to thermal degradation at the time of processing, sharp reductions in strength and impact resistance, and unstable melt viscosity during molding and durability as automotive parts. It has serious drawbacks, such as a problem with its properties.
- Japanese Patent Application Laid-Open No. 58-166564 (claims, lower left column to lower right column on page 364, see Examples 1 to 5) describes the hydrolysis resistance of polyester elastomers. It is described that a monofunctional epoxy compound and a bifunctional epoxy compound are added in an amount of 0.3 to 10% by weight in order to improve the content.
- Japanese Unexamined Patent Publication No. Sho 59-152 947 (see claims, upper left column, lower left column on page 313, Examples 1 and 2) describes a monofunctional or higher functional epoxy compound and weather resistance. The addition of a stabilizer and a tertiary phosphine is described.
- polyester The best way to improve the hydrolysis resistance of polyester is to add polycarboimide, but since conventional polycarboimide also reacts with water, the concentration of carpoimide decreases due to the reaction with water. There is a drawback in that the original role of polycarboimide, which captures protonic acid generated by ester hydrolysis, cannot be sufficiently fulfilled.
- An object of the present invention is to provide a polyester elastomer composition which mainly improves hydrolysis resistance and is excellent in heat resistance, oil resistance, abrasion resistance and impact resistance. Disclosure of the invention
- the present inventor has conducted intensive studies in view of the above-described conventional technology, and as a result, has found that a specific amount of the epoxy compound (B) and a specific polycarboimide compound (A) having low reactivity with water are added to the polyester elastomer (A). It has been found that the incorporation of C) makes it possible to obtain a polyester elastomer composition having better hydrolysis resistance than before, and has completed the present invention.
- the first aspect of the present invention is that an epoxy compound having one or more epoxy groups in a molecule (B) is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polyester elastomer (A). At least two or more carbodiimide groups in the molecule, and carbon atoms on both sides of one carbodiimide group are at least one alkyl group having 1 to 4 carbon atoms or substitution having an electronic reaction rate reduction effect.
- a polyester elastomer composition comprising a polycarboimide compound having a group (C) in an amount of 0.01 to 10 parts by weight.
- a second aspect of the present invention is that the polyester elastomer (A) comprises a crystalline aromatic polyester as a hard segment and at least one selected from the group consisting of an aliphatic polyester, an aliphatic polyether and an aliphatic polycarbonate.
- Soft segment and The present invention provides the polyester elastomer composition according to the first aspect of the present invention, which is characterized in that:
- a third aspect of the present invention provides the polyester elastomer composition according to the second aspect of the present invention, wherein the aliphatic polyester constituting the soft segment comprises a polyprolactone component.
- a fourth aspect of the present invention provides the polyester elastomer composition according to the first aspect, wherein the polycarboimide compound (C) is a compound represented by the following general formula.
- R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituent having an electronic reaction rate reducing effect, and two Rs bonded to the same carbon atom are the same or different. However, they may not be hydrogen atoms at the same time, and n is an integer of 2 or more.
- the polyester elastomer (A) used in the present invention is a polyester elastomer containing, as a soft segment, an aromatic polyester as a hard segment and at least one selected from the group consisting of an aliphatic polyester, an aliphatic polyether and an aliphatic polycarbonate. It is.
- the aromatic polyester as the hard segment has a melting point of 200 to 300, preferably 210 to 28, and includes, for example, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, and the like. And mixtures thereof. Further, even when a part of the terephthalate is substituted with isophthalate within the above melting point range, a copolymer obtained by copolymerizing P-hydroxybenzoic acid, 6-hydroxy-2-oxyl-potoxynaphthalene, or the like. Polyester may be used.
- the soft segment has a melting point of 170 or less and preferably does not show a melting point.
- aliphatic polyester examples include polylactone, condensates of aliphatic dibasic acids and aliphatic glycols, condensates of various aliphatic hydroxyalkyl carboxylic acids, and condensates of these mixtures.
- Aliphatic polyesters examples include polylactone, condensates of aliphatic dibasic acids and aliphatic glycols, condensates of various aliphatic hydroxyalkyl carboxylic acids, and condensates of these mixtures.
- Polylactones include ⁇ -force prolactone, methylated ⁇ -force prolactone,] 3-propiolactone, a-butyrolactone, 6-valerolactone, and enantholactone homopolymers or copolymers of two or more of these monomers. Examples thereof include polymers, or mixtures of these homopolymers or copolymers.
- the polylactone may be obtained by ring-opening polymerization of the above monomer based on a monofunctional or polyfunctional initiator, or may be obtained by condensation polymerization of the corresponding hydroxyalkylcarboxylic acid.
- Polyaliphatic lactones and adipic acid-based polyesters are generally used as the aliphatic polyester. Polyaliphatic lactones are preferred in terms of heat resistance, durability and flexibility.
- the aliphatic polyether as the soft segment is a condensate of a polymer of a cyclic ether and a glycol, and also includes a copolymer with a thioprolactone.
- Specific examples of these include polytetramethylene glycol (polytetramethylene ether glycol), polyethylene glycol, and polypropylene glycol. Among them, polytetramethylene glycol is generally preferably used.
- Examples of the aliphatic polycarbonate as the soft segment include a polymer of a cyclic carbonate, a condensate of polyvalent phenol and glycol, and phosgene or diphenyl carbonate, and the like. Polymers are also included. Examples of the aliphatic polycarbonate include polydimethyltrimethylene carbonate, polymonomethyltrimethylene carbonate, polytrimethylene carbonate, and polyhexamethylene carbonate.
- the composition ratio of the hard segment and the soft segment of the polyester elastomer (A) used in the present invention is such that the content of the hard segment in the polyester elastomer (A) is 50 to 90% by weight, preferably 60 to 8%.
- the range is 0% by weight.
- the content of the hard segment is less than 50% by weight, heat resistance / oil resistance decreases, and when it exceeds 90% by weight, impact resistance decreases, which is not preferable.
- the total of the hard segment and the soft segment is 100% by weight, and when the aromatic polyester resin of 30% by weight or less is co-condensed in the soft segment, the melting point of the aromatic polyester resin is 200%. In the case of 0-300, this proportion is added to the hard segment.
- the molecular weight of the polyester elastomer (A) can be calculated by measuring the intrinsic viscosity or the GPC method.
- Chloroform / hexafluoroisopropanol The standard polystyrene-equivalent number average molecular weight obtained by ordinary GPC measurement using 9/1 (volume ratio) as a solvent is 40,000 to 200,000, preferably 40,000. Those having a thickness of up to 150,000 are preferable because of excellent balance between impact resistance and formability.
- the epoxy compound (B) used in the present invention is not particularly limited as long as it has one or more epoxy groups in the molecule.
- Examples of the epoxy compound (B) include bisphenol-type epoxy compounds obtained by reacting bisphenol A or bisphenol F with epichlorohydrin, novolak resins and nopolak-type epoxy resins obtained from epichlorohydrin Glycidyl esters obtained from aliphatic or aromatic carboxylic acids and epichlorohydrin, alicyclic epoxy compounds obtained from alicyclic compounds having a hydroxyl group or a carboxyl group, aliphatic or aromatic compounds having an alcoholic hydroxyl group There are glycidyl ethers obtained from compounds and epichlorohydrin, epoxidized butadene, and epoxide compounds obtained from compounds having double bonds and peroxides.
- Examples include 4-epoxycyclohexylmethanol-1,3,4-epoxycyclohexancarboxylate, epoxidized polybutadiene, and epoxidized styrene-butadiene-styrene block copolymer (epoxidized SBS).
- it is an epoxy compound having two or more epoxy groups in the molecule.
- Epoxy compound (B) acts as a hydrolysis inhibitor.
- Polycarbodiimide compound (C) The polycarboimide compound (C) used in the present invention has at least two or more carbodiimide groups in the molecule, and a methyl group or a bulkier substituent than this on the carbon on both sides of the carbodiimide group, that is, 1 carbon atom And at least one substituent having an electronic reaction rate lowering effect.
- substituent having an effect of reducing the reaction rate when an electronic carbodiimide group reacts with water include an alkoxy group such as a methoxy group and an ethoxy group, and a halogen atom such as a chloro group and a fluoro group.
- the polycarboimide compound (C) is obtained, for example, by heating and decarboxylation reaction using a diisocyanate compound as a raw material.
- polycarboimide compound (C) examples include a compound represented by the following chemical formula.
- R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituent having an electronic reaction rate reducing effect, and two Rs bonded to the same carbon atom are the same or different.
- R is preferably a methyl group
- n is an integer of 2 or more, preferably 4 or more, and may be a mixture having different degrees of condensation.
- Aromatic rings may be partially or wholly hydrogenated
- the positions of the two carbodiimide groups or the carbodiimide group and the NCO group substituted with one aromatic ring are not particularly limited, but are preferably The m-position or the p-position.
- the polycarboimide compound (C) suppressed the reaction of the carbodiimide group with water. Above, only the protonic acid generated in the system when the composition is exposed to water or when the composition is processed can be selectively captured.
- polyester elastomer composition having 4 or more carpoimide groups in the molecule and having a (number average) molecular weight of 500 or more, preferably 1000 or more are preferable in terms of hydrolysis resistance.
- the carbodiimide group content in the polycarbodiimide compound (C) is at least 3% by weight, preferably 5 to 17% by weight.
- Polyester elastomer composition is at least 3% by weight, preferably 5 to 17% by weight.
- the polyester elastomer composition of the present invention comprises a polyester elastomer
- the amount of the epoxy compound (B) or the polycarboimide compound (C) is too large, the heat resistance, oil resistance, abrasion resistance, rigidity, etc. of the processed product obtained from the polyester elastomer composition will decrease. However, it is not preferable because the effect of improving the hydrolysis resistance is small.
- the hydrolysis resistance of the polyester elastomer is suppressed by the coexistence of the epoxy compound (B) and the specific polycarboimide compound (C). Less is.
- Known means can be used to obtain the polyester elastomer composition of the present invention. For example, a predetermined amount of each component is premixed with a mixer such as a Henschel mixer, evening blender, kneader, or the like, and then kneaded with an extruder, or melt-kneaded with a heating roll or a Banbury mixer, and then pelletized or mixed. By crushing Can be obtained.
- the processed product obtained from the polyester elastomer composition of the present invention has excellent heat resistance, oil resistance, abrasion resistance, impact resistance and hydrolysis resistance.
- the polyester elastomer composition of the present invention may be used alone or in combination with other resins, or may be processed in a multilayer with other materials.
- Processed products are specifically used for parts such as hoses, tubes, belts, gears, connectors, tanks, battery parts, sockets, cord coatings, bumpers, etc., such as automobiles, large machinery, industrial machinery, and home appliances. .
- parts such as hoses, tubes, belts, gears, connectors, tanks, battery parts, sockets, cord coatings, bumpers, etc., such as automobiles, large machinery, industrial machinery, and home appliances. .
- A- 1 Block copolymer of polybutylene terephthalate and polyproprolactone
- C-1 a, a, a ','-a polycarbodiimide compound made from tetramethyl-m-xylylenediisocyanate (Nisshinbo Co., Ltd., trade name "carbodilite V-05", carpoimide group content 5 Weight%, number average molecular weight 1000)
- D-1 Polycarboimide compound using hydrogenated methylene diphenyl 4,4'-diisocyanate as a raw material (Nisshinbo Co., Ltd., trade name "Calpolite HMV-18CA", Carpimide group content 8% by weight, number (Average molecular weight 2000)
- the polyester elastomer (A), the epoxy compound (B), and the polycarboimide compound (C) were mixed at the mixing ratio (unit: parts by weight) shown in Table 1. Then, using a 3 ⁇ twin-screw extruder, melt-knead at 250 ⁇ ⁇ , extruded strands are cooled in a water tank, cut with a pelletizer, and cut into a polyester elastomer composition. A pellet was obtained. The obtained pellets were dried for 5 hours while flowing nitrogen at 120.
- a tensile test specimen and a Charpy impact test specimen were molded at 260 using an injection molding machine.
- Example 1 The procedure was performed in the same manner as in Example 1 except that the mixing ratio was as shown in Table 1. The results are shown in Table 1. Compared with Example 1, the results of the water resistance test were poor and the hydrolysis resistance was low unless an epoxy compound was added.
- Example 1 The procedure was performed in the same manner as in Example 1 except that the mixing ratio was as shown in Table 1. The results are shown in Table 1. As can be seen from Table 1, the results of the water resistance test are clearly poor as compared with Example 1 in which the type of polycarboimide is different. (Mixing unit: parts by weight)
- a polyester elastomer composition having excellent hydrolysis resistance, heat resistance, oil resistance, abrasion resistance and impact resistance can be obtained.
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/587,504 US20070260032A1 (en) | 2004-01-29 | 2005-01-25 | Polyester Elastomer Composition |
EP05704311A EP1710277A4 (en) | 2004-01-29 | 2005-01-25 | COMPOSITION OF POLYESTER ELASTOMER |
Applications Claiming Priority (2)
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JP2004-022012 | 2004-01-29 | ||
JP2004022012A JP2005213374A (ja) | 2004-01-29 | 2004-01-29 | ポリエステルエラストマー組成物 |
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WO2005073315A1 true WO2005073315A1 (ja) | 2005-08-11 |
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PCT/JP2005/001315 WO2005073315A1 (ja) | 2004-01-29 | 2005-01-25 | ポリエステルエラストマー組成物 |
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Country | Link |
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US (1) | US20070260032A1 (ja) |
EP (1) | EP1710277A4 (ja) |
JP (1) | JP2005213374A (ja) |
KR (1) | KR20070007087A (ja) |
CN (1) | CN1914274A (ja) |
TW (1) | TW200535163A (ja) |
WO (1) | WO2005073315A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8414991B2 (en) | 2005-11-14 | 2013-04-09 | Bridgestone Corporation | Conductive endless belt |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2007029768A1 (ja) * | 2005-09-09 | 2007-03-15 | Toyo Boseki Kabushiki Kaisha | ポリエステルエラストマー組成物 |
JP2008189815A (ja) * | 2007-02-05 | 2008-08-21 | Nitto Denko Corp | 分散剤、フィラー、熱伝導性樹脂組成物ならび熱伝導性シート |
JP5266751B2 (ja) * | 2007-12-26 | 2013-08-21 | 東レ株式会社 | 熱可塑性樹脂組成物、その製造方法およびそれからなる成形品 |
JP5257322B2 (ja) * | 2009-10-29 | 2013-08-07 | 東洋紡株式会社 | 熱可塑性ポリエステルエラストマー組成物 |
JP2012219151A (ja) * | 2011-04-06 | 2012-11-12 | Nishikawa Rubber Co Ltd | 樹脂組成物 |
CN103897356B (zh) * | 2012-12-27 | 2016-03-09 | 中纺投资发展股份有限公司 | 一种耐水解耐高温的热塑性聚酯弹性体组合物 |
JP6055353B2 (ja) * | 2013-03-28 | 2016-12-27 | 日清紡ケミカル株式会社 | エステル系樹脂組成物、該エステル系樹脂組成物の製造方法、並びに該エステル系樹脂を用いた成形品 |
CN103333476A (zh) * | 2013-06-21 | 2013-10-02 | 苏州新区佳合塑胶有限公司 | 纳米二氧化钛增强pc组合物 |
CN105482388B (zh) * | 2016-01-29 | 2017-11-17 | 上海益弹新材料有限公司 | 一种聚酯弹性体组合物 |
EP3431538A1 (de) * | 2017-07-17 | 2019-01-23 | LANXESS Deutschland GmbH | Zusammensetzungen enthaltend polymeres carbodiimid, epoxid und polyester-basierte polymere, deren herstellung und verwendung |
CN108129626B (zh) * | 2017-12-20 | 2020-07-17 | 上海朗亿功能材料有限公司 | 一种聚合型碳化二亚胺类化合物及其制备方法 |
EP3755757A1 (en) * | 2018-02-23 | 2020-12-30 | Stepan Company | Solid-solid phase-change materials |
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 |
JP7024915B2 (ja) * | 2019-08-23 | 2022-02-24 | Dic株式会社 | 樹脂組成物及びそれを用いた半導体封止材料、含侵基材、回路基板、ビルドアップフィルム、プリプレグ、炭素繊維複合材料、ソルダーレジスト、ドライフィルム、プリント配線板 |
CN113185809B (zh) * | 2021-03-23 | 2022-03-22 | 会通新材料股份有限公司 | 一种用于薄壁注塑产品的耐热全生物降解复合材料及其制备方法 |
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JP2000159985A (ja) * | 1998-11-30 | 2000-06-13 | Toyobo Co Ltd | 熱可塑性ポリエステルエラストマー組成物 |
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JPS58162654A (ja) * | 1982-03-19 | 1983-09-27 | Toyobo Co Ltd | ポリエステル型ブロツク共重合体組成物 |
DE4442724A1 (de) * | 1994-12-01 | 1996-06-05 | Basf Ag | Stabilisierte Polyesterformmassen |
JP3373996B2 (ja) * | 1996-02-06 | 2003-02-04 | 日清紡績株式会社 | エステル基を有する樹脂用の耐加水分解安定剤及び該安定剤によるエステル基を有する樹脂の耐加水分解安定化方法 |
TW585880B (en) * | 1999-08-05 | 2004-05-01 | Daicel Chem | Process for producing polyester block copolymer |
-
2004
- 2004-01-29 JP JP2004022012A patent/JP2005213374A/ja active Pending
-
2005
- 2005-01-25 US US10/587,504 patent/US20070260032A1/en not_active Abandoned
- 2005-01-25 EP EP05704311A patent/EP1710277A4/en not_active Withdrawn
- 2005-01-25 KR KR1020067016897A patent/KR20070007087A/ko not_active Application Discontinuation
- 2005-01-25 TW TW094102095A patent/TW200535163A/zh unknown
- 2005-01-25 WO PCT/JP2005/001315 patent/WO2005073315A1/ja not_active Application Discontinuation
- 2005-01-25 CN CNA2005800036816A patent/CN1914274A/zh active Pending
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JP2000159985A (ja) * | 1998-11-30 | 2000-06-13 | Toyobo Co Ltd | 熱可塑性ポリエステルエラストマー組成物 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8414991B2 (en) | 2005-11-14 | 2013-04-09 | Bridgestone Corporation | Conductive endless belt |
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Publication number | Publication date |
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US20070260032A1 (en) | 2007-11-08 |
EP1710277A4 (en) | 2008-01-23 |
KR20070007087A (ko) | 2007-01-12 |
CN1914274A (zh) | 2007-02-14 |
JP2005213374A (ja) | 2005-08-11 |
TW200535163A (en) | 2005-11-01 |
EP1710277A1 (en) | 2006-10-11 |
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