JP2004300377A - Polytrimethylene terephthalate resin composition - Google Patents
Polytrimethylene terephthalate resin composition Download PDFInfo
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- JP2004300377A JP2004300377A JP2003098049A JP2003098049A JP2004300377A JP 2004300377 A JP2004300377 A JP 2004300377A JP 2003098049 A JP2003098049 A JP 2003098049A JP 2003098049 A JP2003098049 A JP 2003098049A JP 2004300377 A JP2004300377 A JP 2004300377A
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- JP
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- Prior art keywords
- resin composition
- polytrimethylene terephthalate
- terephthalate resin
- acid
- epoxy compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 Polytrimethylene terephthalate Polymers 0.000 title claims abstract description 53
- 229920002215 polytrimethylene terephthalate Polymers 0.000 title claims abstract description 48
- 239000011342 resin composition Substances 0.000 title claims abstract description 36
- 239000004593 Epoxy Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 16
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 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 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-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
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YJGUVTBNQCVSQB-UHFFFAOYSA-N 2,2-diphenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C(=O)O)C1=CC=CC=C1 YJGUVTBNQCVSQB-UHFFFAOYSA-N 0.000 description 1
- ROVLJQDICPLANK-UHFFFAOYSA-N 2-ethoxy-3-hydroxybenzoic acid Chemical compound CCOC1=C(O)C=CC=C1C(O)=O ROVLJQDICPLANK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000003078 antioxidant 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
- 238000000071 blow moulding Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JSACCUIJPSSQDK-UHFFFAOYSA-N methoxy-[1-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C(C1CO1)OC(CC)[SiH2]OC JSACCUIJPSSQDK-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical class NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- NFRRMEMOPXUROM-UHFFFAOYSA-N triethoxy-[1-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)C(CC)OCC1CO1 NFRRMEMOPXUROM-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、優れた機械特性および成形品外観に加え、耐加水分解性に著しく優れた自動車部品、電気電子部品およびその他有用な工業部品に好適に用いられるポリトリメチレンテレフタレート樹脂組成物に関する。
【０００２】
【従来の技術】
従来、ポリトリメチレンテレフタレート樹脂に代表される熱可塑性ポリエステル樹脂は機械特性、耐薬品性、耐候性、電気的特性等に優れるため、自動車部品、電気・電子部品などの広い分野でその使用が期待されている。中でも、ポリトリメチレンテレフタレート樹脂は結束バンドなどの工業部品において、その優れた機械特性、耐候性、耐薬品性により、従来金属が使用されていた分野での使用が期待されている。しかしながら、ポリトリメチレンテレフタレート樹脂は耐加水分解性に劣るため、屋外で使用することが困難であり、未だ実用可能なレベルには至っていない。
【０００３】
例えば、熱可塑性ポリエステル樹脂に属するポリブチレンテレフタレート樹脂に、耐加水分解特性を向上させる目的で、２．５当量／ｋｇ以上の二級水酸基含量を有するビスフェノールＡ型エポキシ樹脂を配合することが開示されている（例えば特許文献１参照。）。しかしながら、ポリトリメチレンテレフタレート樹脂に上記エポキシ化合物を配合しても、耐加水分解性の改善効果は小さく、実用レベルには至らない。
【０００４】
【特許文献１】
特開平７−１７９７３４号公報
【０００５】
【発明が解決しようとする課題】
優れた機械特性および成形品外観に加え、耐加水分解性に著しく優れた、市場要求を十分満足するポリトリメチレンテレフタレート樹脂組成物を提供することが本発明の課題である。
【０００６】
【課題を解決するための手段】
本発明者等は，前記課題を解決するため鋭意検討を重ねた結果、（Ａ）ポリトリメチレンテレフタレートと（Ｂ）エポキシ化合物からなる樹脂組成物が、特定のＣＯＯＨ末端基濃度、かつ特定範囲の極限粘度である場合に、目的の改良効果を発現することを見出し、本発明を完成するに至った。
すなわち本発明は、以下のとおりである。
【０００７】
１．（Ａ）ポリトリメチレンテレフタレートおよび（Ｂ）エポキシ化合物からなる樹脂組成物であって、該樹脂組成物の末端カルボキシル基濃度が２０ｍｅｑ／ｋｇ以下であり、極限粘度［η］が０．６〜１．５であることを特徴とするポリトリメチレンテレフタレート樹脂組成物。
２．該樹脂組成物の末端カルボキシル基濃度が、１５ｍｅｑ／ｋｇ以下であることを特徴とする上記１に記載のポリトリメチレンテレフタレート樹脂組成物。
３．（Ｂ）エポキシ化合物が下記一般式（１）で表されるジエポキシ化合物であることを特徴とする上記１または２に記載のポリトリメチレンテレフタレート樹脂組成物。
【０００８】
【化２】
４．（Ａ）成分１００重量部に対して、（Ｂ）成分０．０１〜１０重量部配合してなることを特徴とする上記１〜３のいずれかに記載のポリトリメチレンテレフタレート樹脂組成物。
【００１０】
【発明の実施の形態】
以下、本発明に関して具体的に説明する。
まず、本発明組成物の（Ａ）成分としてのポリトリメチレンテレフタレートについて記述する。
本発明のポリトリメチレンテレフタレート樹脂組成物の組成成分である（Ａ）ポリトリメチレンテレフタレート（以下、ＰＴＴと略称することがある。）とは、酸成分としてテレフタル酸を用い、グリコール成分としてトリメチレングリコールを用いたポリエステルポリマーを示している。本発明においてトリメチレングリコールとしては、１，３−プロパンジオール、１，２−プロパンジオール、１，１−プロパンジオール、２，２−プロパンジオール、あるいはこれらの混合物の中から選ばれるが、安定性の観点から１，３−プロパンジオールが特に好ましい。
【００１１】
このほかに、樹脂組成物の重量に対し２０重量％以下で共重合成分を配合してもよい。共重合成分の例として次の化合物が挙げられる。酸成分として、テレフタル酸以外の芳香族ジカルボン酸、例えばフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、ジフェニルジカルボン酸、ジフェニルエーテルジカルボン酸、ジフェノキシエタンジカルボン酸、ジフェニルメタンジカルボン酸、ジフェニルケトンジカルボン酸、ジフェニルスルフォンジカルボン酸等；コハク酸、アジピン酸、セバシン酸等の脂肪族ジカルボン酸；シクロヘキサンジカルボン酸等の脂環族ジカルボン酸；ε−オキシカプロン酸、ヒドロキシ安息香酸、ヒドロキシエトキシ安息香酸等のオキシジカルボン酸を用い、グリコール成分として、エチレングリコール、テトラメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール、オクタメチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノール、キシリレングリコール、ジエチレングリコール、ポリオキシアルキレングリコール、ハイドロキノンなどを一部用いて共重合することができる。
【００１２】
また、上述のポリエステル成分に分岐成分、例えばトリカルバリル酸、トリメシン酸、トリメリット酸等の、三官能または四官能のエステル形成能を持つ酸またはグリセリン、トリメチロールプロパン、ペンタエリトリットなどの三官能または四官能のエステル形成能を持つアルコールを共重合してもよく、その場合にそれらは全ジカルボン酸成分の１．０モル％以下、好ましくは、０．５モル％以下、さらに好ましくは、０．３モル％以下である。更に、ＰＴＴはこれら共重合成分を２種類以上組み合わせて使用しても構わない。
【００１３】
本発明に用いられる（Ａ）ポリトリメチレンテレフタレートの製造方法は、特に限定されるものではないが、例えば、特開昭５１−１４０９９２号公報、特開平５−２６２８６２号公報、特開平８−３１１１７７号公報等に記載されている方法によって、テレフタル酸またはそのエステル形成性誘導体（例えばジメチルエステル、モノメチルエステル等の低級アルキルエステル）とトリメチレングリコールまたはそのエステル形成性誘導体とを、触媒の存在下、好適な温度・時間で加熱反応させ、更に得られるテレフタル酸のグリコールエステルを触媒の存在下、好適な温度・時間で所望の重合度まで重縮合反応させる方法が挙げられる。重合方法は、特に限定されず、溶融重合、界面重合、溶液重合、塊状重合、固相重合、および、これらを組み合わせた方法を利用することができる。
【００１４】
本発明に用いるポリマ−には必要に応じて、各種の添加剤、例えば、熱安定剤、消泡剤、整色剤、難燃剤、酸化防止剤、紫外線吸収剤、赤外線吸収剤、結晶核剤、蛍光増白剤、艶消し剤などを共重合、または混合してもよい。
本発明に用いられる（Ａ）ポリトリメチレンテレフタレートは、その極限粘度［η］が機械特性の面から０．６０〜１．５０ｄｌ／ｇであることが好ましく、０．８０〜１．４０ｄｌ／ｇであることがより好ましく、１．００〜１．３０ｄｌ／ｇであることが最も好ましい。
極限粘度［η］については、オストワルド粘度計を用い、３５℃、ｏ−クロロフェノール中に（Ａ）ポリトリメチレンテレフタレートが１．００ｇ／ｄｌになるように溶解させ、比粘度ηｓｐを測定し、下記式により求めることができる。
［η］＝０．７１３×ηｓｐ／Ｃ＋０．１０８６
Ｃ＝１．００ｇ／ｄｌ
【００１５】
本発明に用いられる（Ｂ）エポキシ化合物は下記一般式（２）の分子構造を分子中に１個以上含有する化合物であれば、特に制限はない。（Ｂ）エポキシ化合物としては具体的にはα−グリシドキシプロピルトリエトキシシラン、α−グリシドキシプロピルメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシランなどのエポキシシラン、ビスフェノールＡ型エポキシ化合物、ビスフェノールＳ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、レゾルシン型エポキシ化合物、ノボラック型エポキシ化合物、環状脂肪族化合物型エポキシ化合物、グリシジルエーテル型化合物、グリシジルエステル型化合物、グリシジルアミン型化合物、エポキシ化ポリブタジエン、トリグリシジルジイソシアネート等が挙げられる。これらのエポキシ化合物は１種または２種以上を使用することができる。中でも、グリシジルエステル型が耐加水分解性の観点から好適に用いられ、特に上記一般式（１）に表されるジグリシジルテレフタレートが耐加水分解性の観点から最も好ましく用いられる。
【００１６】
【化３】
（Ｂ）成分の添加量は、耐加水分解性の観点から（Ａ）成分１００重量部に対して、０．０１〜１０重量部であることが好ましく、０．０５〜５重量部であることがより好ましく、０．１〜３重量部であることが最も好ましい。
本発明のポリトリメチレンテレフタレート樹脂組成物はその極限粘度［η］が機械特性および耐加水分解性の面から０．６０〜１．５０ｄｌ／ｇであり、０．８０〜１．５０ｄｌ／ｇであることがより好ましく、１．００〜１．５０ｄｌ／ｇであることが最も好ましい。
ポリトリメチレンテレフタレート樹脂組成物の極限粘度［η］については、オストワルド粘度計を用い、３５℃、ｏ−クロロフェノール中に該樹脂組成物を溶質（樹脂成分）／溶液＝１．００ｇ／ｄｌになるように溶解させ、比粘度ηｓｐを測定し、下記式により求めることができる。
［η］＝０．７１３×ηｓｐ／Ｃ＋０．１０８６
Ｃ＝１．００ｇ／ｄｌ
【００１８】
本発明のポリトリメチレンテレフタレートのＣＯＯＨ末端基濃度は耐加水分解性の観点から２０ｍｅｑ／ｋｇ以下であり、１５ｍｅｑ／ｋｇ以下であることがより好ましく、１０ｍｅｑ／ｋｇ以下であることが最も好ましい。
ポリトリメチレンテレフタレート樹脂組成物のＣＯＯＨ末端基濃度については、ポリトリメチレンテレフタレート樹脂組成物１ｇにベンジルアルコール２５ｍｇを加え、窒素雰囲気下、２００ で１５分加熱し、その後、フェノールフタレイン指示薬を３滴、クロロホルム２５ｍｌを添加した後、０．０２Ｎの水酸化カリウムのベンジルアルコール溶液で滴定し、求めることが出来る。
本発明では、上記の成分の他に、本発明の特徴および効果を損なわない範囲で必要に応じて他の附加的成分、例えば、酸化防止剤、熱安定剤、難燃剤、結晶核剤、可塑剤、難燃助剤、耐候（光）性改良剤、スリップ剤、各種着色剤、離型剤、無機充填剤等を添加してもかまわない。
【００１９】
さらに、本発明の組成物には、本発明の目的を損なわない範囲で、本発明の組成物にポリカーボネート、ポリスチレン系樹脂（ゴム強化ポリスチレン、アクリロニトリル−ブタジエン−スチレン樹脂など）の熱可塑性樹脂の１種又は２種以上を混合してもよい。
本発明のポリトリメチレンテレフタレート樹脂組成物の製造方法は特に限定されないが、（Ａ）、（Ｂ）成分、さらに上記した添加剤等を単軸または多軸の押出機、ニーダー、ミキシングロール、バンバリーミキサー等の公知の溶融混練機を用いて、２００〜３５０℃の温度で溶融混練する方法を挙げることができる。特に、押出機を用いて溶融混練することが簡便で望ましい。
本発明のポリトリメチレンテレフタレート樹脂組成物は、射出成形、押出成形、圧縮成形、ブロ−成形などの公知の成形方法によって成形することができる。
本発明のポリトリメチレンテレフタレート樹脂組成物は、優れた機械特性、成形品外観に加え、耐加水分解性に著しく優れた適性があり、自動車部品、電気電子部品およびその他有用な工業部品に好適に使用することができる。
【００２０】
【実施例】
以下実施例で本発明をさらに詳細に説明するが、本発明はこれら実施例に限定するものではない。なお、実施例および比較例に記載した諸特性は以下の方法により評価した。
（Ａ） 引張強度、引張伸度、耐加水分解性
試料は、射出成形機を用いてＩＳＯダンベル片を成形した。装置は日精樹脂（株）製ＦＮ３０００を用い、シリンダー温度２６０℃、金型温度９５℃に設定し、射出３０秒、冷却２０秒の射出成形条件で、成形品を得た。
（１）引張強度（ＭＰａ）、引張伸度（％）
ＩＳＯ−５２７に準じて行った。
（２）耐加水分解性試験後の引張強度保持率
引張試験に用いたＩＳＯダンベル片を用いて、１２１℃、２気圧、１００％ＲＨ相対湿度下でのプレッシャー・クッカー試験を４８時間行った。試験後の強度保持率を下記式により求めた。
耐加水分解試験後の引張強度保持率（％）＝引張強度（試験後）／引張強度（試験前）×１００
【００２１】
（Ｂ） 成形品外観（成形条件）
試料は、射出成形機を用いて１００ｍｍ×１００ｍｍ×２ｍｍ厚の平板を成形した。装置は日精樹脂（株）製ＦＮ３０００を用い、シリンダー温度２６０℃、金型温度９５℃に設定し、射出３０秒、冷却２０秒の射出成形条件で、成形品を得た。
（１）成形品外観
ミノルタ（株）社製ＣＭ−２００２分光測色計（Ｄ６５／１０°（ＳＣＥ））を用いて、上記平板のｂ値を測定した。数値が１０未満の場合には○、１０以上の場合には×とした。
【００２２】
（Ｃ） ポリトリメチレンテレフタレート樹脂組成物の極限粘度数［η］
ポリトリメチレンテレフタレート樹脂組成物の極限粘度［η］については、オストワルド粘度計を用い、３５℃、ｏ−クロロフェノール中にプレッシャー・クッカー試験前のダンベル片を溶質（樹脂成分）／溶液＝１．００ｇ／ｄｌになるように溶解させ、比粘度ηｓｐを測定し、下記式により求めることができる。
［η］＝０．７１３×ηｓｐ／Ｃ＋０．１０８６
Ｃ＝１．００ｇ／ｄｌ
（１）ポリトリメチレンテレフタレート樹脂組成物のＣＯＯＨ末端基濃度（ｍｅｑ／ｋｇ）
ポリトリメチレンテレフタレート樹脂組成物のＣＯＯＨ末端基濃度については、ポリトリメチレンテレフタレート樹脂組成物１ｇにベンジルアルコール２５ｍｇを加え、窒素雰囲気下、２００ で１５分加熱した。その後、フェノールフタレイン指示薬を３滴、クロロホルム２５ｍｌを添加した後、０．０２Ｎの水酸化カリウムのベンジルアルコール溶液で滴定し、ＣＯＯＨ末端基濃度を求めた。
【００２３】
（Ｄ） 原材料
（Ａ１）ＰＴＴ１：ポリトリメチレンテレフタレート（極限粘度［η］＝０．８９）
ＳＨＥＬＬ社製 ＣＰ５０９２０１
（Ａ２）ＰＴＴ２：ポリトリメチレンテレフタレート（極限粘度［η］＝１．１１）
ＳＨＥＬＬ社製 ＣＰ５１３０００
（Ａ３）ＰＴＴ３：ポリトリメチレンテレフタレート（極限粘度［η］＝０．８９）
ＳＨＥＬＬ社製 ＣＰ５０９２００
【００２４】
極限粘度［η］については、オストワルド粘度計を用い、３５℃、ｏ−クロロフェノール中に（Ａ）ポリトリメチレンテレフタレート樹脂が１．００ｇ／ｄｌになるように溶解させ、比粘度ηｓｐを測定し、下記式により求めた。
［η］＝０．７１３×ηｓｐ／Ｃ＋０．１０８６
Ｃ＝１．００ｇ／ｄｌ
（Ｂ１）エポキシ化合物１
ナガセケムテックス（株）社製 デナコールＥＸ７１１
（Ｂ２）エポキシ化合物２
ナガセケムテックス（株）社製 デナコールＥＸ８５０
（Ｂ３）エポキシ化合物３
ナガセケムテックス（株）社製 デナコールＥＸ１４５
（Ｂ４）エポキシ化合物４
旭化成エポキシ（株）社製 １２９９
（Ｂ５）エポキシ化合物５
旭化成エポキシ（株）社製 ６０８４
【００２５】
【実施例１〜３および比較例１〜６】
（Ａ１）〜（Ａ３）ＰＴＴと（Ｂ１）〜（Ｂ５）エポキシ化合物を表１に示す配合割合で、ブレンダーを用いて予備混合後、２軸押出機（ＷＥＲＮＥＲ ＆ ＰＦＬＥＩＤＥＲＥＲ社製：ＺＳＫ−２５）を用いて溶融混練した。スクリュー回転数３００ｒｐｍ、シリンダー温度２５０℃（先端ノズル付近のポリマー温度は、２８０℃であった）、押出速度１０Ｋｇ／ｈｒ（滞留時間１分）、減圧度は０．０４ＭＰａで押出を行った。先端ノズルからストランド状にポリマーを排出し、水冷・カッティングを行いペレットとした。該ペレットを１２０℃で５時間、除湿型乾燥機で乾燥した後、上記に示す射出成形方法で成形品を作成し、この成形品を上記測定方法に従って、解析および諸特性の測定した。尚、（Ａ）と（Ｂ）の配合割合であるが、実施例１は（Ａ）のＣＯＯＨ末端基に対して（Ｂ）のエポキシ基が１倍当量、実施例２、３、比較例３〜６は（Ａ）のＣＯＯＨ末端基に対して（Ｂ）のエポキシ基が２倍当量とした。
【００２６】
【表１】
【発明の効果】
本発明により得られたポリトリメチレンテレフタレート樹脂組成物は、機械特性および成形品外観に加え、耐加水分解性に著しく優れた特性を有し、自動車部品、電気電子部品およびその他有用な工業部品に広く用いることが出来る。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polytrimethylene terephthalate resin composition which is excellent in hydrolysis resistance in addition to excellent mechanical properties and appearance of molded articles, and which is suitably used for automobile parts, electric / electronic parts and other useful industrial parts.
[0002]
[Prior art]
Conventionally, thermoplastic polyester resin represented by polytrimethylene terephthalate resin has excellent mechanical properties, chemical resistance, weather resistance, electrical properties, etc., and is expected to be used in a wide range of fields such as automotive parts, electric and electronic parts. Have been. Above all, polytrimethylene terephthalate resin is expected to be used in fields where metals have been conventionally used in industrial parts such as binding bands due to its excellent mechanical properties, weather resistance and chemical resistance. However, polytrimethylene terephthalate resin has poor hydrolysis resistance, so it is difficult to use it outdoors, and it has not yet reached a practical level.
[0003]
For example, it is disclosed that a bisphenol A type epoxy resin having a secondary hydroxyl group content of 2.5 equivalents / kg or more is mixed with a polybutylene terephthalate resin belonging to a thermoplastic polyester resin for the purpose of improving hydrolysis resistance. (For example, see Patent Document 1). However, even if the above-mentioned epoxy compound is blended with the polytrimethylene terephthalate resin, the effect of improving the hydrolysis resistance is small and does not reach a practical level.
[0004]
[Patent Document 1]
Japanese Patent Application Laid-Open No. Hei 7-179934
[Problems to be solved by the invention]
It is an object of the present invention to provide a polytrimethylene terephthalate resin composition which has excellent mechanical properties and appearance of a molded product, as well as remarkably excellent hydrolysis resistance, and which sufficiently satisfies market requirements.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, the resin composition comprising (A) polytrimethylene terephthalate and (B) an epoxy compound has a specific COOH terminal group concentration and a specific range. It has been found that when the viscosity is the intrinsic viscosity, the intended improvement effect is exhibited, and the present invention has been completed.
That is, the present invention is as follows.
[0007]
1. A resin composition comprising (A) polytrimethylene terephthalate and (B) an epoxy compound, wherein the terminal carboxyl group concentration of the resin composition is 20 meq / kg or less, and the intrinsic viscosity [η] is 0.6 to 1 5. A polytrimethylene terephthalate resin composition, wherein
2. 2. The polytrimethylene terephthalate resin composition according to the above item 1, wherein the terminal carboxyl group concentration of the resin composition is 15 meq / kg or less.
3. (B) The polytrimethylene terephthalate resin composition as described in (1) or (2) above, wherein the epoxy compound is a diepoxy compound represented by the following general formula (1).
[0008]
Embedded image
4. 4. The polytrimethylene terephthalate resin composition according to any one of the above items 1 to 3, wherein 0.01 to 10 parts by weight of the component (B) is added to 100 parts by weight of the component (A).
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described specifically.
First, polytrimethylene terephthalate as the component (A) of the composition of the present invention will be described.
The (A) polytrimethylene terephthalate (hereinafter sometimes abbreviated as PTT), which is a component of the polytrimethylene terephthalate resin composition of the present invention, refers to terephthalic acid as an acid component and trimethylene as a glycol component. 3 shows a polyester polymer using glycol. In the present invention, the trimethylene glycol is selected from 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, and a mixture thereof. From the viewpoint of 1,3-propanediol is particularly preferred.
[0011]
In addition, a copolymer component may be blended at 20% by weight or less based on the weight of the resin composition. Examples of the copolymer component include the following compounds. As the acid component, aromatic dicarboxylic acids other than terephthalic acid, such as phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylmethanedicarboxylic acid, and diphenylketonedicarboxylic acid Aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; oxy acids such as ε-oxycaproic acid, hydroxybenzoic acid, and hydroxyethoxybenzoic acid. Using dicarboxylic acid, glycol components such as ethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, neopentyl glycol Le, cyclohexanedimethanol, xylylene glycol, diethylene glycol, polyoxyalkylene glycol, may be copolymerized with such a part hydroquinone.
[0012]
Further, the above-mentioned polyester component may contain a branching component such as tricarballylic acid, trimesic acid, trimellitic acid, etc., or a trifunctional or tetrafunctional ester-forming acid or trifunctional such as glycerin, trimethylolpropane, pentaerythritol. Alternatively, alcohols having tetrafunctional ester-forming ability may be copolymerized, in which case they are 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0 mol% or less of the total dicarboxylic acid component. 0.3 mol% or less. Further, PTT may be used in combination of two or more of these copolymer components.
[0013]
The method for producing (A) polytrimethylene terephthalate used in the present invention is not particularly limited, and examples thereof include, for example, JP-A-51-140992, JP-A-5-262882, and JP-A-8-31177. Terephthalic acid or an ester-forming derivative thereof (for example, a lower alkyl ester such as dimethyl ester or monomethyl ester) and trimethylene glycol or an ester-forming derivative thereof in the presence of a catalyst. A method in which a heat reaction is performed at a suitable temperature and time, and a polycondensation reaction is further performed on the resulting glycol ester of terephthalic acid to a desired degree of polymerization at a suitable temperature and time in the presence of a catalyst. The polymerization method is not particularly limited, and a melt polymerization, an interfacial polymerization, a solution polymerization, a bulk polymerization, a solid phase polymerization, or a method combining these can be used.
[0014]
Various additives may be added to the polymer used in the present invention, if necessary, for example, heat stabilizers, defoamers, tinting agents, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, and crystal nucleating agents. , A fluorescent whitening agent, a matting agent and the like may be copolymerized or mixed.
The polytrimethylene terephthalate (A) used in the present invention preferably has an intrinsic viscosity [η] of 0.60 to 1.50 dl / g, preferably 0.80 to 1.40 dl / g, from the viewpoint of mechanical properties. Is more preferable, and most preferably 1.00 to 1.30 dl / g.
With respect to the intrinsic viscosity [η], (A) polytrimethylene terephthalate was dissolved in o-chlorophenol so as to be 1.00 g / dl using an Ostwald viscometer, and the specific viscosity η sp was measured. , Can be obtained by the following equation.
[Η] = 0.713 × η sp /C+0.1086
C = 1.00 g / dl
[0015]
The epoxy compound (B) used in the present invention is not particularly limited as long as it contains at least one molecular structure represented by the following general formula (2) in the molecule. (B) Specific examples of the epoxy compound include epoxy silanes such as α-glycidoxypropyltriethoxysilane, α-glycidoxypropylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and bisphenol. A type epoxy compound, bisphenol S type epoxy compound, bisphenol F type epoxy compound, resorcinol type epoxy compound, novolak type epoxy compound, cycloaliphatic compound type epoxy compound, glycidyl ether type compound, glycidyl ester type compound, glycidylamine type compound, Epoxidized polybutadiene, triglycidyl diisocyanate and the like can be mentioned. One or two or more of these epoxy compounds can be used. Among them, the glycidyl ester type is suitably used from the viewpoint of hydrolysis resistance, and particularly, diglycidyl terephthalate represented by the above general formula (1) is most preferably used from the viewpoint of hydrolysis resistance.
[0016]
Embedded image
The addition amount of the component (B) is preferably 0.01 to 10 parts by weight, and more preferably 0.05 to 5 parts by weight based on 100 parts by weight of the component (A) from the viewpoint of hydrolysis resistance. Is more preferable, and most preferably 0.1 to 3 parts by weight.
The polytrimethylene terephthalate resin composition of the present invention has an intrinsic viscosity [η] of 0.60 to 1.50 dl / g and 0.80 to 1.50 dl / g from the viewpoint of mechanical properties and hydrolysis resistance. More preferably, it is most preferably 1.00 to 1.50 dl / g.
The intrinsic viscosity [η] of the polytrimethylene terephthalate resin composition was determined using an Ostwald viscometer at 35 ° C. in o-chlorophenol solute (resin component) /solution=1.00 g / dl. And the specific viscosity η sp is measured and can be determined by the following equation.
[Η] = 0.713 × η sp /C+0.1086
C = 1.00 g / dl
[0018]
The COOH terminal group concentration of the polytrimethylene terephthalate of the present invention is 20 meq / kg or less, more preferably 15 meq / kg or less, most preferably 10 meq / kg or less from the viewpoint of hydrolysis resistance.
Regarding the COOH terminal group concentration of the polytrimethylene terephthalate resin composition, 25 mg of benzyl alcohol was added to 1 g of the polytrimethylene terephthalate resin composition, and the mixture was heated under a nitrogen atmosphere at 200 ° C. for 15 minutes, and then 3 drops of a phenolphthalein indicator were added. , 25 ml of chloroform, and then titration with a 0.02N solution of potassium hydroxide in benzyl alcohol to determine the concentration.
In the present invention, in addition to the above-mentioned components, other additional components as necessary within a range that does not impair the features and effects of the present invention, for example, an antioxidant, a heat stabilizer, a flame retardant, a crystal nucleating agent, and a plasticizer. Agents, flame retardant aids, weather (light) resistance improvers, slip agents, various colorants, release agents, inorganic fillers and the like may be added.
[0019]
Further, the composition of the present invention may contain one or more thermoplastic resins such as polycarbonate and polystyrene resin (such as rubber-reinforced polystyrene and acrylonitrile-butadiene-styrene resin) as long as the object of the present invention is not impaired. Species or two or more species may be mixed.
The method for producing the polytrimethylene terephthalate resin composition of the present invention is not particularly limited. A method of melt-kneading at a temperature of 200 to 350 ° C. using a known melt-kneader such as a mixer can be used. Particularly, it is convenient and desirable to perform melt kneading using an extruder.
The polytrimethylene terephthalate resin composition of the present invention can be molded by a known molding method such as injection molding, extrusion molding, compression molding, and blow molding.
The polytrimethylene terephthalate resin composition of the present invention has excellent mechanical properties and appearance of a molded article, and has excellent suitability for remarkably excellent hydrolysis resistance, and is suitable for automobile parts, electric / electronic parts and other useful industrial parts. Can be used.
[0020]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Various properties described in Examples and Comparative Examples were evaluated by the following methods.
(A) For the tensile strength, tensile elongation, and hydrolysis-resistant samples, ISO dumbbell pieces were molded using an injection molding machine. The apparatus used was FN3000 manufactured by Nissei Plastics Co., Ltd., and a molded product was obtained under the injection molding conditions of a cylinder temperature of 260 ° C. and a mold temperature of 95 ° C. for 30 seconds of injection and 20 seconds of cooling.
(1) Tensile strength (MPa), tensile elongation (%)
Performed according to ISO-527.
(2) Tensile strength retention after hydrolysis resistance test A pressure cooker test was performed at 121 ° C., 2 atm, and 100% RH relative humidity for 48 hours using the ISO dumbbell pieces used in the tensile test. The strength retention after the test was determined by the following equation.
Tensile strength retention rate after hydrolysis resistance test (%) = tensile strength (after test) / tensile strength (before test) × 100
[0021]
(B) Molded product appearance (molding conditions)
As the sample, a flat plate having a thickness of 100 mm x 100 mm x 2 mm was formed using an injection molding machine. The apparatus used was FN3000 manufactured by Nissei Plastics Co., Ltd., and a molded product was obtained under the injection molding conditions of a cylinder temperature of 260 ° C. and a mold temperature of 95 ° C. for 30 seconds of injection and 20 seconds of cooling.
(1) Appearance of Molded Product The b value of the flat plate was measured using a CM-2002 spectrophotometer (D65 / 10 ° (SCE)) manufactured by Minolta Co., Ltd. When the numerical value was less than 10, it was evaluated as ○, and when it was 10 or more, it was evaluated as ×.
[0022]
(C) intrinsic viscosity number [η] of the polytrimethylene terephthalate resin composition
The intrinsic viscosity [η] of the polytrimethylene terephthalate resin composition was determined using an Ostwald viscometer at 35 ° C. in o-chlorophenol at dumbbell pieces before the pressure cooker test, solute (resin component) / solution = 1. It is dissolved so as to be 00 g / dl, the specific viscosity η sp is measured, and it can be obtained by the following equation.
[Η] = 0.713 × η sp /C+0.1086
C = 1.00 g / dl
(1) COOH terminal group concentration of polytrimethylene terephthalate resin composition (meq / kg)
Regarding the COOH terminal group concentration of the polytrimethylene terephthalate resin composition, 25 mg of benzyl alcohol was added to 1 g of the polytrimethylene terephthalate resin composition, and the mixture was heated at 200 ° C. for 15 minutes under a nitrogen atmosphere. Thereafter, 3 drops of a phenolphthalein indicator and 25 ml of chloroform were added, and the mixture was titrated with a 0.02N solution of potassium hydroxide in benzyl alcohol to determine the COOH terminal group concentration.
[0023]
(D) Raw material (A1) PTT1: polytrimethylene terephthalate (intrinsic viscosity [η] = 0.89)
SH509 CP509201
(A2) PTT2: polytrimethylene terephthalate (intrinsic viscosity [η] = 1.11)
SH51 CP513000
(A3) PTT3: polytrimethylene terephthalate (intrinsic viscosity [η] = 0.89)
SH509 CP509200
[0024]
For intrinsic viscosity [η], (A) polytrimethylene terephthalate resin was dissolved in o-chlorophenol so as to be 1.00 g / dl at 35 ° C. using an Ostwald viscometer, and the specific viscosity η sp was measured. It was determined by the following equation.
[Η] = 0.713 × η sp /C+0.1086
C = 1.00 g / dl
(B1) Epoxy compound 1
Nagase ChemteX Corporation's Denacol EX711
(B2) Epoxy compound 2
Denasel EX850 manufactured by Nagase ChemteX Corporation
(B3) Epoxy compound 3
Denasel EX145 manufactured by Nagase ChemteX Corporation
(B4) Epoxy compound 4
1299 manufactured by Asahi Kasei Epoxy Corporation
(B5) Epoxy compound 5
6084 manufactured by Asahi Kasei Epoxy Co., Ltd.
[0025]
Examples 1-3 and Comparative Examples 1-6
After premixing (A1) to (A3) PTT and (B1) to (B5) epoxy compound in the mixing ratio shown in Table 1 using a blender, a twin screw extruder (ZSK-25, manufactured by WERNER & PFLEIDERER). And melt-kneaded. Extrusion was performed at a screw rotation speed of 300 rpm, a cylinder temperature of 250 ° C. (the polymer temperature near the tip nozzle was 280 ° C.), an extrusion speed of 10 kg / hr (residence time of 1 minute), and a degree of vacuum of 0.04 MPa. The polymer was discharged in the form of a strand from the tip nozzle, and water-cooled and cut into pellets. After drying the pellets at 120 ° C. for 5 hours using a dehumidifying dryer, a molded article was prepared by the injection molding method described above, and the molded article was analyzed and various characteristics were measured according to the above-described measurement methods. In addition, as for the mixing ratio of (A) and (B), in Example 1, the epoxy group of (B) was 1 equivalent to the COOH terminal group of (A), and Examples 2, 3 and Comparative Example 3 were used. In Nos. To 6, the epoxy group of (B) was twice equivalent to the COOH terminal group of (A).
[0026]
[Table 1]
【The invention's effect】
The polytrimethylene terephthalate resin composition obtained according to the present invention has remarkably excellent hydrolysis resistance in addition to mechanical properties and appearance of a molded product, and is used for automobile parts, electric / electronic parts and other useful industrial parts. Can be widely used.
Claims (4)
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| JP2003098049A JP2004300377A (en) | 2003-04-01 | 2003-04-01 | Polytrimethylene terephthalate resin composition |
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| JP2003098049A JP2004300377A (en) | 2003-04-01 | 2003-04-01 | Polytrimethylene terephthalate resin composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013006906A (en) * | 2011-06-22 | 2013-01-10 | Yazaki Corp | Molded article |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013006906A (en) * | 2011-06-22 | 2013-01-10 | Yazaki Corp | Molded article |
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