JP2020158717A - Polybutylene terephthalate-based resin composition and molded article comprising the same - Google Patents
Polybutylene terephthalate-based resin composition and molded article comprising the same Download PDFInfo
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- 229920001707 polybutylene terephthalate Polymers 0.000 title claims abstract description 99
- 239000011342 resin composition Substances 0.000 title claims abstract description 54
- -1 Polybutylene terephthalate Polymers 0.000 title claims abstract description 36
- 229920001577 copolymer Polymers 0.000 claims abstract description 33
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 238000000071 blow moulding Methods 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000010102 injection blow moulding Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 23
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 abstract description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-L dodecanedioate(2-) Chemical compound [O-]C(=O)CCCCCCCCCCC([O-])=O TVIDDXQYHWJXFK-UHFFFAOYSA-L 0.000 abstract 2
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 27
- 229920005989 resin Polymers 0.000 description 25
- 239000011347 resin Substances 0.000 description 25
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000002537 cosmetic Substances 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 239000004645 polyester resin Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003889 eye drop Substances 0.000 description 3
- 235000011194 food seasoning agent Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004278 EU approved seasoning Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229940012356 eye drops Drugs 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-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
- 235000014214 soft drink Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- LHGMHYDJNXEEFG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminocyclohexa-2,5-dien-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C=CC(=O)C=C1 LHGMHYDJNXEEFG-UHFFFAOYSA-N 0.000 description 1
- 208000029497 Elastoma Diseases 0.000 description 1
- 239000004420 Iupilon Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 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
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction 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
- 230000007423 decrease Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZMCZWKGAWRLZNP-UHFFFAOYSA-N methyl-oxo-phenyltin Chemical compound C[Sn](=O)C1=CC=CC=C1 ZMCZWKGAWRLZNP-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000009747 swallowing Effects 0.000 description 1
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
本発明は、ブロー成形に適したポリブチレンテレフタレート系樹脂組成物、およびそれを成形してなる成形品に関するものである。 The present invention relates to a polybutylene terephthalate resin composition suitable for blow molding, and a molded product obtained by molding the same.
ポリエステル樹脂は、成形性および機械特性に優れるため広範な分野で使用されている。また、二軸延伸が可能であることから、耐熱性、耐クリープ性、耐衝撃性、剛性、ガスバリア性、耐薬品性、透明性に優れた包装用材料として用いられ、特に容器分野では、食品用ボトル（例えば調味料ボトル、炭酸飲料等の清涼飲料用ボトル等）、化粧品ボトル、洗剤用ボトル、医療・医薬用ボトル等として広く使用されている。 Polyester resins are used in a wide range of fields due to their excellent moldability and mechanical properties. In addition, since it can be biaxially stretched, it is used as a packaging material with excellent heat resistance, creep resistance, impact resistance, rigidity, gas barrier property, chemical resistance, and transparency. Especially in the container field, food products It is widely used as bottles for seasonings (for example, bottles for seasonings, bottles for soft drinks such as carbonated drinks, etc.), cosmetic bottles, bottles for detergents, bottles for medical treatment and medicine, and the like.
これらの用途には、ポリエステル樹脂としては、主にポリエチレンテレフタレート樹脂（以下、ＰＥＴと略記することがある。）、ポリカーボネート樹脂（以下、ＰＣと略記することがある。）、その他の樹脂では、ポリプロピレン樹脂、ポリエチレン等のオレフィン系樹脂が使用されることが多い。また、その容器の殆どがダイレクトブロー成形、インジェクションブロー成形、シートブロー成形、フリーブロー成形等のブロー成形により成形される。近年、アタック性の強い洗剤や化粧品などが登場し、これらを内包するボトルにも高い耐薬品性が求められている。 For these uses, the polyester resin is mainly polyethylene terephthalate resin (hereinafter, may be abbreviated as PET), polycarbonate resin (hereinafter, may be abbreviated as PC), and other resins are polypropylene. Olefin resins such as resins and polyethylene are often used. Most of the containers are formed by blow molding such as direct blow molding, injection blow molding, sheet blow molding, and free blow molding. In recent years, detergents and cosmetics with strong attack properties have appeared, and bottles containing them are also required to have high chemical resistance.
一方、ポリエステル樹脂の中でもポリブチレンテレフタレート樹脂（以下、ＰＢＴと略記することがある。）は、ＰＥＴやＰＣよりも優れた耐薬品性を示すが、溶融粘度が低いことからブロー成形や押出成形等の加工が難しい課題があった。特に、ブロー成形においては、溶融粘度が低いことによりパリソンのドローダウンが起こり、肉厚の均一な成形品を得ることが難しい。 On the other hand, among polyester resins, polybutylene terephthalate resin (hereinafter, may be abbreviated as PBT) exhibits superior chemical resistance to PET and PC, but has low melt viscosity, so blow molding, extrusion molding, etc. There was a problem that it was difficult to process. In particular, in blow molding, the low melt viscosity causes drawdown of parison, and it is difficult to obtain a molded product having a uniform wall thickness.
ブロー成形性に優れる樹脂組成物として、固有粘度０．５以上のポリブチレンテレフタレート、α−オレフィンとα、β−不飽和のグリシジルエステルとの共重合体、ガラス繊維を配合してなる樹脂組成物（例えば、特許文献１）、ポリブチレンテレフタレート、直径３〜２０μｍのガラス繊維を配合してなる樹脂組成物（例えば、特許文献２）が提案されている。また、熱可塑性ポリエステル樹脂、スチレン共重合体、繊維状充填剤を配合してなる樹脂組成物（例えば、特許文献３）、ポリエステル樹脂、ポリエーテルエステルブロック共重合体を配合してなる樹脂組成物（例えば、特許文献４）が提案されている。 A resin composition containing polybutylene terephthalate having an intrinsic viscosity of 0.5 or more, a copolymer of α-olefin and α, β-unsaturated glycidyl ester, and glass fiber as a resin composition having excellent blow moldability. (For example, Patent Document 1), polybutylene terephthalate, and a resin composition (for example, Patent Document 2) containing glass fiber having a diameter of 3 to 20 μm have been proposed. Further, a resin composition containing a thermoplastic polyester resin, a styrene copolymer, and a fibrous filler (for example, Patent Document 3), and a resin composition containing a polyester resin and a polyether ester block copolymer. (For example, Patent Document 4) has been proposed.
ブロー成形品とした際の耐衝撃性や外観に優れる樹脂組成物として、固有粘度１．８〜２．３を有する熱可塑性共重合ポリエステル樹脂、ポリブチレンテレフタレートを配合してなる樹脂組成物が提案されている（例えば、特許文献５）。また、融点と結晶化温度の温度差が３７℃以上であるポリエステル系樹脂組成物が提案されている（例えば、特許文献 ６）。 As a resin composition having excellent impact resistance and appearance when made into a blow-molded product, a resin composition containing polybutylene terephthalate, a thermoplastic copolymer resin having an intrinsic viscosity of 1.8 to 2.3, has been proposed. (For example, Patent Document 5). Further, a polyester resin composition in which the temperature difference between the melting point and the crystallization temperature is 37 ° C. or more has been proposed (for example, Patent Document 6).
固相重合活性に優れるブロー成形用樹脂組成物として、特定のリン化合物二種を特定モル比で用いたポリエステル樹脂組成物が提案されている（例えば、特許文献７）。 As a resin composition for blow molding having excellent solid-state polymerization activity, a polyester resin composition using two specific phosphorus compounds in a specific molar ratio has been proposed (for example, Patent Document 7).
ＰＢＴのブロー成形品の製造方法として、固有粘度１．４ｄｌ／ｇ以上のポリブチレンテレフタレート樹脂を用いてカットオフ成形法でブロー成形する製造方法が提案されている（例えば、特許文献８）。 As a method for producing a blow molded product of PBT, a production method for blow molding by a cut-off molding method using a polybutylene terephthalate resin having an intrinsic viscosity of 1.4 dl / g or more has been proposed (for example, Patent Document 8).
まれに、車載用途等においてＰＢＴのブロー成形品が採用されている例があるが、この場合ＰＢＴにガラス繊維やエラストマ等の第二成分を配合することで、パリソンのドローダウンを抑制、賦形性を付与し、ブロー成形性を成立させているケースが多い。しかし、エラストマ等の他のポリマー成分を配合することで、容器とした際の耐薬品性が低下する上、医薬品用途、例えば点眼剤用プラスチック製容器では、薬発第三三六号厚生省薬務局長通知により定められている規格において、「灰化試験時の残分が０．１％以下」とされているため、医薬品用容器用の樹脂組成物に対してはガラス繊維等の無機充填剤を配合することが実質的にできない。 In rare cases, blow-molded PBT products are used for in-vehicle applications, etc. In this case, by blending a second component such as glass fiber or elastomer with PBT, drawdown of parison is suppressed and shaped. In many cases, the properties are imparted and blow moldability is established. However, by blending other polymer components such as elastoma, the chemical resistance of the container is reduced, and for pharmaceutical applications, such as plastic containers for eye drops, Yakuhin No. 336, Ministry of Health and Welfare. Since the standard stipulated by the director's notification states that "the residue during the ashing test is 0.1% or less", inorganic fillers such as glass fiber are used for resin compositions for pharmaceutical containers. Can not be blended practically.
このような背景から、第二成分を極力含まずにブロー成形性と成形品の耐薬品性、耐衝撃性を両立するＰＢＴが求められている。 Against this background, there is a demand for PBT that has both blow moldability, chemical resistance, and impact resistance of the molded product without containing the second component as much as possible.
しかしながら、特許文献１〜４および６に記載の樹脂組成物は、ＰＢＴの固有粘度が低いため溶融パリソンがドローダウンしやすくブロー成形性が不十分であり、またガラス繊維やエラストマ等の第二成分を含んでいることから薬発第三三六号厚生省薬務局長通知により定められている規格を満たさない、もしくは耐薬品性が不十分であった。 However, in the resin compositions described in Patent Documents 1 to 4 and 6, since the intrinsic viscosity of PBT is low, the molten parison is easily drawn down and the blow moldability is insufficient, and the second component such as glass fiber or elastomer is insufficient. Because it contains the above, the standard specified by the notification of the Director of Pharmaceutical Affairs Bureau, Ministry of Health and Welfare No. 336 of Yakuhin was not satisfied, or the chemical resistance was insufficient.
特許文献５および８に記載の樹脂組成物は、ポリブチレンテレフタレート樹脂を含むため固化速度が速く、ブロー成形時の賦形性が不十分であった。 Since the resin compositions described in Patent Documents 5 and 8 contain a polybutylene terephthalate resin, the solidification rate is high, and the shapeability at the time of blow molding is insufficient.
特許文献７に記載の樹脂組成物は、ＰＢＴの固有粘度が低いため、依然として溶融パリソンがドローダウンしやすくブロー成形性が不十分であった。 In the resin composition described in Patent Document 7, since the intrinsic viscosity of PBT is low, the molten parison is still easily drawn down and the blow moldability is insufficient.
本発明は、上記の課題に鑑み、第二成分を含むことなくブロー成形性に優れ、耐衝撃性、耐薬品性に優れたブロー成形品を得ることのできるＰＢＴ系樹脂組成物を提供することを課題とするものである。 In view of the above problems, the present invention provides a PBT-based resin composition capable of obtaining a blow-molded product having excellent blow-moldability, impact resistance and chemical resistance without containing a second component. Is the subject.
上記課題を解決するため、本発明は次の構成を有する。
（１）（Ａ）全ジカルボン酸成分中のドデカンジオン酸成分含有率が５〜２０ｍｏｌ％であるポリブチレン（テレフタレート／ドデカジオエート）共重合体１００重量部に対し、（Ｂ）前記（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体以外の成分０〜０．１重量部からなるポリブチレンテレフタレート系樹脂組成物であって、０．５質量％オルトクロロフェノール溶液で測定した２５℃における相対粘度が１．８５以上であり、示差走査熱量計（ＤＳＣ）を用いて窒素雰囲気下で４０℃から２６０℃まで２０℃／分の速度で昇温した時に観測される吸熱ピークが一つで、その吸熱ピーク温度（融点）が２００〜２２０℃であるポリブチレンテレフタレート系樹脂組成物。
（２）前記樹脂組成物がブロー成形用である、（１）に記載のポリブチレンテレフタレート系樹脂組成物。
（３）（２）に記載のポリブチレンテレフタレート系樹脂組成物をダイレクトブロー成形またはインジェクションブロー成形してなるブロー成形品。
（４）（１）に記載のポリブチレンテレフタレート系樹脂組成物を押出成形してなるフィルムまたはシート。
（５）（１）に記載のポリブチレンテレフタレート系樹脂組成物を押出成形してなるチューブ成形品。
In order to solve the above problems, the present invention has the following configuration.
(1) (A) Polybutylene (A) said above with respect to 100 parts by weight of a polybutylene (terephthalate / dodecadioate) copolymer having a dodecandionic acid component content of 5 to 20 mol% in the total dicarboxylic acid component. (Telephthalate / dodecadioate) A polybutylene terephthalate resin composition consisting of 0 to 0.1 parts by weight of components other than the copolymer, and having a relative viscosity at 25 ° C. measured with a 0.5 mass% orthochlorophenol solution. Is 1.85 or more, and there is one heat absorption peak observed when the temperature is raised from 40 ° C. to 260 ° C. at a rate of 20 ° C./min in a nitrogen atmosphere using a differential scanning calorimeter (DSC). A polybutylene terephthalate resin composition having a heat absorption peak temperature (melting point) of 200 to 220 ° C.
(2) The polybutylene terephthalate-based resin composition according to (1), wherein the resin composition is for blow molding.
(3) A blow molded product obtained by directly blow molding or injection blow molding the polybutylene terephthalate resin composition according to (2).
(4) A film or sheet obtained by extrusion-molding the polybutylene terephthalate resin composition according to (1).
(5) A tube-molded product obtained by extrusion-molding the polybutylene terephthalate-based resin composition according to (1).
本発明のＰＢＴ系樹脂組成物は第二成分を含むことなくブロー成形性に優れ、本発明の樹脂組成物を成形して得られる成形品は耐衝撃性、耐薬品性に優れるため、食品、化粧品、洗剤、医療・医薬用途等における容器あるいは包装材料として有用である。 The PBT-based resin composition of the present invention is excellent in blow moldability without containing the second component, and the molded product obtained by molding the resin composition of the present invention is excellent in impact resistance and chemical resistance. It is useful as a container or packaging material for cosmetics, detergents, medical / pharmaceutical applications, etc.
ポリブチレンテレフタレート樹脂は、結晶化特性、耐熱性、成形性、耐薬品性に優れている。本発明に用いられる（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体とは、テレフタル酸およびドデカンジオン酸と１，４−ブタンジオールとの共重合体であって、テレフタル酸あるいはそのエステル形成性誘導体、およびドデカンジオン酸あるいはそのエステル形成性誘導体と、ブタンジオールあるいはそのエステル形成性誘導体とを通常公知の方法で重縮合して得られるものである。さらに他の成分を共重合してもよい。 Polybutylene terephthalate resin is excellent in crystallization characteristics, heat resistance, moldability, and chemical resistance. The (A) polybutylene (terephthalate / dodecadioate) copolymer used in the present invention is a copolymer of terephthalic acid and dodecandioic acid and 1,4-butanediol, and forms terephthalic acid or an ester thereof. It is obtained by polycondensing a sex derivative, dodecandic acid or an ester-forming derivative thereof, and butanediol or an ester-forming derivative thereof by a commonly known method. Further, other components may be copolymerized.
他の共重合成分としては、テレフタル酸およびドデカン酸以外のジカルボン酸またはそのエステル形成性誘導体、ブタンジオール以外のジオールなどが挙げられる。ジカルボン酸またはそのエステル形成性誘導体としては、例えば、イソフタル酸、ナフタレンジカルボン酸、シクロヘキサンジカルボン酸、４，４’−ジフェノキシエタンジカルボン酸、アジピン酸、セバシン酸やこれらのアルキルエステル等が挙げられる。ジオールとしては、例えば、１，２−ブタンジオール、１，３−ブタンジオール、２，３−ブタンジオール、２−メチル−１，３−プロパンジオール、トリメチレングリコール、プロピレングリコール、ヘキサメチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等が挙げられる。 Examples of other copolymerization components include dicarboxylic acids other than terephthalic acid and dodecanoic acid or ester-forming derivatives thereof, diols other than butanediol, and the like. Examples of the dicarboxylic acid or an ester-forming derivative thereof include isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, 4,4'-diphenoxyetanedicarboxylic acid, adipic acid, sebacic acid and alkyl esters thereof. Examples of the diol include 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, trimethylene glycol, propylene glycol, hexamethylene glycol, and polyethylene. Glycol, polypropylene glycol, polytetramethylene glycol and the like can be mentioned.
本発明の（Ａ）（ポリブチレン（テレフタレート／ドデカジオエート）共重合体を構成する全ジカルボン酸成分中のドデカンジオン酸成分含有率（以下、ドデカンジオン酸含有率とする）は、５〜２０ｍｏｌ％である。ここで、全ジカルボン酸成分とは、ポリブチレンテレフタレート系樹脂を構成するジカルボン酸あるいはそのエステル形成性誘導体の残基を意味する。ドデカンジオン酸成分とは、ポリブチレンテレフタレート系樹脂を構成するドデカンジオン酸あるいはそのエステル形成性誘導体の残基を意味する。ジカルボン酸成分として、ドデカンジオン酸成分を配合することにより、ポリブチレン（テレフタレート／ドデカジオエート）共重合体の固化速度が遅くなる上、分子運動性が向上し柔軟になることで、ブロー成形時の賦形性が良好となる。ドデカンジオン酸含有率が５ｍｏｌ％未満であると、ブロー成形性（賦形性）が低下し、２０ｍｏｌ％を超えると、成形品としたときの剛性が低下する。１０〜１５ｍｏｌ％がより好ましい。 The content of the dodecandionic acid component (hereinafter referred to as the dodecandionic acid content) in the total dicarboxylic acid components constituting the (A) (polybutylene (terephthalate / dodecadioate) copolymer) of the present invention is 5 to 20 mol%. Here, the total dicarboxylic acid component means a residue of dicarboxylic acid or an ester-forming derivative thereof constituting the polybutylene terephthalate resin. The dodecanedioic acid component constitutes the polybutylene terephthalate resin. It means the residue of dodecandioic acid or its ester-forming derivative. By blending the dodecandioic acid component as the dicarboxylic acid component, the solidification rate of the polybutylene (terephthalate / dodecadioate) copolymer is slowed down. As the molecular motility is improved and the material becomes flexible, the formability at the time of blow molding becomes good. If the dodecanedioic acid content is less than 5 mol%, the blow moldability (formability) is lowered. If it exceeds 20 mol%, the rigidity of the molded product decreases. 10 to 15 mol% is more preferable.
本発明に用いられる（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体の製造方法は、特に限定されるものではなく、公知の重縮合法や開環重合法などを挙げることができる。バッチ重合法および連続重合法のいずれでもよく、また、エステル交換反応および直接重合による重縮合反応のいずれも適用することができるが、カルボキシル末端基量を少なくすることができるという点で、連続重合法が好ましく、コストの点で、直接重合法が好ましい。 The method for producing the (A) polybutylene (terephthalate / dodecadioate) copolymer used in the present invention is not particularly limited, and known polycondensation methods and ring-opening polymerization methods can be mentioned. Either the batch polymerization method or the continuous polymerization method may be used, and either the transesterification reaction or the polycondensation reaction by direct polymerization can be applied, but the continuous weight can be reduced in that the amount of carboxyl terminal groups can be reduced. The legal method is preferable, and the direct polymerization method is preferable in terms of cost.
なお、エステル化反応またはエステル交換反応および重縮合反応を効果的に進めるために、これらの反応時に触媒を添加することが好ましい。触媒の具体例としては、有機チタン化合物、スズ化合物、ジルコニア化合物、アンチモン化合物などが挙げられる。これらを２種以上用いてもよい。これらの中でも有機チタン化合物およびスズ化合物が好ましく、有機チタン化合物の中でも、チタン酸のテトラ−ｎ−プロピルエステル、テトラ−ｎ−ブチルエステルおよびテトライソプロピルエステルがより好ましく、チタン酸のテトラ−ｎ−ブチルエステルが特に好ましい。スズ化合物の中では、ジブチルスズオキシド、メチルフェニルスズオキシド、テトラエチルスズが好ましい。触媒の添加量は、機械特性、成形性および色調の点で、（A）ポリブチレン（テレフタレート／ドデカジオエート）共重合体１００重量部に対して、０．００５〜０．５重量部の範囲が好ましく、０．０１〜０．２重量部の範囲がより好ましい。 In order to effectively proceed with the esterification reaction, the transesterification reaction, and the polycondensation reaction, it is preferable to add a catalyst during these reactions. Specific examples of the catalyst include organic titanium compounds, tin compounds, zirconia compounds, antimony compounds and the like. Two or more of these may be used. Among these, organic titanium compounds and tin compounds are preferable, and among the organic titanium compounds, tetra-n-propyl ester of titanium acid, tetra-n-butyl ester and tetraisopropyl ester are more preferable, and tetra-n-butyl of titanoic acid. Esters are particularly preferred. Among the tin compounds, dibutyltin oxide, methylphenyltin oxide and tetraethyltin are preferable. The amount of the catalyst added ranges from 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the (A) polybutylene (terephthalate / dodecadioate) copolymer in terms of mechanical properties, moldability and color tone. It is preferably in the range of 0.01 to 0.2 parts by weight, more preferably.
本発明のＰＢＴ系樹脂組成物は、（Ａ）（ポリブチレン（テレフタレート／ドデカジオエート）共重合体１００重量部に対し、（Ｂ）前記（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体以外の成分を０〜０．１重量部配合してなる。（Ｂ）成分の配合量が０．１重量部を超えると、（Ｂ）成分がガラス繊維などの無機物の場合、薬発第三三六号厚生省薬務局長通知により定められている灰化試験時の残分規格を満たさない。（Ｂ）成分がＰＢＴ以外のポリマーの場合、耐薬品性が低下する。（Ｂ）成分の例としては、（Ａ）成分以外の樹脂（たとえばＰＢＴやＰＢＴ以外の熱可塑性樹脂）、着色剤、可塑剤、抗菌剤、離型剤、滑剤、帯電防止剤、良流動化剤等の各種添加剤などが挙げられる。ただし、（Ｂ）成分を配合する場合には、０．１重量部未満かつ、ＰＢＴ系樹脂組成物として、薬発第三三六号厚生省薬務局長通知により定められている灰化試験時の残分規格を満たすような配合量としなければならない。このため基本的には、（Ｂ）成分は配合しないことが望ましい。 The PBT-based resin composition of the present invention comprises (B) other than the (A) polybutylene (terephthalate / dodecadioate) copolymer with respect to 100 parts by weight of the (A) (polybutylene (terephthalate / dodecadioate) copolymer. When the amount of the component (B) exceeds 0.1 parts by weight, the component (B) is an inorganic substance such as glass fiber. No. 6 Does not meet the residue standard at the time of incineration test specified by the notification of the Director of Pharmaceutical Affairs Bureau, Ministry of Health and Welfare. If the component (B) is a polymer other than PBT, the chemical resistance is lowered. As an example of the component (B) Is a resin other than the component (A) (for example, PBT or a thermoplastic resin other than PBT), a colorant, a plastic agent, an antibacterial agent, a mold release agent, a lubricant, an antioxidant, various additives such as a good fluidizing agent, etc. However, when the component (B) is blended, the ash is less than 0.1 parts by weight and is specified as a PBT-based resin composition by the notification of the Director of Pharmaceutical Affairs Bureau, Ministry of Health and Welfare No. 336. The blending amount must meet the residue standard at the time of the conversion test. Therefore, basically, it is desirable not to blend the component (B).
本発明のＰＢＴ系樹脂組成物の０．５質量％オルトクロロフェノール溶液で測定した２５℃における相対粘度は、１．８５以上である。相対粘度はポリマー溶液と溶媒粘度の比（ηｒ＝η／η０）であり、ウベローデ粘度計を使用してＰＢＴ溶液の流出時間（ｔ）と溶媒の流出時間（ｔ０）を測定し、（１）式より算出する。
ηｒ＝η／η０＝ｔ／ｔ０・・・（１）
The relative viscosity of the PBT-based resin composition of the present invention measured with a 0.5% by mass orthochlorophenol solution at 25 ° C. is 1.85 or more. The relative viscosity is the ratio of the polymer solution to the solvent viscosity (ηr = η / η 0 ), and the outflow time (t) of the PBT solution and the outflow time of the solvent (t 0 ) were measured using an Ubbelohde viscous meter. Calculate from equation 1).
ηr = η / η 0 = t / t 0 ... (1)
このような手法で測定した相対粘度が、１．８５以上であると、溶融パリソンのドローダウンが抑制され、ブロー成形性が良好である。一方、１．８５未満であると、溶融パリソンのドローダウンが起こりやすくブロー成形性が低下する。１．９〜７．０がより好ましい。ＰＢＴ重合時の温度、反応時間を調整することにより、相対粘度が１．８５以上であるＰＢＴ系樹脂組成物を得ることができる。 When the relative viscosity measured by such a method is 1.85 or more, the drawdown of the molten parison is suppressed and the blow moldability is good. On the other hand, if it is less than 1.85, drawdown of the molten parison is likely to occur and the blow moldability is lowered. 1.9 to 7.0 is more preferable. By adjusting the temperature and reaction time during PBT polymerization, a PBT-based resin composition having a relative viscosity of 1.85 or more can be obtained.
本発明のＰＢＴ系樹脂組成物は、示差走査熱量計（ＤＳＣ）を用いて窒素雰囲気下で４０℃から２６０℃まで２０℃／分の速度で昇温した時に観測される吸熱ピークが一つで、その吸熱ピーク温度（融点）が２００〜２２０℃の範囲である。融点が２００℃未満であると、成形品としての耐熱性が低下する。融点が２２０℃を超えると、ブロー成形時により高い温度で溶解させる必要があり、パリソンのドローダウンが起こりやすくなる。また、融点とともに結晶化温度も高くなるため、賦形性が悪化する。２００〜２１０℃がより好ましい。（Ａ）（ポリブチレン（テレフタレート／ドデカジオエート）共重合体を構成する全ジカルボン酸成分中のドデカンジオン酸含有率を、５〜２０ｍｏｌ％の範囲とすることで、吸熱ピーク温度が２００〜２２０℃であるＰＢＴ系樹脂組成物を得ることができる。 The PBT-based resin composition of the present invention has one endothermic peak observed when the temperature is raised from 40 ° C. to 260 ° C. at a rate of 20 ° C./min under a differential scanning calorimeter (DSC) using a differential scanning calorimeter (DSC). The endothermic peak temperature (melting point) is in the range of 200 to 220 ° C. If the melting point is less than 200 ° C., the heat resistance of the molded product is lowered. If the melting point exceeds 220 ° C., it needs to be melted at a higher temperature during blow molding, and the drawdown of the parison is likely to occur. In addition, the crystallization temperature rises with the melting point, so that the shapeability deteriorates. More preferably, it is 200 to 210 ° C. (A) The endothermic peak temperature is 200 to 220 ° C. by setting the dodecandioic acid content in the total dicarboxylic acid components constituting the polybutylene (terephthalate / dodecadioate) copolymer in the range of 5 to 20 mol%. A PBT-based resin composition is obtained.
本発明のＰＢＴ系樹脂組成物は、（Ａ）（ポリブチレン（テレフタレート／ドデカジオエート）共重合体のカルボキシル末端基濃度が３０当量／ｔ以下であることが好ましい。カルボキシル末端基濃度が３０当量／ｔ以下であると、成形品とした際の耐湿熱性に優れる。より好ましくは、２５当量／ｔ以下である。 In the PBT-based resin composition of the present invention, the carboxyl terminal group concentration of the (A) (polybutylene (terephthalate / dodecadioate) copolymer is preferably 30 equivalents / t or less. The carboxyl terminal group concentration is 30 equivalents / t. When it is t or less, it is excellent in moisture and heat resistance when it is made into a molded product. More preferably, it is 25 equivalents / t or less.
本発明のＰＢＴ系樹脂組成物は、ＩＳＯ１７８に準拠して測定した曲げ弾性率が２５０〜１５００ＭＰａの範囲であることが好ましい。曲げ弾性率が２５０ＭＰａ以上であれば、成形品とした際の形状保持力が十分であり、１５００ＭＰａ以下であれば、点眼薬容器や洗剤ボトル容器のような成形品とした際、容器胴体を押して内容物を出すときのスクイズ性が良好といえる。より好ましくは、４００〜８００ＭＰａの範囲である。 The PBT-based resin composition of the present invention preferably has a flexural modulus in the range of 250 to 1500 MPa measured in accordance with ISO178. If the flexural modulus is 250 MPa or more, the shape holding force when made into a molded product is sufficient, and if it is 1500 MPa or less, the container body is pushed when made into a molded product such as an eye drop container or a detergent bottle container. It can be said that the squeeze property when putting out the contents is good. More preferably, it is in the range of 400 to 800 MPa.
本発明のＰＢＴ系樹脂組成物は、（Ｂ）前記（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体以外の成分を極力配合しないことが望ましいが、例えば、化粧品ボトルのような意匠性を重視する成形品として用いる場合には、成形加工の工程で顔料、染料などの着色剤を配合してもよい。 It is desirable that the PBT-based resin composition of the present invention does not contain components other than (B) the polybutylene (terephthalate / dodecadioate) copolymer (B) as much as possible, but for example, it has a design like a cosmetic bottle. When used as an important molded product, a colorant such as a pigment or a dye may be blended in the molding process.
本発明のＰＢＴ系樹脂組成物は、公知のブロー成形、押出成形、プレス成形、射出成形、紡糸などの任意の方法で成形することにより、各種成形部品に加工し利用することができる。成形部品としては例えば、ブロー成形部品、押出成形部品、フィルム、シート、射出成形部品、繊維などが挙げられる。本発明のＰＢＴ樹脂組成物は、特にブロー成形において好適に用いることができる。ブロー成形の方法としては、インジェクションブロー成形、ダイレクトブロー成形などが挙げられる。 The PBT-based resin composition of the present invention can be processed into various molded parts and used by molding by any known method such as blow molding, extrusion molding, press molding, injection molding, and spinning. Examples of molded parts include blow molded parts, extrusion molded parts, films, sheets, injection molded parts, fibers and the like. The PBT resin composition of the present invention can be suitably used particularly in blow molding. Examples of the blow molding method include injection blow molding and direct blow molding.
本発明において、上記各種成形品は、食品、洗剤、化粧品、医薬・医療用途をはじめ、日用品、生活雑貨および衛生用品、自動車部材、電気・電子部材、建築部材など各種用途に利用することができる。特に、本発明のＰＢＴ系樹脂組成物は、ブロー成形性に優れ、耐衝撃性、耐薬品性に優れた成形品を得ることができるため、食品、化粧品、洗剤、医療・医薬用途等における容器あるいは包装材料等として好適に用いられる。食品用途としては、調味液ボトル、清涼飲料ボトル、香料ボトル等が挙げられる。医療・医薬用途としては、具体的には液体飲み薬用容器、点眼薬用容器、のど用に噴霧するミストボトルなどの投薬瓶、注射製剤用容器等の薬品用容器が挙げられる。また、ブロー成形の他に押出成形性も良好であることから、フィルム、シート、チューブ等として、鋼板用フィルムや、自動車塗装工程のマスキングフィルム、カテーテルなどの用途に好適に用いられる。 In the present invention, the various molded products can be used for various purposes such as foods, detergents, cosmetics, pharmaceuticals / medical applications, daily necessities, household goods and hygiene products, automobile parts, electric / electronic parts, and building parts. .. In particular, since the PBT-based resin composition of the present invention can obtain a molded product having excellent blow moldability, impact resistance, and chemical resistance, it is a container for foods, cosmetics, detergents, medical / pharmaceutical applications, and the like. Alternatively, it is preferably used as a packaging material or the like. Examples of food applications include seasoning liquid bottles, soft drink bottles, and flavor bottles. Specific examples of medical / pharmaceutical applications include liquid swallowing medicine containers, eye drops medicine containers, medication bottles such as mist bottles sprayed for the throat, and medicine containers such as injection preparation containers. Further, since it has good extrusion moldability in addition to blow molding, it is suitably used as a film for steel plates, masking films in automobile painting processes, catheters, etc. as films, sheets, tubes, and the like.
以下に、実施例を挙げて本発明をさらに詳細に説明する。実施例、比較例で使用する原料の略号および内容を以下に示す。 Hereinafter, the present invention will be described in more detail with reference to examples. The abbreviations and contents of the raw materials used in Examples and Comparative Examples are shown below.
（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体
（Ａ−１）ドデカンジオン酸含有量１３ｍｏｌ％共重合ＰＢＴ樹脂：
テレフタル酸１０６．２重量部、ドデカンジオン酸２２．０重量部、１，４−ブタンジオール８４．１重量部および触媒としてテトラブチルチタネート０．０８重量部、モノブチルスズオキシド０．０７重量部とを精留塔および撹拌機のついた反応缶に仕込み、常圧下にて１５０℃から２３５℃まで４時間かけて昇温し、エステル化反応させた。生成した水とテトラヒドロフランとを精留塔を通して留去してテトラヒドロフラン含有物を得た。次に得られたエステル化反応生成物に着色防止剤のリン酸０．０３重量部と重縮合触媒のテトラブチルチタネート０．０８重量部を加えた後、重縮合反応缶に移し、常圧から６７Ｐａまで５０分かけて徐々に減圧し、同時に２４５℃まで昇温して、２時間５０分重縮合反応を行い、０．５質量％オルトクロロフェノール溶液で測定した２５℃における相対粘度が１．４８であり、ドデカンジオン酸含有量が１３ｍｏｌ％である共重合ポリブチレンテレフタレート樹脂を得た。得られた共重合体を真空乾燥器内に仕込み、真空度７６０ｍｍＨｇ、１６０℃の条件で８０時間固相重合を行った。得られた共重合体の０．５質量％オルトクロロフェノール溶液で測定した２５℃における相対粘度は２．０１であった。
（Ａ−２）ドデカンジオン酸含有量６ｍｏｌ％共重合ＰＢＴ樹脂：ドデカンジオン酸の配合量を９．４重量部とする他は、（Ａ−１）と同様にして調製した。
（Ａ−３）ドデカンジオン酸含有量１０ｍｏｌ％共重合ＰＢＴ樹脂：ドデカンジオン酸の配合量を１６．４重量部とする他は、（Ａ−１）と同様にして調整した。
（Ａ−４）ドデカンジオン酸含有量１５ｍｏｌ％共重合ＰＢＴ樹脂：ドデカンジオン酸の配合量を２６．０重量部とする他は、（Ａ−１）と同様にして調整した。
（Ａ−５）ドデカンジオン酸含有量２０ｍｏｌ％共重合ＰＢＴ樹脂：ドデカンジオン酸の配合量を３６．８重量部とする他は、（Ａ−１）と同様にして調整した。
（Ａ−６）ドデカンジオン酸含有量１３ｍｏｌ％共重合ＰＢＴ樹脂（相対粘度１．８８）：固相重合の反応時間を７０時間とする他は、（Ａ−１）と同様にして調整した。
（Ａ’−１）ドデカンジオン酸含有量４ｍｏｌ％共重合ＰＢＴ樹脂：ドデカンジオン酸の配合量を６．１重量部とする他は、（Ａ−１）と同様にして調整した。
（Ａ’−２）ドデカンジオン酸含有量２２ｍｏｌ％共重合ＰＢＴ樹脂：ドデカンジオン酸の配合量を４１．５重量部とする他は、（Ａ−１）と同様にして調整した。
（Ａ’−３）ドデカンジオン酸含有量１３ｍｏｌ％共重合ＰＢＴ樹脂（相対粘度１．４８）：（Ａ−１）の調整過程で得られる相対粘度１．４８のドデカンジオン酸含有量１３ｍｏｌ％共重合ＰＢＴ樹脂を使用した。
（Ａ’−４）ドデカンジオン酸含有量１３ｍｏｌ％共重合ＰＢＴ樹脂（相対粘度１．８４）：固相重合の反応時間を６５時間とする他は、（Ａ−１）と同様にして調整した。
(A) Polybutylene (terephthalate / dodecadioate) copolymer (A-1) Dodecaneic acid content 13 mol% Copolymerized PBT resin:
106.2 parts by weight of terephthalic acid, 22.0 parts by weight of dodecandionic acid, 84.1 parts by weight of 1,4-butanediol and 0.08 parts by weight of tetrabutyl titanate and 0.07 parts by weight of monobutyltin oxide as a catalyst. The mixture was placed in a reaction can equipped with a rectification tower and a stirrer, and the temperature was raised from 150 ° C. to 235 ° C. over 4 hours under normal pressure for an esterification reaction. The generated water and tetrahydrofuran were distilled off through a rectification column to obtain a tetrahydrofuran-containing substance. Next, 0.03 part by weight of phosphoric acid as a color inhibitor and 0.08 part by weight of tetrabutyl titanate as a polycondensation catalyst were added to the obtained esterification reaction product, and the mixture was transferred to a polycondensation reaction can and subjected to normal pressure. The pressure was gradually reduced to 67 Pa over 50 minutes, the temperature was raised to 245 ° C at the same time, the polycondensation reaction was carried out for 2 hours and 50 minutes, and the relative viscosity at 25 ° C measured with a 0.5 mass% orthochlorophenol solution was 1. A copolymerized polybutylene terephthalate resin having a dodecandonic acid content of 13 mol% was obtained. The obtained copolymer was charged in a vacuum dryer and subjected to solid-phase polymerization for 80 hours under the conditions of a vacuum degree of 760 mmHg and 160 ° C. The relative viscosity of the obtained copolymer at 25 ° C. measured with a 0.5% by mass orthochlorophenol solution was 2.01.
(A-2) Dodecaneic acid content 6 mol% copolymerized PBT resin: Prepared in the same manner as in (A-1) except that the blending amount of dodecaneic acid was 9.4 parts by weight.
(A-3) Dodecaneic acid content 10 mol% copolymerized PBT resin: Adjusted in the same manner as in (A-1) except that the blending amount of dodecaneic acid was 16.4 parts by weight.
(A-4) Dodecaneic acid content 15 mol% copolymerized PBT resin: The amount of dodecaneic acid was adjusted to 26.0 parts by weight in the same manner as in (A-1).
(A-5) Dodecaneic acid content 20 mol% copolymerized PBT resin: The amount of dodecaneic acid was adjusted to 36.8 parts by weight in the same manner as in (A-1).
(A-6) Dodecanedic acid content 13 mol% copolymerized PBT resin (relative viscosity 1.88): Adjusted in the same manner as in (A-1) except that the reaction time for solid phase polymerization was 70 hours.
(A'-1) Dodecaneic acid content 4 mol% copolymerized PBT resin: The amount of dodecaneic acid was adjusted to 6.1 parts by weight in the same manner as in (A-1).
(A'-2) Dodecaneic acid content 22 mol% copolymerized PBT resin: The amount of dodecaneic acid was adjusted to 41.5 parts by weight in the same manner as in (A-1).
(A'-3) Dodecaneic acid content 13 mol% Copolymerized PBT resin (relative viscosity 1.48): Dodecaneic acid content 13 mol% with relative viscosity 1.48 obtained in the adjustment process of (A-1) A polymerized PBT resin was used.
(A'-4) Dodecaneic acid content 13 mol% copolymerized PBT resin (relative viscosity 1.84): Adjusted in the same manner as in (A-1) except that the reaction time for solid phase polymerization was 65 hours. ..
（Ｂ）（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体以外の成分
（Ｂ−１）ポリブチレン（テレフタレート／イソフタレート）共重合体（ＰＢＴ−Ｉ）：テレフタル酸６５．６重量部、イソフタル酸７．３重量部、１，４−ブタンジオール６１．４重量部および触媒としてテトラブチルチタネート０．０５重量部、モノブチルスズオキシド０．０４重量部とを精留塔および撹拌機のついた反応缶に仕込み、常圧下にて１５０℃から２３５℃まで４時間かけて昇温し、エステル化反応をさせた。生成した水とテトラヒドロフランとを精留塔を通して留去してテトラヒドロフラン含有物を得た。次に得られたエステル化反応生成物に着色防止剤のリン酸０．０２重量部と重縮合触媒のテトラブチルチタネート０．０５重量部を加えた後、重縮合反応缶に移し、常圧から６７Ｐａまで５０分かけて徐々に減圧し、同時に２４５℃まで昇温して、２時間５０分重縮合反応を行い、イソフタル酸（ＩＰＡ）含有量が１０ｍｏｌ％である共重合ポリブチレンテレフタレート樹脂を得た。得られた共重合体を真空乾燥器内に仕込み、真空度７６０ｍｍＨｇ、１６０℃の条件で８０時間固相重合を行った。得られた共重合体の０．５質量％オルトクロロフェノール溶液で測定した２５℃における相対粘度は２．０１であった。
（Ｂ−２）ポリブチレンテレフタレート：０．５質量％オルトクロロフェノール溶液で測定した２５℃における粘度が１．８８であるＰＢＴを使用した。
（Ｂ−３）ポリカーボネート：三菱エンジニアリングプラスチックス（株）製“ユーピロン” （登録商標）S−１０００（商品名）
（Ｂ−４）ステアリン酸カルシウム：川村化成工業（株）製のステアリン酸カルシウムを用いた。
（Ｂ）成分を配合する場合は、ペレット形状の（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体に対し、所定量の（Ｂ）をペレットブレンドもしくはドライブレンドにより混合した。
(B) (A) Components other than polybutylene (terephthalate / dodecadioate) copolymer (B-1) Polybutylene (terephthalate / isophthalate) copolymer (PBT-I): 65.6 parts by weight of terephthalic acid, isophthalic acid Reaction of 7.3 parts by weight of acid, 61.4 parts by weight of 1,4-butanediol and 0.05 parts by weight of tetrabutyl titanate and 0.04 parts by weight of monobutyltin oxide as a catalyst with a rectification column and a stirrer. It was charged into a can and heated from 150 ° C. to 235 ° C. over 4 hours under normal pressure to cause an esterification reaction. The generated water and tetrahydrofuran were distilled off through a rectification column to obtain a tetrahydrofuran-containing substance. Next, 0.02 parts by weight of phosphoric acid as a color inhibitor and 0.05 parts by weight of tetrabutyl titanate as a polycondensation catalyst were added to the obtained esterification reaction product, and the mixture was transferred to a polycondensation reaction can and subjected to normal pressure. The pressure was gradually reduced to 67 Pa over 50 minutes, and at the same time, the temperature was raised to 245 ° C., and a polycondensation reaction was carried out for 2 hours and 50 minutes to obtain a copolymer polybutylene terephthalate resin having an isophthalic acid (IPA) content of 10 mol%. It was. The obtained copolymer was charged in a vacuum dryer and subjected to solid-phase polymerization for 80 hours under the conditions of a vacuum degree of 760 mmHg and 160 ° C. The relative viscosity of the obtained copolymer at 25 ° C. measured with a 0.5% by mass orthochlorophenol solution was 2.01.
(B-2) Polybutylene terephthalate: PBT having a viscosity of 1.88 at 25 ° C. measured with a 0.5 mass% orthochlorophenol solution was used.
(B-3) Polycarbonate: "Iupilon" manufactured by Mitsubishi Engineering Plastics Co., Ltd. (registered trademark) S-1000 (trade name)
(B-4) Calcium stearate: Calcium stearate manufactured by Kawamura Kasei Kogyo Co., Ltd. was used.
When the component (B) was blended, a predetermined amount of (B) was mixed with the pellet-shaped (A) polybutylene (terephthalate / dodecadioate) copolymer by pellet blending or dry blending.
実施例および比較例におる評価方法を以下にまとめて示す。 The evaluation methods in Examples and Comparative Examples are summarized below.
（１）ブロー成形性
タハラ製電動ブロー成形機”ＴＺ−３５３２Ｍ”（スクリュ径３５ｍｍ）を用い、各実施例および比較例で得られたＰＢＴ系樹脂組成物をシリンダ温度２４５℃、ダイ温度２１５℃の条件で、外径２０ｍｍ、厚み３ｍｍのパリソンとして４０ｒｐｍの速度で押し出し、さらに吹き込み圧０．６MPa、吹き込み時間１５秒の条件で空気の吹きこみを行い、高さ９０ｍｍ、直径３６ｍｍの円柱型容器を作成した。この際、目視でパリソンが大きくドローダウンしたものは、成形性不良として表中「×」で示した。また、パリソン押出し直後に、ダイ付近で固化が始まったものや、吹き込み後に、成形品の透明性に差（肉厚のばらつき）があったものは、賦形性不良として表中「×」で示した。ドローダウンが起こらず、賦形性良好なものは「〇」で示した。
(1) Blow Moldability Using a Tahara electric blow molding machine "TZ-3532M" (screw diameter 35 mm), the PBT resin compositions obtained in each Example and Comparative Example were subjected to a cylinder temperature of 245 ° C. and a die temperature of 215 ° C. Under the conditions of, extrude as a parison with an outer diameter of 20 mm and a thickness of 3 mm at a speed of 40 rpm, and then blow air under the conditions of a blow pressure of 0.6 MPa and a blow time of 15 seconds. A cylindrical container with a height of 90 mm and a diameter of 36 mm. It was created. At this time, those in which the parison was visually drawn down significantly were indicated by "x" in the table as poor moldability. In addition, those that started to solidify near the die immediately after parison extrusion and those that had a difference in transparency (variation in wall thickness) of the molded product after blowing were marked with "x" in the table as poor shapeability. Indicated. Those with good shapeability without drawdown are indicated by "○".
（２）耐衝撃性
住友重工業製射出成形機“ＳＥ７５ＤＵ”を使用して、各実施例および比較例で得られたＰＢＴ樹脂組成物を用いて、シリンダ温度２６０℃、金型温度８０℃の条件で、ＩＳＯ１７９に従って試験片（８０ｍｍ×１０ｍｍ×４．０ｍｍ）を成形した。得られた試験片各５本に、８ｍｍ残るようにノッチを入れ、ＩＳＯ１７９に準拠してシャルピー衝撃強度を測定した。得られた衝撃強度を試験片の厚みと幅の積で割った値を、シャルピー衝撃強度とした。シャルピー衝撃強度が5０ｋＪ／ｍ２以上であれば、耐衝撃性は良好といえる。１0０ｋＪ／ｍ２以上が望ましい。
(2) Impact resistance Using the injection molding machine "SE75DU" manufactured by Sumitomo Heavy Industries, Ltd., using the PBT resin compositions obtained in each Example and Comparative Example, the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Then, a test piece (80 mm × 10 mm × 4.0 mm) was molded according to ISO179. Each of the five test pieces obtained was notched so as to remain 8 mm, and the Charpy impact strength was measured in accordance with ISO179. The value obtained by dividing the obtained impact strength by the product of the thickness and width of the test piece was taken as the Charpy impact strength. If the Charpy impact strength is 50 kJ / m 2 or more, it can be said that the impact resistance is good. It is preferably 100 kJ / m 2 or more.
（３）耐薬品性
日精樹脂工業射出成形機“ＰＳ４０”を使用して、各実施例および比較例で得られたＰＢＴ樹脂組成物を用い、短冊状試験片（１２７ｍｍ×１２．７ｍｍ×１．５ｍｍ）を成形した。射出条件は、シリンダ温度２７０℃、金型温度５０℃、射出時間１０秒、冷却時間１０秒、射出圧力は各樹脂組成物の下限圧力＋７ＭＰａで実施した。得られた試験片をリモネン原液に４８時間浸漬し、浸漬前後の重量から重量変化率を算出した。重量変化率が、０．１％以下であれば耐薬品性は良好といえる。
(3) Chemical resistance Using the injection molding machine "PS40" of Nissei Resin Industry Co., Ltd., and using the PBT resin compositions obtained in each Example and Comparative Example, a strip-shaped test piece (127 mm × 12.7 mm × 1. 5 mm) was molded. The injection conditions were a cylinder temperature of 270 ° C., a mold temperature of 50 ° C., an injection time of 10 seconds, a cooling time of 10 seconds, and an injection pressure of the lower limit pressure of each resin composition + 7 MPa. The obtained test piece was immersed in a limonene stock solution for 48 hours, and the weight change rate was calculated from the weight before and after the immersion. If the weight change rate is 0.1% or less, it can be said that the chemical resistance is good.
（４）曲げ弾性率
住友重工業製射出成形機“ＳＥ７５ＤＵ”を使用して、各実施例および比較例で得られたＰＢＴ樹脂組成物を用いて、シリンダ温度２６０℃、金型温度８０℃の条件で、ＩＳＯ１７８に従って試験片（８０ｍｍ×１０ｍｍ×４．０ｍｍ）を成形した。得られた試験片各５本を用いて、ＩＳＯ１７８に準拠して曲げ弾性率を測定した。
(4) Bending elastic modulus Using the injection molding machine "SE75DU" manufactured by Sumitomo Heavy Industries, Ltd., using the PBT resin compositions obtained in each Example and Comparative Example, the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Then, a test piece (80 mm × 10 mm × 4.0 mm) was molded according to ISO178. The flexural modulus was measured according to ISO178 using each of the five test pieces obtained.
（５）カルボキシル末端基濃度
各実施例および比較例で得られたＰＢＴ樹脂組成物を、ｏ−クレゾール／クロロホルム（２／１，ｖｏｌ／ｖｏｌ）混合溶液５０ｍＬに溶解させた溶液を、１％ブロモフェノールブルーを指示薬として、０．０５ｍｏｌ／Ｌエタノール性水酸化カリウムで滴定し、組成物中のカルボキシル末端基濃度を算出した。
(5) Carboxyl end group concentration A solution prepared by dissolving the PBT resin compositions obtained in each Example and Comparative Example in 50 mL of an o-cresol / chloroform (2/1, vol / vol) mixed solution is 1% bromo. Using phenol blue as an indicator, titration was carried out with 0.05 mol / L ethanolic potassium hydroxide, and the concentration of carboxyl terminal groups in the composition was calculated.
［実施例１〜７］
表１に示すＰＢＴ系樹脂組成物について、上記方法で評価した結果を表１に記した。
[Examples 1 to 7]
The results of evaluation of the PBT-based resin compositions shown in Table 1 by the above method are shown in Table 1.
得られたＰＢＴ系樹脂組成物は、いずれもブロー成形性優れ、耐衝撃性、耐薬品性に優れた成形品を得ることができた。実施例１〜４に示すように、ポリブチレン（テレフタレート／ドデカジオエート）共重合体の全ジカルボン酸成分中のドデカンジオン酸含有率が高いほど融点が低下し、成形品の耐衝撃性が向上した。また、ドデカンジオン酸含有率が低いほど耐薬品性が向上した。実施例５に示すように、（Ｂ）（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体以外の成分を０．１重量部以下で配合した場合、耐薬品性が良好である。実施例５に示す滑剤を配合した場合は、ブロー成形機投入時のペレットの噛み込み安定性が良好である。実施例６、７に示すように、相対粘度が高いほどブロー成形性、成形品の耐衝撃性が向上した。実施例７は、ブロー成形性、成形品の耐衝撃性、耐薬品性のバランスが最も優れたものであった。 All of the obtained PBT-based resin compositions were able to obtain molded products having excellent blow moldability, impact resistance, and chemical resistance. As shown in Examples 1 to 4, the higher the dodecandioic acid content in the total dicarboxylic acid component of the polybutylene (terephthalate / dodecadioate) copolymer, the lower the melting point and the better the impact resistance of the molded product. .. In addition, the lower the dodecanedic acid content, the better the chemical resistance. As shown in Example 5, when components other than the (B) and (A) polybutylene (terephthalate / dodecadioate) copolymers are blended in an amount of 0.1 parts by weight or less, the chemical resistance is good. When the lubricant shown in Example 5 is blended, the biting stability of the pellets when the blow molding machine is charged is good. As shown in Examples 6 and 7, the higher the relative viscosity, the better the blow moldability and the impact resistance of the molded product. In Example 7, the balance between blow moldability, impact resistance of the molded product, and chemical resistance was the best.
［比較例１〜７］
表２に示す配合組成に変更した以外は実施例１〜７と同様に評価し、結果を表２に記した。
[Comparative Examples 1 to 7]
Evaluation was carried out in the same manner as in Examples 1 to 7 except that the composition was changed to the composition shown in Table 2, and the results are shown in Table 2.
比較例１、２に示すように、（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体の全ジカルボン酸成分中のドデカンジオン酸含有率が５ｍoｌ％未満であると、ブロー成形時の賦形性、耐衝撃性が低下した。一方、２０ｍoｌ％を超えると、成形品の耐薬品性が低下した。また融点が２００℃を下回り、成形品としての耐熱性が低下した。比較例３に示すように、（Ｂ）（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体以外の成分を０．１重量部以上配合すると、耐薬品性が低下した。比較例４、５に示すように、（Ａ）ポリブチレン（テレフタレート／ドデカジオエート）共重合体以外のＰＢＴ系樹脂を用いた場合、耐衝撃性が低下した。比較例６、７に示すように、相対粘度が１．８５未満であると、パリソンがドローダウンしブロー成形性が低下した。 As shown in Comparative Examples 1 and 2, when the dodecandioic acid content in the total dicarboxylic acid component of the (A) polybutylene (terephthalate / dodecadioate) copolymer is less than 5 mol%, the shaping at the time of blow molding The property and impact resistance were reduced. On the other hand, when it exceeds 20 mol%, the chemical resistance of the molded product is lowered. Further, the melting point was lower than 200 ° C., and the heat resistance of the molded product was lowered. As shown in Comparative Example 3, when 0.1 part by weight or more of the components other than the (B) and (A) polybutylene (terephthalate / dodecadioate) copolymer was blended, the chemical resistance was lowered. As shown in Comparative Examples 4 and 5, when a PBT resin other than the (A) polybutylene (terephthalate / dodecadioate) copolymer was used, the impact resistance was lowered. As shown in Comparative Examples 6 and 7, when the relative viscosity was less than 1.85, the parison was drawn down and the blow moldability was lowered.
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