JPH0543749B2 - - Google Patents
Info
- Publication number
- JPH0543749B2 JPH0543749B2 JP59089548A JP8954884A JPH0543749B2 JP H0543749 B2 JPH0543749 B2 JP H0543749B2 JP 59089548 A JP59089548 A JP 59089548A JP 8954884 A JP8954884 A JP 8954884A JP H0543749 B2 JPH0543749 B2 JP H0543749B2
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene terephthalate
- glycol
- component
- weight
- acid
- 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.)
- Expired - Lifetime
Links
- -1 polyethylene terephthalate Polymers 0.000 claims description 30
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 21
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920000620 organic polymer Polymers 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000010954 inorganic particle 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
- 239000012046 mixed solvent Substances 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-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 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical group C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920008651 Crystalline Polyethylene terephthalate Polymers 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000011162 core material Substances 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 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
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
本発明は、射出成形用途において有用な結晶化
速度の速い結晶性ポリエチレンテレフタレート樹
脂組成物に関する。ポリエチレンテレフタレート
は、その優れた性質を生かして繊維、フイルム、
ボトル等の分野に広く使用されているが、こと射
出成形分野についてみると本来極めて優れた成形
材料となる可能性を有しているにもかかわらず、
それ程使用されていない。これはポリエチレンテ
レフタレートの低温での結晶化速度が遅いため、
射出成形時に金型温度を160℃以上に保持する必
要があり、このような高い金型温度では成形サイ
クルが著しく長くなり生産上好ましくない事情に
よる。成形サイクルを短縮するため、金型温度を
100℃近くに設定すると結晶化がほとんど進行せ
ず、成形品の機械的性質、寸法安定性、表面外観
が極めて悪い。
このような欠点を改良すべく従来より種々の方
法が提案されている。例えば、特公昭44−7542号
公報にはタルクを代表例とする無機粒子やステア
リン酸ソーダ等の有機酸塩がポリエチレンテレフ
タレートの結晶化速度を速くする事が示されい
る。かかる方法により金型温度は低下させること
が出来るものの、依然として150〜130℃の高温が
必要であり、余り実用上歓迎されていない。
また、特公昭47−3027号公報には、タルク等の
無機粒子に、一般式R1−O〔―R2−O〕o――R1(ここ
でR1は、C1〜C10の芳香族、脂肪族、それらの組
合せよりなる炭化水素基、またはその一部に窒
素、硫黄、リン、酸素を含む炭化水素系有機基、
R2は、C2〜C22の脂肪族系炭化水素または連鎖〔−
R2−O〕o−−の一部もしくは全部のR2に窒素、酸
素、リン、硫黄を含む脂肪族炭化水素系有機基、
nは1〜200の整数である。)で示される分子量
100以上の化合物を配合し、ポリエチレンテレフ
タレートの結晶化を促進する方法が示されてい
る。
本方法は確かに金型温度を低下させる良い方法
であるが100℃以下に低下させようとすると、一
般式R1−O〔−R2−O〕―R1で示される化合物を多
量に配合する必要があり、それに伴い該配合物が
ブリードアウトしたり、組成物の一般機械物性を
低下させる。また、ブリードアウトを無くするた
めに該配合物の分子量を大きくするとポリエチレ
ンテレフタレートとの相溶性が悪くなり組成物の
一般機械物性を低下させるという欠点があつた。
本発明者等は、上記の如き従来技術の有する欠
点を解消すべく鋭意研究の結果、これら問題点を
解消した本発明の組成物に到達した。
すなわち本発明は、
(A) 成分:
ポリエチレンテレフタレート100重量部と、
(B) 成分:
一般式
で示される有機重合体1〜20重量部
〔式中、R1は炭素数2〜5のアルキレン基、
R2は炭素数1以上の脂肪族、脂環式、芳香族
またはそれらの組合せよりなる炭化水素基、も
しくはその一部に窒素、硫黄、リン、酸素、ハ
ロゲンを含む炭化水素系末端基、R3は水素ま
たはメチル基、nは1〜50の整数、mは10〜
200の整数である。〕
とを混練してなるポリエチレンテレフタレート樹
脂組成物である。
次に本発明を詳細に説明する。本発明の(A)成分
として使用されるポリエチレンテレフタレートと
は、エチレンテレフタレートの繰返し単位を主体
とするポリエステルである。
一般にポリエチレングリコール、テレフタレー
ト酸を用いて製造され、結晶性を損わない範囲で
他の酸成分、グリコール成分を共重合させても良
い。酸成分としてはイソフタル酸、ナフタレンジ
カルボン酸、アジピン酸、セバシン酸およびシク
ロヘキサンジカルボン酸等のジカルボン酸、グリ
コール成分としてはトリメチレングリコール、テ
トラメチレングリコール、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、ポ
リエチレングリコールとポリプロピレングリコー
ルの共重合体等を挙げる事が出来る。
一般に、酸成分およびグリコール成分の少なく
とも80モル%、好ましくは90モル%以上がそれぞ
れエチレングリコール、テレフタール酸であるも
のが用いられ、好ましくは少なくとも80モル%以
上、さらに好ましくは90モル%以上のエチレンテ
レフタレート繰返し単位を含むポリエチレンテレ
フタレートが用いられる。
この(A)成分のポリエチレンテレフタレートは、
フエノールとテトラクロルエタンの1:1重量比
混合溶媒中で30℃で測定した固有粘度が0.3以上、
好ましくは0.5以上のもので、溶融重縮合反応、
またはこれと固相重合反応の組合された方法で製
造される。
(B)成分は、一般式
で示される有機重合体で、R1は炭素数2〜5の
アルキレン基、R2は炭素数1以上の脂肪族、脂
環式、芳香族またはそれらの組合せよりなる炭化
水素基、もしくはその一部に窒素、硫黄、リン、
酸素、ハロゲンを含む炭化水素系末端基、R3は
水素またはメチル基、nは1〜50、好ましくは2
〜30、mは20〜200の整数である。
かかる重合体は、次の単量体を重合することに
よつて得ることができる。それにはポリエチレン
グリコールモノメチルエール(メタ)アクリレー
ト、ポリプロピレングリコールモノメチルエーテ
ル(メタ)アクリレート、ポリテトラメチレング
リコールモノエチルエーテル(メタ)アクリレー
ト、エチレングリコールとプロピレングリコール
の共重合体のモノメチルエーテル(メタ)アクリ
レート等の(ポリ)アルキレングリコールモノア
ルキルエーテル(メタ)アクリレート類や、フエ
ノキシポリアルキレングリコール(メタ)アクリ
レートがある。
ここで言う有機重合体としては、10〜200量体
が用いられる。
かかる(B)成分の有機重合体は、その単量体の重
合性能に応じ無触媒熱重合、ラジカル重合、カチ
オン重合、アニオン重合、配位重合等適宜選択す
る方法で重合する事が出来る。
その配合量はポリエチレンテレフタレート100
重量部に対し1〜20重量部であり、1重量部に満
たざる場合は本発明の効果はなく、また20重量部
を越えると機械的性質や耐熱性の低下を招き好ま
しくない。
本発明により、前記従来技術の有する欠点、す
なわち、金型温度を低下させるために配合物の添
加量を増加させると該配合物がブリードアウトし
たり、またそれを押える目的で該配合物の分子量
を増加させるとポリエチレンテレフタレートとの
相溶性が低下し、結果として組成物の一般機械物
性が低下する事が改良される。その理由は定かで
ないが、一般式〔―R1−O〕―R2で示される低分子
アルキレングリコール鎖を側鎖に有しつつ高分子
量化することによりポリエチレンテレフタレート
への相溶性は側鎖で維持されつつ高分子化されて
いるため多量に配合してもブリードアウトや一般
機械物性を著しく低下させない事にあると推定さ
れる。本発明は従来使用されている核材、結晶化
促進剤を併用することにより一層の効果を期待す
ることが出来る。これらの核剤、結晶化促進剤と
しては、例えばタルク、クルー、マイカ、シリ
カ、等の無機化合物、ステアリン酸、モンタン
酸、エチレンとメタアクリル酸共重合体等のアル
カリ金属塩等が挙げられる。
本発明のポリエチレンテレフタレートにはガラ
ス繊維、炭素繊維、ワラストナイト、ウイスカー
等の強化剤を加える事が出来る。特に、ガラス繊
維を全組成物中5〜60重量%加える事は機械的性
質を著しく向上させ好ましい。
更に、本発明は難燃剤、紫外線吸収剤、酸化防
止剤、着色剤、耐加水分解剤を配合しても良い。
更にまた、他の熱可塑性樹脂、例えばポリエチレ
ン、ポリプロピレン、変性ポリオレフイン、ポリ
スチレン、ポリカーボネート、ポリアミド、ポリ
ブチレンテレフタレート等を配合しても良い。
本発明のポリエチレンテレフタレート樹脂組成
物は通常の方法で製造される。例えば(A)成分のポ
リエチレンテレフタレート、(B)成分の有機重合
体、好ましくは前記核剤、結晶化促進剤、必要に
応じて強化剤、難燃剤、着色剤、酸化防止剤等を
適当な混合機中でドライブレンドし、押出機、ニ
ーダー、バーバリーミキサー等で溶融混練し製造
される。
次に本発明の実施例、比較例を述べるが、本発
明は以下の例によりなんら限定されるものではな
い。
製造例 1
ポリエチレングリコールモノメチルエーテルメ
タアクリレート重合体(イ)、(ロ)の製造
ポリエチレングリコールモノメチルエーテルメ
タクリレートモノマー(平均分子量400および
1000)各々10重量部に対し、エタノール100重量
部、アゾビスイソブチロニトリルを各モノマーに
対し2モル%をガラス製反応器に仕込み、窒素気
流下で撹拌しつつ80℃、3時間重合した。得られ
た重合体溶液からエタノールを蒸発回収し、本発
明の重合体(イ)、(ロ)を各々得た。分子量は得られた
重合体を水溶液とし浸透圧法により決定した。
(イ)、(ロ)の数平均分子量は11000(重合度27.5)、
19000(重合度19)であつた。
実施例1〜5、比較例1〜10
ポリエチレンテレフタレート(クラレ製、フエ
ノール/テトラクロルエタン1対1混合溶媒、30
℃固有粘度0.68)と製造例1の重合体(イ)、(ロ)およ
び公知の核剤タルク(富士タルク製、LSM100)、
強化剤ガラス繊維(旭フアイバーグラス製、
CS03JA429)、比較のためにポリエチレングリコ
ールモノメチルエーテルメタクリレートの単量体
および低重合体(平均分子量400、1000、4000;
単量体、1600;4量体、2800;2.8量体)を表1
に示す割合でドライブレンドした後、40mmφ、
L/D=28の単軸スクリユー押出機にて混練造粒
した(シリンダー温度最大280℃)。得られたペレ
ツトを130℃、10時間熱風乾燥した後、日本製鋼
製射出成形機N−100Bにて、280℃、射出圧力
400〜600Kg/cm2、冷却時間20秒、成形サイクル40
秒、金型温度90℃で成形した。ブリードアウトの
程度は射出成形シート(80×120×2mm)を180
℃、1日ギヤーオープン中に放置後シート表面を
観察し、オイル状または粉末状物が表面に存在す
るときは“有”、これらが存在しないときは“無”
と判断した。また、結晶化促進効果は、各ペレツ
トを溶融後氷水で急冷して作成した試料につき、
パーキンエルマー社製差動熱量計DSC型で60
℃から290℃まで10℃/分で昇温、降温させた場
合に観測される各結晶化温度Tcc、Tc290が、
各々低温側、高温側に移動するかにより判断し
た。Tccが低い程金型温度は低く設定でき、
Tc290が高い程成形サイクルが早くなる。引張強
度の測定はASTM D−638に準拠した。結果を
表1に示す。
本表より、本発明による(B)成分の重合体(イ)、(ロ)
を配合した組成物は、分子量がポリエチレングリ
コールジメチルエーテルを配合した比較例に比べ
著しく大きいにもかかわらず、ポリエチレンテレ
フタレートとの相溶性が良く、引張強度の低下が
認められない事がわかる。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to crystalline polyethylene terephthalate resin compositions with fast crystallization rates useful in injection molding applications. Polyethylene terephthalate takes advantage of its excellent properties to be used in fibers, films,
Although it is widely used in fields such as bottles, in the field of injection molding, it has the potential to become an extremely excellent molding material.
It's not used that much. This is because polyethylene terephthalate has a slow crystallization rate at low temperatures.
It is necessary to maintain the mold temperature at 160° C. or higher during injection molding, and such a high mold temperature significantly lengthens the molding cycle, which is unfavorable in terms of production. To shorten the molding cycle, reduce mold temperature.
If the temperature is set near 100°C, crystallization will hardly proceed, and the mechanical properties, dimensional stability, and surface appearance of the molded product will be extremely poor. Various methods have been proposed in the past to improve these drawbacks. For example, Japanese Patent Publication No. 44-7542 discloses that inorganic particles, typically talc, and organic acid salts, such as sodium stearate, increase the crystallization rate of polyethylene terephthalate. Although the mold temperature can be lowered by such a method, a high temperature of 150 to 130° C. is still required, which is not very practical. Furthermore, in Japanese Patent Publication No. 47-3027, inorganic particles such as talc are given the general formula R 1 -O [-R 2 -O] o - R 1 (where R 1 is C 1 to C 10 Aromatic, aliphatic, hydrocarbon groups consisting of a combination thereof, or hydrocarbon organic groups containing nitrogen, sulfur, phosphorus, or oxygen as a part thereof,
R 2 is a C 2 to C 22 aliphatic hydrocarbon or a chain [−
an aliphatic hydrocarbon organic group containing nitrogen, oxygen, phosphorus, or sulfur in part or all of R 2 of R 2 −O] o --;
n is an integer from 1 to 200. ) molecular weight
A method of promoting crystallization of polyethylene terephthalate by blending more than 100 compounds is shown. This method is certainly a good method for lowering the mold temperature, but in order to lower it to 100℃ or less, a large amount of the compound represented by the general formula R 1 -O [-R 2 -O] - R 1 is blended. This may cause the compound to bleed out or deteriorate the general mechanical properties of the composition. Furthermore, if the molecular weight of the compound is increased in order to eliminate bleed-out, the compatibility with polyethylene terephthalate deteriorates, resulting in a disadvantage that the general mechanical properties of the composition deteriorate. The inventors of the present invention have conducted intensive research to solve the above-mentioned drawbacks of the prior art, and as a result, have arrived at the composition of the present invention that solves these problems. That is, the present invention comprises (A) component: 100 parts by weight of polyethylene terephthalate, and (B) component: General formula 1 to 20 parts by weight of an organic polymer represented by [wherein R 1 is an alkylene group having 2 to 5 carbon atoms,
R 2 is an aliphatic, alicyclic, aromatic, or a combination thereof hydrocarbon group having 1 or more carbon atoms, or a hydrocarbon terminal group containing nitrogen, sulfur, phosphorus, oxygen, or halogen as a part thereof, R 3 is hydrogen or methyl group, n is an integer from 1 to 50, m is from 10 to
200 integers. ] This is a polyethylene terephthalate resin composition obtained by kneading the following. Next, the present invention will be explained in detail. The polyethylene terephthalate used as component (A) of the present invention is a polyester mainly composed of repeating units of ethylene terephthalate. Generally, it is produced using polyethylene glycol and terephthalate acid, and other acid components and glycol components may be copolymerized within a range that does not impair crystallinity. Acid components include dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, adipic acid, sebacic acid, and cyclohexanedicarboxylic acid, and glycol components include trimethylene glycol, tetramethylene glycol, hexamethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene. Examples include glycol, a copolymer of polyethylene glycol and polypropylene glycol, and the like. Generally, at least 80 mol%, preferably 90 mol% or more of the acid component and glycol component are ethylene glycol and terephthalic acid, respectively, and preferably at least 80 mol% or more, more preferably 90 mol% or more of ethylene. Polyethylene terephthalate containing terephthalate repeat units is used. This (A) component polyethylene terephthalate is
Intrinsic viscosity measured at 30℃ in a 1:1 weight ratio mixed solvent of phenol and tetrachloroethane is 0.3 or more,
Preferably 0.5 or more, melt polycondensation reaction,
Alternatively, it can be produced by a method combining this and solid phase polymerization reaction. Component (B) has the general formula In the organic polymer represented by, R 1 is an alkylene group having 2 to 5 carbon atoms, and R 2 is an aliphatic, alicyclic, aromatic, or a combination thereof hydrocarbon group having 1 or more carbon atoms, or one thereof. Nitrogen, sulfur, phosphorus,
Hydrocarbon terminal group containing oxygen or halogen, R 3 is hydrogen or methyl group, n is 1 to 50, preferably 2
~30, m is an integer from 20 to 200. Such a polymer can be obtained by polymerizing the following monomers. These include polyethylene glycol monomethyl ale (meth)acrylate, polypropylene glycol monomethyl ether (meth)acrylate, polytetramethylene glycol monoethyl ether (meth)acrylate, and monomethyl ether (meth)acrylate, which is a copolymer of ethylene glycol and propylene glycol. There are (poly)alkylene glycol monoalkyl ether (meth)acrylates and phenoxypolyalkylene glycol (meth)acrylate. The organic polymer used here is a 10-200 mer. The organic polymer of component (B) can be polymerized by an appropriately selected method such as non-catalytic thermal polymerization, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, etc. depending on the polymerization performance of the monomer. Its blending amount is polyethylene terephthalate 100
The amount is 1 to 20 parts by weight, and if it is less than 1 part by weight, the effect of the present invention is not achieved, and if it exceeds 20 parts by weight, mechanical properties and heat resistance will deteriorate, which is not preferable. The present invention solves the disadvantages of the prior art, that is, when the amount of the compound added is increased to lower the mold temperature, the compound bleeds out, and in order to suppress this, the molecular weight of the compound is increased. Increasing this will reduce the compatibility with polyethylene terephthalate, and as a result, the general mechanical properties of the composition will be improved. The reason for this is not clear, but by increasing the molecular weight while having a low-molecular alkylene glycol chain represented by the general formula [-R 1 -O]-R 2 in the side chain, the compatibility with polyethylene terephthalate is improved by the side chain. It is presumed that because it is polymerized while being maintained, even if it is blended in a large amount, it will not significantly deteriorate the bleed-out or general mechanical properties. The present invention can be expected to be even more effective by using the conventionally used core materials and crystallization promoters together. Examples of these nucleating agents and crystallization promoters include inorganic compounds such as talc, crew, mica, and silica, and alkali metal salts such as stearic acid, montanic acid, and ethylene and methacrylic acid copolymers. A reinforcing agent such as glass fiber, carbon fiber, wollastonite, whiskers, etc. can be added to the polyethylene terephthalate of the present invention. In particular, it is preferable to add glass fiber in an amount of 5 to 60% by weight based on the total composition, as this significantly improves mechanical properties. Furthermore, in the present invention, flame retardants, ultraviolet absorbers, antioxidants, colorants, and hydrolysis-resistant agents may be added.
Furthermore, other thermoplastic resins such as polyethylene, polypropylene, modified polyolefin, polystyrene, polycarbonate, polyamide, polybutylene terephthalate, etc. may be blended. The polyethylene terephthalate resin composition of the present invention is produced by a conventional method. For example, polyethylene terephthalate as the component (A), an organic polymer as the component (B), preferably the above-mentioned nucleating agent, a crystallization promoter, and optionally a reinforcing agent, a flame retardant, a coloring agent, an antioxidant, etc. are mixed appropriately. It is manufactured by dry blending in a machine and then melt-kneading in an extruder, kneader, Burberry mixer, etc. Next, Examples and Comparative Examples of the present invention will be described, but the present invention is not limited in any way by the following examples. Production Example 1 Production of polyethylene glycol monomethyl ether methacrylate polymers (a) and (b) Polyethylene glycol monomethyl ether methacrylate monomer (average molecular weight 400 and
1000) For each 10 parts by weight, 100 parts by weight of ethanol and 2 mol% of azobisisobutyronitrile for each monomer were charged into a glass reactor, and polymerized at 80°C for 3 hours with stirring under a nitrogen stream. . Ethanol was recovered by evaporation from the obtained polymer solution to obtain polymers (a) and (b) of the present invention, respectively. The molecular weight was determined by osmotic pressure method using the obtained polymer as an aqueous solution.
The number average molecular weight of (a) and (b) is 11000 (degree of polymerization 27.5),
It was 19000 (degree of polymerization 19). Examples 1 to 5, Comparative Examples 1 to 10 Polyethylene terephthalate (manufactured by Kuraray, 1:1 mixed solvent of phenol/tetrachloroethane, 30
°C intrinsic viscosity 0.68), polymers (a) and (b) of Production Example 1 and known nucleating agent talc (manufactured by Fuji Talc, LSM100),
Reinforcement glass fiber (manufactured by Asahi Fiberglass,
CS03JA429), for comparison, polyethylene glycol monomethyl ether methacrylate monomers and low polymers (average molecular weights 400, 1000, 4000;
Monomer, 1600; tetramer, 2800; 2.8mer) in Table 1
After dry blending at the ratio shown in 40mmφ,
The mixture was kneaded and granulated using a single screw extruder with L/D=28 (maximum cylinder temperature 280°C). After drying the obtained pellets with hot air at 130°C for 10 hours, the pellets were heated to 280°C and injection pressure using a Nippon Steel injection molding machine N-100B.
400-600Kg/cm 2 , cooling time 20 seconds, molding cycle 40
molding at a mold temperature of 90°C. The degree of bleed-out is 180 mm for injection molded sheet (80 x 120 x 2 mm)
°C, after leaving the gear open for one day, observe the sheet surface. If oily or powdery substances are present on the surface, "Yes", and if these do not exist, "No".
I decided that. In addition, the crystallization promotion effect was confirmed for samples prepared by melting each pellet and then rapidly cooling it with ice water.
PerkinElmer differential calorimeter DSC type 60
The crystallization temperatures Tcc and Tc 290 observed when increasing and decreasing the temperature from ℃ to 290℃ at a rate of 10℃/min are as follows:
Judgment was made based on whether the temperature moved to the lower temperature side or higher temperature side. The lower the Tcc, the lower the mold temperature can be set.
The higher the Tc 290 , the faster the molding cycle. The tensile strength was measured in accordance with ASTM D-638. The results are shown in Table 1. From this table, polymers (a) and (b) of component (B) according to the present invention
Although the composition containing polyethylene glycol dimethyl ether has a significantly larger molecular weight than the comparative example containing polyethylene glycol dimethyl ether, it has good compatibility with polyethylene terephthalate, and no decrease in tensile strength is observed. 【table】
Claims (1)
R2は炭素数1以上の脂肪族、脂環式、芳香族
またはそれらの組合せよりなる炭化水素基、も
しくはその一部に窒素、硫黄、リン、酸素、ハ
ロゲンを含む炭化水素系末端基、R3は水素ま
たはメチル基、nは1〜50の整数、mは10〜
200の整数である。〕 とを混練してなるポリエチレンテレフタレート樹
脂組成物。[Claims] 1. Component (A): 100 parts by weight of polyethylene terephthalate; Component (B): General formula 1 to 20 parts by weight of an organic polymer represented by [wherein R 1 is an alkylene group having 2 to 5 carbon atoms,
R2 is an aliphatic, alicyclic, aromatic, or a combination thereof hydrocarbon group having 1 or more carbon atoms, or a hydrocarbon terminal group containing nitrogen, sulfur, phosphorus, oxygen, or halogen as a part thereof, R 3 is hydrogen or methyl group, n is an integer from 1 to 50, m is from 10 to
200 integers. ] A polyethylene terephthalate resin composition obtained by kneading.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8954884A JPS60233148A (en) | 1984-05-07 | 1984-05-07 | Polyethylene terephthalate resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8954884A JPS60233148A (en) | 1984-05-07 | 1984-05-07 | Polyethylene terephthalate resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60233148A JPS60233148A (en) | 1985-11-19 |
JPH0543749B2 true JPH0543749B2 (en) | 1993-07-02 |
Family
ID=13973872
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8954884A Granted JPS60233148A (en) | 1984-05-07 | 1984-05-07 | Polyethylene terephthalate resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60233148A (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5842644A (en) * | 1981-09-07 | 1983-03-12 | Kanegafuchi Chem Ind Co Ltd | Modified polyester composition for molding |
JPS5893754A (en) * | 1981-11-30 | 1983-06-03 | Asahi Chem Ind Co Ltd | Resin composition |
JPS59206458A (en) * | 1983-05-10 | 1984-11-22 | Unitika Ltd | Polyester composition |
JPS6084352A (en) * | 1983-10-13 | 1985-05-13 | Unitika Ltd | Polyester resin composition |
JPS6096645A (en) * | 1983-11-01 | 1985-05-30 | Mitsubishi Rayon Co Ltd | Polyethylene terephthalate resin composition |
JPS60228554A (en) * | 1984-04-26 | 1985-11-13 | Mitsubishi Rayon Co Ltd | Polyethylene terephthalate resin composition |
-
1984
- 1984-05-07 JP JP8954884A patent/JPS60233148A/en active Granted
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5842644A (en) * | 1981-09-07 | 1983-03-12 | Kanegafuchi Chem Ind Co Ltd | Modified polyester composition for molding |
JPS5893754A (en) * | 1981-11-30 | 1983-06-03 | Asahi Chem Ind Co Ltd | Resin composition |
JPS59206458A (en) * | 1983-05-10 | 1984-11-22 | Unitika Ltd | Polyester composition |
JPS6084352A (en) * | 1983-10-13 | 1985-05-13 | Unitika Ltd | Polyester resin composition |
JPS6096645A (en) * | 1983-11-01 | 1985-05-30 | Mitsubishi Rayon Co Ltd | Polyethylene terephthalate resin composition |
JPS60228554A (en) * | 1984-04-26 | 1985-11-13 | Mitsubishi Rayon Co Ltd | Polyethylene terephthalate resin composition |
Also Published As
Publication number | Publication date |
---|---|
JPS60233148A (en) | 1985-11-19 |
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