JPH0372559A - Polyester resin composition improved in crystallinity and fluidity - Google Patents
Polyester resin composition improved in crystallinity and fluidityInfo
- Publication number
- JPH0372559A JPH0372559A JP20853189A JP20853189A JPH0372559A JP H0372559 A JPH0372559 A JP H0372559A JP 20853189 A JP20853189 A JP 20853189A JP 20853189 A JP20853189 A JP 20853189A JP H0372559 A JPH0372559 A JP H0372559A
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- oligomer
- fluidity
- crystalline polyester
- resin composition
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 23
- 239000004645 polyester resin Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims abstract description 5
- 239000011342 resin composition Substances 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 10
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000002667 nucleating agent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000021736 acetylation Effects 0.000 description 3
- 238000006640 acetylation reaction Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- QXYLYYZZWZQACI-UHFFFAOYSA-N 2,3,4,5-tetrafluorophenol Chemical compound OC1=CC(F)=C(F)C(F)=C1F QXYLYYZZWZQACI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- IROLGKFFZFZJQS-UHFFFAOYSA-M [Li+].O.O.O.CC([O-])=O Chemical compound [Li+].O.O.O.CC([O-])=O IROLGKFFZFZJQS-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical class OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 238000000465 moulding Methods 0.000 description 1
- YZPOQCQXOSEMAZ-UHFFFAOYSA-N pbt2 Chemical compound ClC1=CC(Cl)=C(O)C2=NC(CN(C)C)=CC=C21 YZPOQCQXOSEMAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 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)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高い結晶性を有するために機械的特性が優れ、
かつ流動性も改良された結晶性ポリエステル樹脂組成物
に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention has excellent mechanical properties due to its high crystallinity.
The present invention also relates to a crystalline polyester resin composition with improved fluidity.
ポリエチレンテレフタレート（以下、ＰＥＴという）を
始めとする結晶性ポリエステルは、従来、合成繊維やフ
ィルム用途が主体であったが、その優れたガスバリアー
性を生かしてブローボトルなどにも使用されるようにな
ってきた。Crystalline polyesters such as polyethylene terephthalate (hereinafter referred to as PET) have traditionally been used mainly for synthetic fibers and films, but due to their excellent gas barrier properties, they are now being used in blow bottles, etc. It has become.
また、ガラス繊維が充填されたＰＥＴ （以下、ＧＦ−
ＰＥＴという）樹脂は優れた耐熱性を有し、射出成形に
より電気・電子および自動車部品としての開発が進んで
いる。In addition, PET filled with glass fiber (hereinafter referred to as GF-
PET resin has excellent heat resistance and is being developed for use in electrical, electronic, and automobile parts through injection molding.
しかしながら、ＰＥＴ樹脂を射出成形する場合、結晶化
速度が遅く金型温度を１３０℃以上にしなければならな
いなど成形性に問題があり、その優れた物性の割には需
要が少なかった。また、電子分野では高集積化に伴い、
従来以上に精密成形された電子部品が要求されており流
動性のより優れたＰＥＴ樹脂の開発が望まれている。However, when injection molding PET resin, there are problems with moldability, such as slow crystallization rate and the need for a mold temperature of 130° C. or higher, and there has been little demand for it despite its excellent physical properties. In addition, in the electronic field, with the increase in integration,
Electronic parts that are precisely molded are required more than ever before, and the development of PET resin with better fluidity is desired.
これまでに、ＰＥＴ樹脂の結晶性を改良するように、金
属酸化物、無機物、有機酸塩、粘土類などを結晶核の核
発生剤（以下、造核剤という）として添加することが検
討されてきた。Up to now, studies have been conducted to add metal oxides, inorganic substances, organic acid salts, clays, etc. as nucleating agents for crystal nuclei (hereinafter referred to as nucleating agents) in order to improve the crystallinity of PET resin. It's here.
しかし、無機物を例にとると、その粒径、粒径分布、お
よび分散性などによって造核剤としての効果が大きく異
なり、かつ添加量を増やしても十分な効果が得られない
といった問題があった。However, when using inorganic substances as an example, their effectiveness as nucleating agents varies greatly depending on their particle size, particle size distribution, dispersibility, etc., and there is a problem that sufficient effects cannot be obtained even if the amount added is increased. Ta.
また、有機酸塩としては、有機スルホン酸のアルカリ金
属またはアルカリ土類金属（特公昭６０−５６１８０号
公報、特公昭６２−７６１号公報）、炭素数２６以上の
高級脂肪酸のアルカリ金属またはカルシウム塩（特開昭
５６−１３９５５０号公報、特開昭５６−１４１３４７
号公報）などが知られているが、さらに優れた機能を有
する有機酸塩の探索が続けられている。Examples of organic acid salts include alkali metal or alkaline earth metal salts of organic sulfonic acids (Japanese Patent Publication No. 60-56180, Japanese Patent Publication No. 62-761), alkali metal or calcium salts of higher fatty acids having 26 or more carbon atoms. (Unexamined Japanese Patent Publication No. 56-139550, Unexamined Japanese Patent Publication No. 56-141347
However, the search for organic acid salts with even better functionality continues.
しかしながら、これまでに知られている造核剤ではその
効果が十分でないか、十分であっても流動性の改良効果
を同時に合わせ持つものはなかった。However, none of the nucleating agents known so far have a sufficient effect, or even if they are sufficient, they also have the effect of improving fluidity.
本発明者らは、従来を上回る性能を有し、かつ流動性の
改良効果も合わせ持つ造核剤について鋭し構成単位から
なる液晶性オリゴマーを特定量添加することにより、上
記目的が達成されることを見出し、本発明に到達したも
のである。The present inventors have discovered that the above objective can be achieved by adding a specific amount of a liquid crystalline oligomer consisting of sharp structural units to a nucleating agent that has performance superior to conventional ones and also has the effect of improving fluidity. This discovery led to the present invention.
すなわち、本発明は、結晶性ポリエステル樹脂１００重
量部に対して、下記の方法で求めた流動温り返し構造単
位からなる液晶性オリゴマーを０．０１〜３０重量部添
加してなる結晶性および流動性の改良されたポリエステ
ル樹脂組成物を提供するものである。That is, the present invention provides crystallinity and fluidity obtained by adding 0.01 to 30 parts by weight of a liquid crystalline oligomer consisting of a fluidized reheating structural unit determined by the following method to 100 parts by weight of a crystalline polyester resin. The present invention provides a polyester resin composition with improved properties.
流動温度： 内径１ｍｍ、長さ１０ｍｍのノズルをもつ
毛細管型レオメータ−を用い、４℃／分の昇温速度で加
熱溶融体をノズルから押し出すときに、溶融粘度が４８
．０００ボイズを示す温度。Flow temperature: Using a capillary rheometer with a nozzle with an inner diameter of 1 mm and a length of 10 mm, when extruding the heated melt through the nozzle at a heating rate of 4°C/min, the melt viscosity was 48.
．． Temperature indicating 000 voids.
本発明に使用される結晶性ポリエステル樹脂としては、
エチレングリコールとテレフタル酸を主成分とし公知の
方法で製造される重縮合体、またはエチレングリコール
とテレフタル酸およびイソフタル酸とを主成分とし公知
の方法で製造される重縮合体が、耐熱性、耐薬品性、加
工性、経済性の面から好ましく用いられる。The crystalline polyester resin used in the present invention includes:
A polycondensate containing ethylene glycol and terephthalic acid as the main components and produced by a known method, or a polycondensate containing ethylene glycol, terephthalic acid, and isophthalic acid as the main components and produced by a known method, has excellent heat resistance and resistance. It is preferably used from the viewpoint of chemical properties, processability, and economic efficiency.
本発明に使用される特定の流動温度をもつ液晶性オリゴ
マー（以下ＰＯＢオリゴマーという）は、ｐ−ヒドロキ
シ安息香酸、あるいはその誘導体を出発原料として、ア
セチトーション法、フェニルエステル化法と呼ばれる一
般的な反応により、高沸点溶媒を用いる溶液重合、実質
的に溶媒を含まない溶融重合により得ることができる。The liquid crystalline oligomer (hereinafter referred to as POB oligomer) with a specific flow temperature used in the present invention is produced using a general method called the acetitorsion method or phenyl esterification method using p-hydroxybenzoic acid or its derivative as a starting material. The reaction can be obtained by solution polymerization using a high boiling point solvent or melt polymerization substantially free of solvent.
さらに、末端基としてカルボキシル基と水酸基をもつも
のが、溶融時の化学的安定性から特に好ましい。Furthermore, those having a carboxyl group and a hydroxyl group as terminal groups are particularly preferred from the viewpoint of chemical stability during melting.
該オリゴマーの流動温度は、毛細管型レオメータ−を用
いた前記の方法により測定したときの値が３５０℃以下
である。この場合、溶融状態の結晶性ポリエステル樹脂
が固化し結晶核が生成する温度において、オリゴマーは
結晶構造を形成しており、造核剤としての優れた機能を
はたす。流動温度が３５０℃より高い場合は、溶融混線
時にオリゴマーが溶融せず均一な組成物を得ることがで
きない。The flow temperature of the oligomer is 350° C. or less when measured by the method described above using a capillary rheometer. In this case, at the temperature at which the molten crystalline polyester resin solidifies and crystal nuclei are generated, the oligomer forms a crystal structure and functions as an excellent nucleating agent. If the flow temperature is higher than 350°C, the oligomer will not melt during melt mixing, making it impossible to obtain a uniform composition.
該オリゴマーの流動温度と分子量の関係については、流
動温度の低いオリゴマーのみがテトラフルオロフェノー
ルのような特殊な溶媒にわずかに溶解するのみで、明か
にすることは難しい。It is difficult to clarify the relationship between the flow temperature and molecular weight of the oligomer because only oligomers with a low flow temperature are slightly soluble in special solvents such as tetrafluorophenol.
しかしながら、アセチトーション法では酢酸の留出量、
フェニルエステル化法ではフェノールの留出量を正確に
測定することにより、該オリゴマーの数平均重合度を推
定することができ、実施例に述べるように流動温度との
相関関係を得ることができる。However, in the acetitorsion method, the amount of distilled acetic acid,
In the phenyl esterification method, by accurately measuring the amount of phenol distilled out, the number average degree of polymerization of the oligomer can be estimated, and a correlation with the flow temperature can be obtained as described in the examples.
Ｏ
構造単位からなるオリゴマーの添加量は、該オリゴマー
の流動温度によるが、総じて結晶性ポリヱステル樹脂１
００重量部に対して０．０１〜３０重量部の範囲である
。該オリゴマーの添加量が０．０１重量部未満の場合は
結晶性および流動性改良効果がほとんど見られず、３０
重量部を越える場合は流動性は非常に改良されるものの
、成形時に該オリゴマーが一部分解し成形品表面に発泡
を伴う。造核効果、流動性改良効果と他の物性のバラン
スから、該オリゴマーの結晶性ポリエステル１００重量
部に対する添加量としては０．１〜２０重量部の範囲が
特に好ましい。The amount of the oligomer consisting of the O structural unit depends on the flow temperature of the oligomer, but in general, the amount of the oligomer consisting of the crystalline polyester resin 1
The range is from 0.01 to 30 parts by weight per 00 parts by weight. When the amount of the oligomer added is less than 0.01 part by weight, almost no effect of improving crystallinity and fluidity is observed;
If the amount exceeds parts by weight, the fluidity is greatly improved, but the oligomer is partially decomposed during molding, resulting in foaming on the surface of the molded product. In view of the balance between the nucleating effect, the fluidity improving effect, and other physical properties, the amount of the oligomer added to 100 parts by weight of the crystalline polyester is particularly preferably in the range of 0.1 to 20 parts by weight.
さらに、本発明においては、必要に応じて結晶性ポリエ
ステル樹脂に使用される充填剤を配合することができる
。すなわち、ガラス繊維、シリカアルミナ繊維、ウオラ
ストナイト、炭素繊維、チタン酸カリウム繊維などの繊
維状の補強剤、炭酸カルシウム、タルク、マイカ、クレ
イ、ガラスピーズなどの無機充填剤、ポリテトラフルオ
ロエチレンやグラファイトに代表される固体潤滑剤、酸
化防止剤、熱安定剤などを必要に応じて添加してよい。Furthermore, in the present invention, fillers used in crystalline polyester resins can be added as necessary. In other words, fibrous reinforcing agents such as glass fiber, silica alumina fiber, wollastonite, carbon fiber, and potassium titanate fiber, inorganic fillers such as calcium carbonate, talc, mica, clay, and glass peas, polytetrafluoroethylene, and A solid lubricant represented by graphite, an antioxidant, a heat stabilizer, etc. may be added as necessary.
本発明の成形材料を得るための原料成分の配合手段は特
に限定されない。すなわち、結晶性ポリエステル樹脂と
該オリゴマーに、ガラス繊維などの充填剤や顔料、熱安
定剤などをヘンシェルミキサー、タンブラ−などを用い
て混合したのち、造粒機などによって溶融混練するのが
一般的である。There are no particular limitations on the means for blending raw material components to obtain the molding material of the present invention. That is, it is common to mix fillers such as glass fiber, pigments, heat stabilizers, etc. with the crystalline polyester resin and the oligomer using a Henschel mixer, tumbler, etc., and then melt-knead them using a granulator, etc. It is.
特定の流動温度を持つ該オリゴマーは混練時には溶融し
ており、無機物質の造核剤のように二次凝集による分散
不良を起こすことなく、均一な組成物を得ることができ
る。また、該オリゴマーはマトリックスである結晶性ポ
リエステルが固化し結晶核が生成する温度においては、
結晶構造を形成しており、造核剤としての優れた機能を
はたす。The oligomer, which has a specific flow temperature, is molten during kneading, and a uniform composition can be obtained without causing poor dispersion due to secondary aggregation, unlike inorganic nucleating agents. In addition, at the temperature at which the crystalline polyester matrix solidifies and crystal nuclei are generated, the oligomer
It forms a crystalline structure and performs an excellent function as a nucleating agent.
また、該オリゴマーは結晶性ポリエステルと良く相溶す
るため、他の物性を損なうことなく結晶性ポリエステル
の流動性改良剤として有効に働く。Furthermore, since the oligomer is well compatible with the crystalline polyester, it works effectively as a fluidity improver for the crystalline polyester without impairing other physical properties.
以下、本発明の実施例を示すが、本発明はこれらに限定
されるものではない。なお、実施例中の物性は次の方法
で測定された。Examples of the present invention will be shown below, but the present invention is not limited thereto. In addition, the physical properties in Examples were measured by the following method.
○流動温度： （株）島津製作所製のフローテスター
ＣＦＴ−５００型で測定され、４℃／分の昇温速度で
加熱溶融されたオリゴマーを荷重１００ｋｇ／ｃｍｔの
下で内径１ｍｍ１長さ１０ｍｍのノズルから押し出すと
きに、該溶融粘度が４８．０００ボイズを示す点におけ
る温度である。この温度は重合度の目安になる。○Flow temperature: Measured with a flow tester CFT-500 model manufactured by Shimadzu Corporation. The oligomer heated and melted at a heating rate of 4°C/min was passed through a nozzle with an inner diameter of 1 mm and a length of 10 mm under a load of 100 kg/cmt. This is the temperature at which the melt viscosity shows 48,000 voids when extruded from the melt. This temperature is a measure of the degree of polymerization.
Ｏ光学異方性： 溶融状態における樹脂の光学異方性は
、加熱ステージ上に置かれた粉末状のオリゴマーを偏光
下１０６０７分で昇温して肉眼観察により行った。なお
、静置下で完全溶融しない場合はスプリング圧を利用し
加圧下で行った。O optical anisotropy: The optical anisotropy of the resin in the molten state was determined by visual observation of a powdered oligomer placed on a heating stage, heated for 10,607 minutes under polarized light. In addition, if complete melting was not achieved under standing conditions, spring pressure was used to perform the melting under increased pressure.
○溶液粘度： ウベローデ型粘度計を用いて、フェノー
ル／テトラクロロエタン（＝ ６／４．体積）を溶媒と
し２０℃で測定した。Solution viscosity: Measured at 20°C using an Ubbelohde viscometer using phenol/tetrachloroethane (=6/4.vol.) as a solvent.
○結晶化温度： 該組成物１０Ｂを３３０℃で５分間加
熱溶融したのち、１０’Ｃ／分の降温速度で示差走査熱
量計（ＤＳＣ）によって結晶化に伴う発熱ピークを測定
し、ピーク温度を結晶化温度とした。○Crystallization temperature: After heating and melting the composition 10B at 330°C for 5 minutes, the exothermic peak accompanying crystallization was measured using a differential scanning calorimeter (DSC) at a cooling rate of 10'C/min, and the peak temperature was determined. It was taken as the crystallization temperature.
○薄肉流動性： 肉厚０．３ｍｍ、長さ４６ｍｍ、幅５
ｍｍの矩形を有する４個取りの金型を用いて本発明の組
成物を溶融状態で一定の射出条件のもとで充填したとき
の４つの矩形における長さ方向の流動長を測定し、平均
値を求め流動長として表した。○Thin wall fluidity: wall thickness 0.3mm, length 46mm, width 5
When the composition of the present invention is filled in a molten state under certain injection conditions using a four-cavity mold having a rectangular shape of mm, the flow length in the longitudinal direction in the four rectangles is measured, and the average The value was determined and expressed as flow length.
なお、結晶化温度測定用の試料は、東洋精機製作新製ブ
ラベンダープラストミルを用いて、真空下１３０℃で５
時間乾燥した結晶性ポリエステルと該オリゴマーとの混
合物に、リン酸トリフェニルを結晶性ポリエステル１０
０重量部に対して０．１重量部添加し、全量４０ｇを２
９０℃、高純度窒素下、５０ｒｐｍで１０分間溶融混練
することによって作成した。The sample for crystallization temperature measurement was prepared using Toyo Seiki's new Brabender Plastomill at 130℃ under vacuum for 55 minutes.
Add triphenyl phosphate to a mixture of the crystalline polyester and the oligomer that has been dried for 10 minutes.
Add 0.1 part by weight to 0 parts by weight, and add 2 parts by weight to 40g of total amount.
It was prepared by melt-kneading at 90° C. under high-purity nitrogen at 50 rpm for 10 minutes.
参考例１〜３ （結晶性ポリエステルの合成）３種類の
ＰＥＴ樹脂を以下に述べる公知の方法で合成した。Reference Examples 1 to 3 (Synthesis of crystalline polyester) Three types of PET resins were synthesized by the known method described below.
（１）ビス−β−ヒドロキシエチルテレフタレート（以
下、ＢＨＢＴという）の合成
高純度テレフタル酸とエチレングリコールから酢酸リチ
ウム（三水和物）を触媒とし、蒸留塔といかり型撹拌翼
を有するオートクレーブによって窒素ガス雰囲気下２４
０℃で、直接エステル化法により合成した。(1) Synthesis of bis-β-hydroxyethyl terephthalate (hereinafter referred to as BHBT) from high-purity terephthalic acid and ethylene glycol using lithium acetate (trihydrate) as a catalyst, using nitrogen in an autoclave equipped with a distillation column and anchored stirring blades. Under gas atmosphere 24
Synthesized by direct esterification method at 0°C.
（２）ＰＥＴ樹脂の合成
次に、このＢＨＥＴを５０Ｘ亜リン酸水溶液存在下で、
生成してくるエチレングリコールを系外に除去しながら
減圧重合した。得られたＰＥＴ樹脂（ＰＢＴＩ）の溶液
粘度は０．５５ｄ ｌ／ｇであった。さらに、このＰＥ
Ｔ樹脂を固相重合することにより溶液粘度は０．８９ｄ
ｉ／ｇまで上昇した（ ＰＥＴ２）。(2) Synthesis of PET resin Next, this BHET was mixed in the presence of a 50X aqueous phosphorous acid solution,
Polymerization was carried out under reduced pressure while removing the produced ethylene glycol from the system. The solution viscosity of the obtained PET resin (PBTI) was 0.55 dl/g. Furthermore, this PE
Solution viscosity is 0.89d by solid phase polymerization of T resin
i/g (PET2).
また、テレフタル酸とイソフタル酸混合物（９５１５ｗ
ｔＸ）およびエチレングリコールから同様にして溶液粘
度が０゜８０ｄ ｌ／ｇである共重合ＰＥＴ樹脂（ＰＥ
Ｔ３）を合成した。In addition, a mixture of terephthalic acid and isophthalic acid (9515w
Similarly, a copolymerized PET resin (PE
T3) was synthesized.
実施例１−１０、比較例１〜３
（ＰＯＢオリゴマーの合成）
ｎ量体（ｎ ＝ ２． ３．４．５．７．９． １２）
のＰＯＢオリゴマーの合成を以下の手順で行った。１０
モルのｐ−ヒドロキシ安息香酸と１０（ｎ−１）／ｎモ
ルの無水酢酸を十分窒素置換したいかり型撹拌翼を有す
る重合槽に仕込み、窒素ガス雰囲気下で撹拌しながら昇
温させ、１８０℃に到達した時点で還流下３時間反応を
行いアセチル化を行った。その後３００℃まで温度を上
げアセチル化により副生した酢酸および縮合により副生
した酢酸の留出が止まるまで反応を続け、強力な撹拌の
もとて反応物を粉砕しながら系を徐々に冷却し、１２０
℃以下の温度に到達してから反応混合物を系外に取り出
した。これを線用ミクロン製パンタムミルで粉砕し２０
０μｍ以下の粒子とした。Examples 1-10, Comparative Examples 1-3 (Synthesis of POB oligomer) n-mer (n = 2. 3. 4. 5. 7. 9. 12)
The POB oligomer was synthesized using the following procedure. 10
Moles of p-hydroxybenzoic acid and 10 (n-1)/n moles of acetic anhydride were charged into a polymerization tank equipped with an anchor-type stirring blade that was sufficiently purged with nitrogen, and the temperature was raised to 180°C while stirring in a nitrogen gas atmosphere. At the time when the reaction temperature reached 1, the reaction was carried out under reflux for 3 hours to effect acetylation. Thereafter, the temperature was raised to 300°C, and the reaction was continued until the distillation of acetic acid by-produced by acetylation and acetic acid by-produced by condensation stopped, and the system was gradually cooled while crushing the reactants under strong stirring. , 120
After reaching a temperature below .degree. C., the reaction mixture was taken out of the system. Grind this with a wire Micron pantam mill to 20
The particles were 0 μm or less.
アセチル化が１００ｘ達成されていると仮定し、副生じ
た酢酸の留出量から計算するとｎ ＝ ２．３．４゜５
、７．９．１２のｎ量体に相当するＰＯＢオリゴマーの
数平均重合度は、それぞれ、１．８．２．６．３．５．
４．３．６．２．８．０．１０．６であった。またこれ
らのオリゴマーの流動温度、光学異方性を示す温度を前
述した方法で求めた。数平均重合度が１０．６のオリゴ
マーについては３５０℃以下の温度では流動せず、加圧
下でも光学異方性を示さなかった。これらの結果を表１
にまとめて示す。Assuming that 100x acetylation has been achieved, n = 2.3.4゜5 calculated from the distilled amount of by-produced acetic acid.
The number average degrees of polymerization of POB oligomers corresponding to n-mers of , 7.9.12 are 1.8.2.6.3.5., respectively.
It was 4.3.6.2.8.0.10.6. Furthermore, the flow temperature and the temperature at which optical anisotropy of these oligomers was determined were determined using the methods described above. The oligomer with a number average degree of polymerization of 10.6 did not flow at temperatures below 350°C and did not exhibit optical anisotropy even under pressure. These results are shown in Table 1.
are summarized in
さらにこれらのオリゴマーの末端基を確認するためＫＢ
ｒ法により赤外吸収スペクトルを測定した結果、いずれ
のオリゴマーについても３．５００ｃ１’付近にヒドロ
キシル基に基づくピークが検出され１、３７０ｃｍ−’
のアセチル基に基づくピークは検出されなかった。従っ
ていずれのオリゴマーもアセチル化を受けなかったｐ−
ヒドロキシ安息香酸で末端が停止されていることが示さ
れた。In order to further confirm the terminal groups of these oligomers, KB
As a result of measuring infrared absorption spectra using the r method, a peak based on hydroxyl groups was detected around 3.500c1' for all oligomers, and a peak based on hydroxyl groups was detected at 1,370cm-'
No peak based on the acetyl group was detected. Therefore, neither oligomer was acetylated p-
It was shown to be terminally terminated with hydroxybenzoic acid.
（組成物の特性）
結晶性ポリエステル樹脂ＰＲＴＩに上記の方法で合成し
た各種ＰＯＢオリゴマーをそれぞれ族２に示した組成で
混合し、前述の通り溶融混練した（実施例１−１０、比
較例２〜３）。同様にしてＰＯＢオリゴマーを含まない
結晶性ポリエステル樹脂ＰＥＴｌも溶融混練したく比較
例１）。これらの試料について前述の方法で結晶化温度
を測定し、結果を族２にまとめた。(Characteristics of the composition) Various POB oligomers synthesized by the above method were mixed with the crystalline polyester resin PRTI in the composition shown in Group 2, and melt-kneaded as described above (Examples 1-10, Comparative Examples 2- 3). Comparative Example 1) A crystalline polyester resin PETl containing no POB oligomer was also melt-kneaded in the same manner. The crystallization temperatures of these samples were measured using the method described above, and the results were summarized in Group 2.
本発明の組成からなる実施例１−１０の組成物は、いず
れもＰＯＢオリゴマーを含まない組成物（比較例１）に
比べ高い結晶化温度を有し、結晶性が改良されているこ
とがわかる。また、流動温度が２８８℃で酢酸留出量か
ら求めた数平均重合度が６．２のＰＯＢオリゴマーを添
加した系でみると、添加量が０．０１重量部未満のもの
（比較例２）では結晶化温度の上昇はわずかで、酢酸留
出量から求めた数平均重合度が１Ｏ１６のＰＯＢオリゴ
マーを添加した系では（比較例３）、溶融混線時にオリ
ゴマーが溶融せず均一な組成物を得ることができなかっ
た。It can be seen that the compositions of Examples 1 to 10, which are composed of the compositions of the present invention, all have higher crystallization temperatures than the composition containing no POB oligomer (Comparative Example 1), and have improved crystallinity. . In addition, in a system in which a POB oligomer with a flow temperature of 288°C and a number average degree of polymerization determined from the amount of acetic acid distilled out is 6.2, the amount added is less than 0.01 part by weight (Comparative Example 2) In this case, the increase in the crystallization temperature was slight, and in the system in which POB oligomers with a number average degree of polymerization determined from the amount of acetic acid distilled out was 1O16 (Comparative Example 3), the oligomers did not melt during melt mixing and a uniform composition was obtained. I couldn't get it.
実施例１１〜２０、比較例４〜６
実施例１〜１０と同様にして、結晶性ポリエステル樹脂
ＰＢＴ２と各種ＰＯＢオリゴマーから表３に示す混合比
の組成物を得た。これらの結晶化温度を測定し表３にま
とめた。結晶性ポリエステル樹脂ＰｇＴ１の場合と同様
の結果となっていることがわかる。Examples 11-20, Comparative Examples 4-6 In the same manner as Examples 1-10, compositions having the mixing ratios shown in Table 3 were obtained from the crystalline polyester resin PBT2 and various POB oligomers. These crystallization temperatures were measured and summarized in Table 3. It can be seen that the results are similar to those for the crystalline polyester resin PgT1.
実施例２１〜２５、比較例７．８
結晶性ポリエステル樹脂ｐＨ！Ｔ２の１００重量部、ガ
ラス繊維（セントラル硝子（株）製ＥＦＨ７５−０１）
６７重量部、およびリン酸トリフェニル０．１重量部
に、流動温度が２５０℃で酢酸留出量から求めた数平均
重合度が４．３のＰＯＢオリゴマーを表４の組成になる
ようヘンシェルミキサーで混合し、二軸押出機（池貝鉄
工（株）製ＰＣＭ−３０）により、２６５℃の温度で溶
融混練することによりペレットを得た。そして、このペ
レットから射出成形により、前述の方法に従って薄肉流
動性を測定し、結果を表４にまとめた。なお、射出条件
はシリンダー温度２７０℃、全形温度７５℃、射出速度
６０％である。Examples 21 to 25, Comparative Example 7.8 Crystalline polyester resin pH! 100 parts by weight of T2, glass fiber (EFH75-01 manufactured by Central Glass Co., Ltd.)
67 parts by weight and 0.1 part by weight of triphenyl phosphate were mixed with a POB oligomer having a flow temperature of 250°C and a number average degree of polymerization of 4.3 determined from the amount of acetic acid distilled out, using a Henschel mixer to obtain the composition shown in Table 4. Pellets were obtained by melt-kneading at a temperature of 265° C. using a twin-screw extruder (PCM-30 manufactured by Ikegai Tekko Co., Ltd.). The pellets were then injection molded and the thin wall fluidity was measured according to the method described above, and the results are summarized in Table 4. The injection conditions were a cylinder temperature of 270°C, a total temperature of 75°C, and an injection speed of 60%.
本発明の組成からなる実施例２１〜２５の組成物はいず
れもＰＯＢオリゴマーを含まない組成物（比較例７）に
比べ、ＰＯＢオリゴマーの添加量とともに流動性が改良
されていることがわかる。また、添加量が３０重量部を
越えるもの（比較例８）は流動性改良効果は著しいが、
成形品表面が激しく発泡した。It can be seen that all of the compositions of Examples 21 to 25, which are composed of the compositions of the present invention, have improved fluidity as the amount of POB oligomer added increases compared to the composition containing no POB oligomer (Comparative Example 7). In addition, when the amount added exceeds 30 parts by weight (Comparative Example 8), the fluidity improvement effect is remarkable, but
The surface of the molded product foamed violently.
実施例２６〜３６、比較例９〜１１
実施例１−１０と同様にして、結晶性ポリエステル樹脂
ＰＥＴ３と各種ＰＯＢオリゴマーから表５に示す混合比
の組成物を得た。これらの結晶化温度を測定し表５にま
とめた。結晶性ポリエステル樹脂が共重合ＰＥＴ樹脂の
場合においてもＰＯＢオリゴマーが造核剤として有効で
あることがわかる。Examples 26 to 36, Comparative Examples 9 to 11 In the same manner as in Examples 1 to 10, compositions having the mixing ratios shown in Table 5 were obtained from the crystalline polyester resin PET3 and various POB oligomers. These crystallization temperatures were measured and summarized in Table 5. It can be seen that the POB oligomer is effective as a nucleating agent even when the crystalline polyester resin is a copolymerized PET resin.
さらに実施例２１〜２５と同様にして、結晶性ポリエス
テル樹脂ＰＥ７３と、流動温度が２５０℃で酢酸留出量
から求めた数平均重合度が４．３のＰＯＢオリゴマーか
ら表６に示す組成比のペレットを得た。そして、このペ
レットから実施例２１〜２５と同様の条件で薄肉流動性
を測定し、結果を表６にまとめた。Furthermore, in the same manner as in Examples 21 to 25, the composition ratios shown in Table 6 were obtained from crystalline polyester resin PE73 and a POB oligomer with a flow temperature of 250°C and a number average degree of polymerization of 4.3 determined from the amount of acetic acid distilled. Obtained pellets. Then, the thin wall fluidity of these pellets was measured under the same conditions as in Examples 21 to 25, and the results are summarized in Table 6.
共重合ＰＥＴ樹脂の場合もＰＯＢオリゴマーの添加によ
って流動性が改良されることがわかる。また、添加量が
３０重量部を越えるもの（比較例１１）は流動性改良効
果は著しいが、成形品表面が激しく発泡した。It can be seen that in the case of copolymerized PET resin as well, the fluidity is improved by adding POB oligomer. Further, when the amount added exceeds 30 parts by weight (Comparative Example 11), the fluidity improvement effect was remarkable, but the surface of the molded product foamed violently.
表２ 表１ 表 ３ 表Table 2 Table 1 table 3 table
Claims (2)
下記の方法で求めた流動温度が３５０℃以下であり、▲
数式、化学式、表等があります▼の繰り返し構造単位か
ら なる液晶性オリゴマーを０．０１〜３０重量部添加して
なる結晶性および流動性の改良されたポリエステル樹脂
組成物。 流動温度：内径１ｍｍ、長さ１０ｍｍのノズルをもつ毛
細管型レオメーターを用い、４℃／分の昇温速度で加熱
溶融体をノズルから押し出すときに、溶融粘度が４８，
０００ポイズを示す温度。(1) For 100 parts by weight of crystalline polyester resin,
The flow temperature determined by the method below is 350℃ or less, and ▲
A polyester resin composition with improved crystallinity and fluidity, which is made by adding 0.01 to 30 parts by weight of a liquid crystalline oligomer consisting of the repeating structural unit ▼, which includes mathematical formulas, chemical formulas, tables, etc. Flow temperature: Using a capillary rheometer with a nozzle with an inner diameter of 1 mm and a length of 10 mm, when extruding the heated melt through the nozzle at a heating rate of 4°C/min, the melt viscosity is 48,
Temperature indicating 000 poise.
酸基をもつことを特徴とする請求項１記載の樹脂組成物
。(2) The resin composition according to claim 1, wherein the oligomer has a carboxyl group and a hydroxyl group as terminal groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20853189A JPH0372559A (en) | 1989-08-11 | 1989-08-11 | Polyester resin composition improved in crystallinity and fluidity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20853189A JPH0372559A (en) | 1989-08-11 | 1989-08-11 | Polyester resin composition improved in crystallinity and fluidity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0372559A true JPH0372559A (en) | 1991-03-27 |
Family
ID=16557730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20853189A Pending JPH0372559A (en) | 1989-08-11 | 1989-08-11 | Polyester resin composition improved in crystallinity and fluidity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0372559A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9988529B2 (en) | 2015-11-20 | 2018-06-05 | Ticona Llc | High flow polyaryletherketone composition |
-
1989
- 1989-08-11 JP JP20853189A patent/JPH0372559A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9988529B2 (en) | 2015-11-20 | 2018-06-05 | Ticona Llc | High flow polyaryletherketone composition |
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