JPH0428768A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH0428768A JPH0428768A JP13373890A JP13373890A JPH0428768A JP H0428768 A JPH0428768 A JP H0428768A JP 13373890 A JP13373890 A JP 13373890A JP 13373890 A JP13373890 A JP 13373890A JP H0428768 A JPH0428768 A JP H0428768A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- resin composition
- resin
- acid
- liquid crystal
- 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
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 18
- 239000011342 resin composition Substances 0.000 title claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims description 30
- -1 polyethylene terephthalate Polymers 0.000 abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 13
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 13
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract description 12
- 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
- 229920000728 polyester Polymers 0.000 abstract description 8
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 abstract description 6
- 229920001155 polypropylene Polymers 0.000 abstract description 6
- 239000004743 Polypropylene Substances 0.000 abstract description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 5
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 229920001903 high density polyethylene Polymers 0.000 abstract description 2
- 239000004700 high-density polyethylene Substances 0.000 abstract description 2
- 238000004898 kneading Methods 0.000 abstract description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 11
- 229920006038 crystalline resin Polymers 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- PSAGPCOTGOTBQB-UHFFFAOYSA-N 4-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(O)C2=C1 PSAGPCOTGOTBQB-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- HIZCTWCPHWUPFU-UHFFFAOYSA-N Glycerol tribenzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(OC(=O)C=1C=CC=CC=1)COC(=O)C1=CC=CC=C1 HIZCTWCPHWUPFU-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、熱可塑性樹脂組成物に関するものである。自
動車部品や電気電子部品の分野などで種々の熱可塑性樹
脂が広く用いられているが、機構部品などにおいては、
耐熱性、剛性、寸法安定性のより一層の改良が望まれて
いる。本発明はそのような用途に好適な、耐熱性、剛性
、寸法安定性の改良された成形材料を提供する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermoplastic resin composition. Various thermoplastic resins are widely used in the fields of automobile parts and electrical and electronic parts, but in mechanical parts etc.
Further improvements in heat resistance, rigidity, and dimensional stability are desired. The present invention provides a molding material with improved heat resistance, rigidity, and dimensional stability that is suitable for such uses.
熱可塑性樹脂の耐熱性、剛性および寸法安定性を改良す
る目的で、ガラス繊維、カーボン繊維を配合することは
周知であるが、繊維状充填物を配合することにより成形
性が低下するばかりてなく、成形品の外観が損なわれる
。It is well known that glass fibers and carbon fibers are added to thermoplastic resins to improve their heat resistance, rigidity, and dimensional stability, but adding fibrous fillers not only reduces moldability but also reduces moldability. , the appearance of the molded product is impaired.
一方、異方性溶融相を形成しうる樹脂（以下、液晶性樹
脂と記すことがある）は、剛性、耐熱性等に極めて優れ
た材料であり、特開昭６４−９０２５５号には、ポリエ
ステル樹脂に繊維状液晶性樹脂を分散させた、強度、弾
性率の改良された繊維が開示されている。特開昭５７−
５１７３９号には、ポリフェニレンサルファイドに液晶
性樹脂と配合することにより、液晶性樹脂の機械的性質
を大きく損なわない、液晶性樹脂よりも安価な材料を提
供する効果、ポリフェニレンサルファイドの成形加工性
を改良する効果が記載されている。特開平１２５２６５
７号には、液晶性樹脂に熱可塑性樹脂を添加することに
より、耐熱性などを改良する方法が示されている。しか
しながらこれらの技術においては、基材熱可塑性樹脂の
好ましい性質を損なわないような少量の液晶性樹脂の配
合において、最大限の補強効果を発現させる特定の技術
については同等示唆されていない。On the other hand, resins that can form an anisotropic melt phase (hereinafter sometimes referred to as liquid crystal resins) are materials with extremely excellent rigidity, heat resistance, etc. A fiber with improved strength and modulus of elasticity is disclosed in which a fibrous liquid crystalline resin is dispersed in a resin. Japanese Unexamined Patent Publication 1987-
No. 51739 discloses that by blending polyphenylene sulfide with a liquid crystal resin, it provides a material that does not significantly impair the mechanical properties of the liquid crystal resin, is cheaper than the liquid crystal resin, and improves the moldability of polyphenylene sulfide. The effects of this are described. Japanese Patent Publication No. 125265
No. 7 discloses a method of improving heat resistance etc. by adding a thermoplastic resin to a liquid crystal resin. However, none of these techniques suggests a specific technique for achieving the maximum reinforcing effect by adding a small amount of liquid crystal resin that does not impair the desirable properties of the base thermoplastic resin.
熱可塑性樹脂に液晶性樹脂を配合して、耐熱性、剛性、
寸法安定性を改良しようとする場合、液晶性樹脂を大量
に配合するとこれらの補強効果は増大傾向にあるものの
、衝撃強度低下、強度異方性などの好ましくない性質も
増大する場合が多い。By blending liquid crystal resin with thermoplastic resin, it achieves heat resistance, rigidity,
When attempting to improve dimensional stability, blending a large amount of liquid crystalline resin tends to increase these reinforcing effects, but often also increases unfavorable properties such as a decrease in impact strength and strength anisotropy.
従って本発明者らは、比較的少量の液晶性樹脂を配合し
て、上記の補強効果を最大限に発現させる方法を見いだ
すべく検討を行った。Therefore, the present inventors conducted studies to find a method of maximizing the above-mentioned reinforcing effect by blending a relatively small amount of liquid crystalline resin.
本発明は、熱可塑性樹脂（Ａ）６０ないし９５重量％と
、異方性溶融相を形成しうる樹脂（液晶性樹脂）（Ｂ）
４０ないし５重量％からなる組成物であって、成分（Ｂ
）が５〜５０ミクロンの平均粒子径で粒子状に分散して
いる熱可塑性樹脂組成物な提供する。以下に構成成分を
説明する。The present invention comprises a thermoplastic resin (A) in an amount of 60 to 95% by weight, and a resin (liquid crystalline resin) (B) capable of forming an anisotropic melt phase.
A composition comprising 40 to 5% by weight of component (B).
) is dispersed in the form of particles with an average particle size of 5 to 50 microns. The constituent components will be explained below.
１塑 Ａ
本発明は、周知の成形用樹脂材料の耐熱性、剛性、寸法
安定性を効果的に改良する。従って、上記の未達要求性
能を有する熱可塑性樹脂であれば、特に限定はされない
が、ポリエチレンテレフタレート、ポリエチレンテレフ
タレート、ポリアミド６、ポリアミド−６，６、ポリフ
ェニレンサルファイド、ポリエチレン、ポリプロピしン
などの結晶性樹脂が好ましい。また上記結晶性樹脂とポ
リカーボネート、ポリスチレン、ポリフェニレンエーテ
ル、ポリビニルクロライドなどの非品性樹脂の混合物を
用いることも好ましい。特に好ましい樹脂は、ポリエチ
レンテレフタレート、ポリブチレンテレフタレート、高
密度ポリエチレン、ポリプロピレンである。1 Plastic A The present invention effectively improves the heat resistance, rigidity, and dimensional stability of known molding resin materials. Therefore, as long as the thermoplastic resin has the above-mentioned unachieved performance requirements, crystalline resins such as polyethylene terephthalate, polyethylene terephthalate, polyamide 6, polyamide-6,6, polyphenylene sulfide, polyethylene, polypropylene, etc. Resins are preferred. It is also preferable to use a mixture of the above crystalline resin and a non-grade resin such as polycarbonate, polystyrene, polyphenylene ether, polyvinyl chloride. Particularly preferred resins are polyethylene terephthalate, polybutylene terephthalate, high density polyethylene, and polypropylene.
方性 を 成しうる樹脂（Ｂ）
本発明において用いられる異方性溶融相を形成しうる樹
脂は、いわゆる液晶性樹脂として周知である。異方性溶
融相の確認は、溶融状態の試料の偏光顕微鏡観察によっ
て実施できる。すなわち偏光子、検光子の直交条件下で
、光学異方性により光が透過することが認められる。Resin capable of forming anisotropic melt phase (B) The resin capable of forming an anisotropic melt phase used in the present invention is well known as a so-called liquid crystal resin. Confirmation of the anisotropic melt phase can be performed by observing a sample in a molten state using a polarizing microscope. That is, under the orthogonal conditions of the polarizer and analyzer, it is recognized that light is transmitted due to optical anisotropy.
液晶性樹脂の一般構造としては、脂肪族ジオールと芳香
族ジカルボン酸および芳香族ヒドロキシカルボン酸から
なる半芳香族ポリエステルと、芳香族ジオールと芳香族
ジカルボン酸、または、芳香族ジオールと芳香族ジカル
ボン酸および芳香族ヒドロキシカルボン酸、または、芳
香族ヒドロキシカルボン酸のみ、からなる全芳香族ポリ
エステルが知られている。ここで、脂肪族ジオールとし
ては、例えば、エチレングリコール、１．３−プロピレ
ンクリコール、１，４−ブテングリコール、１．６ヘキ
セングリコール、１．１２−ドデカメチレングリコール
等、芳香族ジオールとしては、例えば、１．４−または
１，３−ジヒドロキシベンゼン、４．４′または３．３
′−ジヒドロキシジフェニル、２．２−ビス（４′−ヒ
ドロキシフェニル）プロパン、４，４′−ジヒドロキシ
ジフェニルエーテル、４．４′−ジヒドロキジジフェニ
ルサルフオン、４．４′−ジヒドロキシジフェニルサル
ファイド、１，４−ジヒドロキシナフタレン、２．６−
ジヒドロキシナフタレン、１．６ジヒドロキシナフタレ
ン等、芳香族ジカルボン酸としては、テレフタル酸、イ
ソフタル酸、ジフェニル−４４′−ジカルボン酸、ナフ
タレン−１，４ジカルボン酸、ナフタレン−２，６−ジ
カルボン酸、シフェニルサルフオン−４，４′−ジカル
ホン酸、ンフェニルエーテルー４，４′−ジカルボン散
等、芳香族ヒドロキシカルボン酸としては、４−ヒドロ
キン安７！＋、香酸、４−ヒドロキシジフェニル−４−
力ルボン酸、２−ヒドロキシ−６−ナフトエ酸、１ヒド
ロキシ−４−ナフトエ酸等が挙げられる。The general structure of liquid crystal resin is a semi-aromatic polyester consisting of an aliphatic diol, an aromatic dicarboxylic acid, and an aromatic hydroxycarboxylic acid, an aromatic diol and an aromatic dicarboxylic acid, or an aromatic diol and an aromatic dicarboxylic acid. A wholly aromatic polyester consisting of an aromatic hydroxycarboxylic acid or only an aromatic hydroxycarboxylic acid is known. Here, examples of aliphatic diols include ethylene glycol, 1,3-propylene glycol, 1,4-butene glycol, 1.6-hexene glycol, and 1,12-dodecamethylene glycol; examples of aromatic diols include For example, 1,4- or 1,3-dihydroxybenzene, 4.4' or 3.3
'-dihydroxydiphenyl, 2,2-bis(4'-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 1,4 -dihydroxynaphthalene, 2.6-
Aromatic dicarboxylic acids such as dihydroxynaphthalene and 1.6 dihydroxynaphthalene include terephthalic acid, isophthalic acid, diphenyl-44'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, and cyphenyl. Examples of aromatic hydroxycarboxylic acids include sulfone-4,4'-dicarphonic acid, nphenyl ether-4,4'-dicarboxylic acid, and 4-hydroquine 7! +, aromatic acid, 4-hydroxydiphenyl-4-
Examples include carboxylic acid, 2-hydroxy-6-naphthoic acid, 1-hydroxy-4-naphthoic acid, and the like.
なお、ベンゼン環およびナフタレン環は低級アルキル基
、アリール基、ハロゲン基によって置換されていても良
い。Note that the benzene ring and naphthalene ring may be substituted with a lower alkyl group, an aryl group, or a halogen group.
本発明において用いられる（Ｃ）成分の具体例としては
、エチレングリコールとテレフタル酸および４−ヒドロ
キシ安息香酸とからなるポリエステル、１，４−ジヒド
ロキシベンゼンとテレフタル酸および４−ヒドロキシ安
息香酸とからなるポリエステル、４，４′−ジヒドロキ
シジフェニルとテレフタル酸および４−ヒドロキシ安息
香酸とからなるポリエステル、４，４′−ジヒドロキシ
ジフェニルとイソフタル酸および４−ヒドロキシ安息香
酸とからなるポリエステル、２−ヒドロキシ−６−ナフ
トエ酸と４−ヒドロキシ安息香酸とからなるポリエステ
ル等が代表的なものとして挙げられる。これらは、例え
ば、イーストマン社からｒＸ−７Ｇｊ、三菱化成社から
［ツバキュレート」、ユニチカ社から「ロッドラン」、
出光石油化学社から「出光ＬＣＰ」、ダートコ社、日水
石油化学社から「ザイダー」、住方化学工業社から「エ
コノール」、ヘキストセラニーズ社、ポリプラスチック
社から「ベクトラ」、アイシーアイジャパン社から「ピ
クトレックス」との商品名で、各々市販されている。Specific examples of component (C) used in the present invention include polyesters consisting of ethylene glycol, terephthalic acid and 4-hydroxybenzoic acid, and polyesters consisting of 1,4-dihydroxybenzene, terephthalic acid and 4-hydroxybenzoic acid. , polyester consisting of 4,4'-dihydroxydiphenyl and terephthalic acid and 4-hydroxybenzoic acid, polyester consisting of 4,4'-dihydroxydiphenyl and isophthalic acid and 4-hydroxybenzoic acid, 2-hydroxy-6-naphthoate Typical examples include polyester made of an acid and 4-hydroxybenzoic acid. These include, for example, rX-7Gj from Eastman, [Tubaculate] from Mitsubishi Kasei, and [Rodrun] from Unitika.
Idemitsu LCP from Idemitsu Petrochemicals, Dartco, Xider from Nissui Petrochemicals, Econol from Sumikata Chemical, Vectra from Hoechst Celanese and Polyplastics, and ICI Japan. Each is commercially available under the trade name ``Pictrex''.
分ＪＬＬ工
本発明の組成物は、熱可塑性樹脂の連続相に液晶性樹脂
が、適切な粒子径で粒子状に分散していることを特徴と
する。粒子径は次のようにして決定できる。位相差顕微
鏡、偏光顕微鏡、微分干渉顕微鏡などの光学票微鏡や、
走査型電子顕微鏡を用いて、観察した顕微鏡写真から、
分散粒子数か２００個以上になるように領域を定め、各
粒子の面積相当円直径を測定する。粒子径は市販の画像
解析装置を用いることができる。求めた各粒子像の相当
円直径から体積平均直径を計算し、平均粒子径とする。The composition of the present invention is characterized in that a liquid crystalline resin is dispersed in a continuous phase of a thermoplastic resin in the form of particles with an appropriate particle size. Particle size can be determined as follows. Optical microscopes such as phase contrast microscopes, polarizing microscopes, and differential interference microscopes,
From the micrographs observed using a scanning electron microscope,
A region is defined so that the number of dispersed particles is 200 or more, and the area-equivalent circular diameter of each particle is measured. A commercially available image analysis device can be used to measure the particle size. The volume average diameter is calculated from the equivalent circular diameter of each particle image obtained, and is taken as the average particle diameter.
平均粒子径はらないし５０ミクロン、好ましくは１０な
いし４０ミクロンである。平均粒子径が５ミクロン未満
では耐熱性、剛性、寸法安定性における改良効果が小さ
い。平均粒子径が５０ミクロンを越えると、成形時の配
向が著しくなり、層剥離を生じる場合があり、外観の不
良、強度の低下をもたらすことがある。一般にポリマー
ブレンドの技術分野では、分散粒子径の微細化により補
強効果の増大を目指しているのに対し、本発明の組成物
の構造では、好適な粒子径にミクロンオーダーの下限が
ある。The average particle size is from 0 to 50 microns, preferably from 10 to 40 microns. If the average particle diameter is less than 5 microns, the effect of improving heat resistance, rigidity, and dimensional stability is small. If the average particle diameter exceeds 50 microns, orientation during molding becomes significant, which may cause layer peeling, resulting in poor appearance and reduced strength. Generally, in the technical field of polymer blends, the aim is to increase the reinforcing effect by making the dispersed particle size finer, whereas in the structure of the composition of the present invention, there is a lower limit of the preferred particle size on the order of microns.
炙光皿り
成分（Ａ）熱可塑性樹脂６０ないし９５重量％、好まし
くは７０ないし９０重量％、および成分（Ｂ）異方性溶
融相を形成しうる樹脂、５ないし４０重量％、好ましく
は１０ないし３０重量％である。成分（Ｂ）が５重量％
未満ては、耐熱性、剛性、寸法安定性の改良効果が小さ
く、４０重量％超過では、これら効果は増大する傾向に
あるが、強度異方性、衝撃強度の低下なとの好ましくな
い性質が順著となる。Component (A) 60 to 95% by weight of a thermoplastic resin, preferably 70 to 90% by weight, and component (B) a resin capable of forming an anisotropic melt phase, 5 to 40% by weight, preferably 10% by weight. and 30% by weight. Component (B) is 5% by weight
If it is less than 40% by weight, the effect of improving heat resistance, rigidity, and dimensional stability is small, and if it exceeds 40% by weight, these effects tend to increase, but unfavorable properties such as strength anisotropy and decrease in impact strength occur. Authored in order.
」炎ｑ
本発明の組成物は、ロール、バンバリーミキサ−軸およ
び二軸混練機などて、用いる液晶性樹脂が異方性溶融相
を形成しうる温度の範囲て゛溶融混練することにより製
造できる。分散相の粒子径の制御には両成分の粘度比、
両成分の親和性なとの当業者周知の因子を適宜選定する
ことにより達成できる。混線条件に近い剪断速度条件で
求めた両成分の粘度比が１に近付くほど粒子径は細かく
なる。また両成分の親和性が良好であるほど分散粒子径
は小さくなる。また、親和性の調整には、いわゆる相溶
化剤を用いることができる。相溶化剤とは、ポリマーア
ロイの技術分野で良く知られている、非相溶の二成分の
両方に親和性を有する第三添加物であり、両成分の各々
を部分鎖とするグラフト共重合体、プロ・ンク共重合体
か一般に用いられている。また混合方法によって分散粒
子径を制御することも可能である。一般には、剪断履歴
が大であるほど粒子径は小さくなる。Flame q The composition of the present invention can be produced by melt-kneading using rolls, a Banbury mixer shaft, a twin-screw kneader, or the like, within a temperature range in which the liquid crystalline resin used can form an anisotropic melt phase. To control the particle size of the dispersed phase, the viscosity ratio of both components,
This can be achieved by appropriately selecting factors known to those skilled in the art regarding the affinity of both components. The particle size becomes finer as the viscosity ratio of both components approaches 1, which is determined under shear rate conditions close to the crosstalk conditions. Furthermore, the better the affinity between the two components, the smaller the dispersed particle size. Furthermore, a so-called compatibilizer can be used to adjust the affinity. A compatibilizer is a third additive that has affinity for both two incompatible components, which is well known in the technical field of polymer alloys, and is a graft copolymer that has partial chains of both components. Copolymer and Pro-Nc copolymers are commonly used. It is also possible to control the dispersed particle size by the mixing method. Generally, the greater the shear history, the smaller the particle size.
［実施例〕
第１表に実施例および比較例の組成を示す。組成物の製
造は、所定の配合物を池貝鉄工（株）製ＰＣＭ二軸押出
機を用い、液晶性樹脂の融点より約２０″Ｃ高い温度で
、混合後水冷しペレットを得た。このベレットを１２０
℃に設定された減圧乾燥機にて１２時間乾燥後、名ｉ製
作所（株）製Ｍ４０ Ａ −Ｓ 、Ｊ型射出成形機を用
いて、所定の試験片を作成した。成形温度は、液晶性樹
脂の融点より２０℃高い温度に設定した。[Examples] Table 1 shows the compositions of Examples and Comparative Examples. The composition was manufactured by mixing a predetermined mixture using a PCM twin-screw extruder manufactured by Ikegai Tekko Co., Ltd. at a temperature approximately 20"C higher than the melting point of the liquid crystal resin, and then cooling with water to obtain pellets. 120
After drying for 12 hours in a vacuum dryer set at .degree. C., predetermined test pieces were prepared using an M40 A-S, J-type injection molding machine manufactured by Mei Seisakusho Co., Ltd. The molding temperature was set at a temperature 20° C. higher than the melting point of the liquid crystal resin.
曲げ弾性率は、ＪＩＳ Ｋ７２０３に準拠して、２３°
Ｃで測定した。熱変形温度はＪＩＳ Ｋ７１１０に準拠
して荷重４．６ｋｇにて測定した。線膨張率は＾ＳＴＭ
Ｄ６９６−７９に準拠して作成された市販の石英管式
膨張計を用いて、長さ９０ｍｍ、幅１０ＩＩＩｎ、厚さ
４鴎−の試駒片を１２０°Ｃ１１時間熱処理した後、温
度３０℃〜８０℃の範囲て測定した。The bending elastic modulus is 23° according to JIS K7203.
Measured at C. The heat distortion temperature was measured under a load of 4.6 kg in accordance with JIS K7110. The coefficient of linear expansion is ^STM
Using a commercially available quartz tube dilatometer made in accordance with D696-79, a test piece with a length of 90 mm, a width of 10 mm, and a thickness of 4 mm was heat treated at 120°C for 11 hours, and then the temperature was increased to 30°C. Measurements were made within a range of 80°C.
液晶性樹脂の分散粒子径は、ペレットから圧縮成形した
試片から一部を切り出し、ミクロトームにて電子顕微鏡
観察用試料を調整し、イオンエツチング装置を用いて減
圧度０．９Ｔｏｒｒ、エツチング時間１０分の条件てイ
オンエツチングしたのち、走査型電子詔微鏡（明石製作
断裂ＭＳＭ−９）にて分散粒子径写真を撮影した。写真
上の粒子径を測定粒子像の数が２００を越えるように測
定領域を設定して、画像解析装置（日本アビオニクス社
製５ＰＩＣＣΔ■）によって面積相当円直径を計測し、
間隔０．５ミクロンのヒストグラムを作成する。The dispersed particle size of the liquid crystalline resin was determined by cutting out a portion of a test piece compression-molded from a pellet, preparing a sample for electron microscopy observation using a microtome, and etching it using an ion etching device at a reduced pressure of 0.9 Torr and an etching time of 10 minutes. After ion etching under the following conditions, a photograph of the dispersed particle size was taken using a scanning electronic microscope (Akashi Separation MSM-9). Measuring the particle diameter on the photograph The measurement area was set so that the number of particle images exceeded 200, and the area-equivalent circle diameter was measured using an image analysis device (5PICCΔ■ manufactured by Nippon Avionics Co., Ltd.).
Create a histogram with intervals of 0.5 microns.
Ｄ−Σ口ｉＤ ｉ’／ΣｎｉＤ ｉ３（ヒストグラムの
代表値Ｄｉに属する粒子数ｎｉ）によって計算される体
積平均粒子径りによって平均粒子径を評価した。The average particle diameter was evaluated based on the volume average particle diameter calculated by D-ΣiD i'/ΣniD i3 (number of particles ni belonging to the representative value Di of the histogram).
第１表の各組成物の評価結果を第２表に示した。The evaluation results for each composition in Table 1 are shown in Table 2.
第１表（組成）
１〉
ポリプロピレン
三菱油化（株）「三菱ポリ
プロＭＡ８．１
メルトフローレート１
、Ｏｙ／１
分、
２）ベクトラ
・ポリプラスチック社製液晶性樹
脂［ベクトラＡ９
Ｏ」
３）ポリアミド−６：三菱化成（株）製「ツバミント１
０４０Ｊ、
４）ポリエチレンテレフタトート、日本ユニペット製ｒ
ＲＴ５８０ｃＡ」、
５）ンラン変性ポリプロピレン、試作品、メルトフロー
レートｌｏ、５ｇ／１０分、ビニルトリメＩ−キシシラ
ンの含量２．６重量％。Table 1 (Composition) 1> Polypropylene Mitsubishi Yuka Co., Ltd. "Mitsubishi Polypro MA8.1 Melt flow rate 1, Oy/1 min, 2) Liquid crystalline resin manufactured by Vectra Polyplastics [Vectra A9 O"] 3) Polyamide -6: Mitsubishi Kasei Corporation “Tubamint 1”
040J, 4) Polyethylene terephthalate tote, Nippon Unipet r
RT580cA'', 5) Polypropylene modified with polymer, prototype, melt flow rate lo, 5 g/10 min, content of vinyl trime I-xysilane 2.6% by weight.
／ ／ ／ ／′ ／ 第２表（結果） 本成形後１２０°Ｃ１時間熱処理後に評価。/ / / /′ / Table 2 (results) Evaluation was performed after heat treatment at 120°C for 1 hour after main molding.
第２表の結果より、平均粒子径５〜５０ミクロンに分散
させた液晶性樹脂の補強効果は、１０重量部配合でも著
しく、配合量の増加とともに、増大することが明らかで
ある。本発明の熱可塑性樹脂組成物は、耐熱性と剛性、
寸法安定性を要求される高温下の使用環境に用いられる
機構部品に望ましい組成物の構成を提示するものである
。From the results in Table 2, it is clear that the reinforcing effect of the liquid crystal resin dispersed with an average particle size of 5 to 50 microns is remarkable even when 10 parts by weight is added, and increases as the amount is increased. The thermoplastic resin composition of the present invention has heat resistance and rigidity,
The present invention presents a desirable composition for mechanical parts used in high-temperature operating environments that require dimensional stability.
特 許 出 願 人 三菱油化株式会社Special permission Out wish Man Mitsubishi Yuka Co., Ltd.
Claims (1)
融相を形成しうる樹脂（Ｂ）４０ないし５重量％からな
り、異方性溶融相を形成しうる樹脂（Ｂ）は、平均粒子
径５〜５０ミクロンの粒子状で分散していることを特徴
とする熱可塑性樹脂組成物。The thermoplastic resin (A) is composed of 60 to 95% by weight, and the resin (B) capable of forming an anisotropic melt phase is composed of 40 to 5% by weight, and the resin (B) capable of forming an anisotropic melt phase has an average A thermoplastic resin composition characterized in that it is dispersed in the form of particles with a particle size of 5 to 50 microns.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13373890A JPH0428768A (en) | 1990-05-25 | 1990-05-25 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13373890A JPH0428768A (en) | 1990-05-25 | 1990-05-25 | Thermoplastic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0428768A true JPH0428768A (en) | 1992-01-31 |
Family
ID=15111766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13373890A Pending JPH0428768A (en) | 1990-05-25 | 1990-05-25 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0428768A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0790280A1 (en) * | 1994-10-18 | 1997-08-20 | Polyplastics Co. Ltd. | Thermoplastic resin composition, injection molding method thereof and injection molded article |
| US6361827B1 (en) | 1997-12-26 | 2002-03-26 | Showa Sangyo Co., Ltd. | Method of imparting water resistance to molded polysaccharide |
| JP4639442B2 (en) * | 2000-08-25 | 2011-02-23 | 東レ株式会社 | Resin structure, and chemical or gas transport and / or storage container comprising the resin structure and its accessories. |
-
1990
- 1990-05-25 JP JP13373890A patent/JPH0428768A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0790280A1 (en) * | 1994-10-18 | 1997-08-20 | Polyplastics Co. Ltd. | Thermoplastic resin composition, injection molding method thereof and injection molded article |
| EP0790280A4 (en) * | 1994-10-18 | 1998-08-12 | Polyplastics Co | Thermoplastic resin composition, injection molding method thereof and injection molded article |
| US6361827B1 (en) | 1997-12-26 | 2002-03-26 | Showa Sangyo Co., Ltd. | Method of imparting water resistance to molded polysaccharide |
| JP4639442B2 (en) * | 2000-08-25 | 2011-02-23 | 東レ株式会社 | Resin structure, and chemical or gas transport and / or storage container comprising the resin structure and its accessories. |
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