JPH0578563A - Production of thermoplastic resin composition - Google Patents
Production of thermoplastic resin compositionInfo
- Publication number
- JPH0578563A JPH0578563A JP24377291A JP24377291A JPH0578563A JP H0578563 A JPH0578563 A JP H0578563A JP 24377291 A JP24377291 A JP 24377291A JP 24377291 A JP24377291 A JP 24377291A JP H0578563 A JPH0578563 A JP H0578563A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resin
- parts
- zinc oxide
- polyamide resin
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、ポリアリレート樹脂、
ポリアミド樹脂、酸化亜鉛又はシリカ及び/又はアルミ
ナ中に酸化亜鉛を均一に分散させた触媒を所定量配合
し、それを所定条件で溶融反応させることにより得られ
るポリマーアロイの相溶化に有用な熱可塑性樹脂組成物
に関する。The present invention relates to a polyarylate resin,
Thermoplastic useful for compatibilizing a polymer alloy obtained by blending a predetermined amount of a catalyst in which zinc oxide is uniformly dispersed in polyamide resin, zinc oxide or silica and / or alumina, and melting and reacting the catalyst under predetermined conditions. It relates to a resin composition.
【0001】[0001]
【従来の技術】結晶性熱可塑性樹脂は、堅くて剛直、耐
摩擦摩耗性、耐溶剤性に優れる、流動性が良好である等
の長所を有する反面脆くて割れ易い、不透明、成形収縮
が大きいなどの欠点を有している。一方、非晶性熱可塑
性樹脂は、結晶性樹脂と反対に透明性、柔軟性に優れ
る、成形収縮率が小さいTgが高いなどの長所を有する
反面耐薬品性、耐摩擦摩耗性が悪い、流動性が低い等の
欠点を有している。2. Description of the Related Art A crystalline thermoplastic resin has advantages such as being hard and rigid, excellent in abrasion and wear resistance, solvent resistance, and having good fluidity, but it is brittle and easily cracked, opaque, and has a large molding shrinkage. It has drawbacks such as On the other hand, an amorphous thermoplastic resin has advantages such as transparency and flexibility, which are opposite to those of a crystalline resin, a small molding shrinkage ratio and a high Tg, but it has poor chemical resistance, poor abrasion resistance, and fluidity. It has drawbacks such as poor property.
【0002】一般に耐熱性、耐衝撃性、成形性、耐薬品
性などの諸特性がいずれも良好な樹脂組成物は単一の樹
脂から得ることは困難であるため、結晶性樹脂の場合
は、その欠点を補うため非晶性の樹脂とのポリマーアロ
イが行われる。しかしながら、通常結晶性樹脂と非晶性
樹脂とは相溶性が悪く、単に二つの樹脂を混ぜ合わせた
だけでは非相溶ミクロ相分離型海島構造をとることがで
きないため、二つの樹脂の長所を合わせ持つような熱可
塑性樹脂組成物を得ることは困難である。相溶性の改善
を図る手法としては、結晶性樹脂、非晶性樹脂の両方に
親和性を有する相溶化剤を添加する方法が一般に行われ
るが、ポリアミド樹脂とPET,PBT、PC、ポリア
リレート、液晶ポリマー等のポリエステル系ポリマーの
場合好適な相溶化剤がなく、ポリマーアロイ化は困難で
あった。Generally, it is difficult to obtain a resin composition having good properties such as heat resistance, impact resistance, moldability and chemical resistance from a single resin. Therefore, in the case of a crystalline resin, In order to make up for the drawback, a polymer alloy with an amorphous resin is performed. However, the compatibility between the crystalline resin and the amorphous resin is usually poor, and the incompatibility micro phase separation type sea-island structure cannot be taken simply by mixing the two resins, so that the advantages of the two resins are It is difficult to obtain a thermoplastic resin composition that can be held together. As a method for improving the compatibility, a method of adding a compatibilizing agent having an affinity for both the crystalline resin and the amorphous resin is generally performed, and a polyamide resin and PET, PBT, PC, polyarylate, In the case of polyester-based polymers such as liquid crystal polymers, there is no suitable compatibilizing agent, and polymer alloying is difficult.
【0003】[0003]
【発明が解決しようとする課題】本発明が目的とすると
ころは、ポリアリレート樹脂、ポリアミド樹脂、酸化亜
鉛又はシリカ及び/又はアルミナ中に酸化亜鉛を均一に
分散させた触媒を所定量配合し、それを所定条件で溶融
反応させることにより得られる、ポリアミド樹脂とポリ
エステル系樹脂の相溶化に有用な熱可塑性樹脂組成物を
提供することにある。The object of the present invention is to blend a predetermined amount of a catalyst in which zinc oxide is uniformly dispersed in polyarylate resin, polyamide resin, zinc oxide or silica and / or alumina, It is to provide a thermoplastic resin composition useful for compatibilizing a polyamide resin and a polyester resin, which is obtained by melting and reacting the resin under predetermined conditions.
【0004】[0004]
【課題を解決するための手段】本発明者らは、ポリアミ
ド樹脂とポリエステル系樹脂の相溶性改善を図るため種
々検討した結果、ポリアリレート樹脂、ポリアミド樹
脂、酸化亜鉛又はシリカ及び/又はアルミナ中に酸化亜
鉛を均一に分散させた触媒を所定量配合し、それらをさ
らに所定条件で溶融反応させることにより得られる熱可
塑性樹脂組成物が、ポリアミド樹脂とポリエステル系樹
脂との相溶性改善に顕著な効果を有することを見いだし
本発明を完成するに到った。Means for Solving the Problems As a result of various studies aimed at improving the compatibility of a polyamide resin and a polyester resin, the present inventors have found that polyarylate resin, polyamide resin, zinc oxide or silica and / or alumina A thermoplastic resin composition obtained by blending a predetermined amount of a catalyst in which zinc oxide is uniformly dispersed and further subjecting them to a melt reaction under predetermined conditions has a remarkable effect on improving the compatibility between the polyamide resin and the polyester resin. The present invention has been completed and the present invention has been completed.
【0005】すなわち本発明は、(a)ポリアリレート
樹脂80〜20重量部、(b)ポリアミド樹脂20〜8
0重量部及び(c)前記ポリアルレート樹脂と前記ポリ
アミド樹脂の合計100重量部に対して酸化亜鉛を0.
01〜10重量部添加し、240〜300℃で10〜2
40分溶融反応させることにより得られることを特徴と
する熱可塑性樹脂組成物の製造方法、及び(a)ポリア
リレート樹脂80〜20重量部、(b)ポリアミド樹脂
20〜80重量部及び(c)前記ポリアリレート樹脂と
前記ポリアミド樹脂の合計100重量部に対して、シリ
カ及び/又はアルミナ中に酸化亜鉛を均一に分散させた
触媒を0.01〜10重量部添加し、240〜300℃
で10〜240分溶融反応させることにより得られるこ
とを特徴とする熱可塑性樹脂組成物の製造方法に関する
ものである。That is, the present invention relates to (a) 80 to 20 parts by weight of polyarylate resin, and (b) 20 to 8 of polyamide resin.
0 parts by weight and (c) zinc oxide to 0.1 part by weight based on 100 parts by weight of the polyallate resin and the polyamide resin.
Add 01 to 10 parts by weight and add 10 to 2 at 240 to 300 ° C.
A method for producing a thermoplastic resin composition, which is obtained by performing a melt reaction for 40 minutes, and (a) polyarylate resin 80 to 20 parts by weight, (b) polyamide resin 20 to 80 parts by weight, and (c). To the total of 100 parts by weight of the polyarylate resin and the polyamide resin, 0.01 to 10 parts by weight of a catalyst in which zinc oxide is uniformly dispersed in silica and / or alumina is added, and 240 to 300 ° C.
It relates to a method for producing a thermoplastic resin composition, which is obtained by performing a melting reaction for 10 to 240 minutes.
【0006】本発明で用いられるポリアリレート樹脂は
特に限定するものでなく市販されているものであり、2
価のフェノール類と芳香族ジカルボン酸を高温溶融状態
で反応させる溶融重合法、脱酸剤としてのアミン存在
下、二価のフェノール類と芳香族ジカルボン酸ジクロラ
イドを有機溶媒中で反応させる溶液重合法、二価のフェ
ノール類と芳香族ジカルボン酸ジクロライドとを互いに
相溶しない2種溶媒に溶解した後、アルカリ存在下で2
液を撹はんして、その界面で重縮合反応を行わせる界面
重合法などにより製造することが出来る。The polyarylate resin used in the present invention is not particularly limited and is commercially available.
Melt polymerization method in which divalent phenols and aromatic dicarboxylic acids are reacted in a high temperature molten state, solution polymerization method in which divalent phenols and aromatic dicarboxylic acid dichlorides are reacted in an organic solvent in the presence of an amine as a deoxidizing agent , Divalent phenols and aromatic dicarboxylic acid dichloride are dissolved in two kinds of solvents which are incompatible with each other, and then 2
It can be produced by an interfacial polymerization method in which the liquid is stirred and a polycondensation reaction is carried out at the interface.
【0007】これらのポリアリレート樹脂の製造に使用
し得る適切な2価フェノール類としては、2、2ービ
ス(4ーヒドロキシフェニル)プロパン(ビスフェノー
ルA)、レゾルシノール、ハイドロキノン、2、2’ー
ジヒドロキシジフェニル、2、6ージヒドロキシナフタ
レン、ビス(4ーヒドロキシフェニル)スルホン、ビス
(4ーヒドロキシフェニル)スルホキシド、ビス(4ー
ヒドロキシフェニル)ケトン、ビス(4ーヒドロキシフ
ェニル)エーテルが有る。ポリアリレート樹脂を製造す
る際、2価フェノール類を2種以上用いたり、2価フェ
ノール類のホモポリマーまたは2種以上用いたコポリマ
ーあるいはこれらの混合物であってもよい。又、これら
のポリアリレート樹脂の製造に使用し得る適切なジカル
ボン酸としては、例えば、テレフタル酸、イソフタル
酸、ナフタレンジカルボン酸及びそれらの混合物、並び
にこれら芳香族ジカルボン酸のアルキル置換同族体、ハ
ロゲン化物などがある。Suitable dihydric phenols which can be used in the production of these polyarylate resins include 2,2-bi-phenols.
Sus (4-hydroxyphenyl) propane (bisphenol A), resorcinol, hydroquinone, 2,2′-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, There are bis (4-hydroxyphenyl) ketone and bis (4-hydroxyphenyl) ether. When the polyarylate resin is produced, two or more dihydric phenols may be used, a homopolymer of dihydric phenols, a copolymer using two or more dihydric phenols, or a mixture thereof. Suitable dicarboxylic acids that can be used in the production of these polyarylate resins include, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and mixtures thereof, and alkyl-substituted homologues of these aromatic dicarboxylic acids and halides. and so on.
【0008】本発明で用いられるポリアミド樹脂は、特
に限定するものではなく市販されているものであり、ヘ
キサメチレンジアミン、デカメチレンジアミン、ドデカ
メチレンジアミン、1,3−又は1,4−ビス(アミノ
メチル)シクロヘキサン、m−又はp−キシリレンジア
ミンのような脂肪族、脂環族、芳香族などのジアミン
と、アジピン酸、セバチン酸、シクロヘキサンジカルボ
ン酸、テレフタル酸、イソフタル酸などの脂肪族、脂環
族、芳香族などのジカルボン酸から製造されるポリアミ
ド樹脂、あるいはε−カプロラクタム、ω−ドデカラク
タムのようなラクタムから製造されるポリアミド樹脂及
びこれらの混合物あるいはこれらの成分からなる共重合
ポリアミド樹脂などが例示される。The polyamide resin used in the present invention is not particularly limited and is commercially available. Hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,3- or 1,4-bis (amino) Methyl) cyclohexane, diamines such as aliphatic, alicyclic and aromatic such as m- or p-xylylenediamine, and aliphatic and fats such as adipic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid and isophthalic acid Polyamide resins produced from dicarboxylic acids such as aromatics and aromatics, polyamide resins produced from lactams such as ε-caprolactam and ω-dodecaractam, and mixtures or copolymerized polyamide resins containing these components. Is exemplified.
【0009】具体例としては、ポリカプロアミド(ナイ
ロン6)、ポリヘキサメチレンアジパミド(ナイロン6
6)、ポリヘキサメチレンセバカミド(ナイロン6,1
0)、ポリヘキサメチレンドデカミド(ナイロン6,1
2)、ポリウンデカンアミド(ナイロン11)、ポリド
デカンアミド(ナイロン12)、ポリキシリレンアジパ
ミド、ポリヘキサメチレンテレフタラミド、ポリフェニ
レンフタラミド等が挙げられる。ここで用いられるポリ
アミド樹脂の重合度は特に制限なく、通常相対粘度が
2.0〜5.0の範囲のものが好ましい。Specific examples include polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 6).
6), polyhexamethylene sebacamide (nylon 6,1
0), polyhexamethylene dodecamide (nylon 6,1
2), polyundecane amide (nylon 11), polydodecane amide (nylon 12), polyxylylene adipamide, polyhexamethylene terephthalamide, polyphenylene phthalamide and the like. The degree of polymerization of the polyamide resin used here is not particularly limited, and one having a relative viscosity of 2.0 to 5.0 is usually preferable.
【0010】本発明において、ポリアリレート樹脂
(a)とポリアミド樹脂(b)は、(a):(b)=8
0:20〜20:80重量部、好ましくは70:30〜
30:70重量部、さらに好ましくは(a):(b)=
60:40〜40:60重量部の範囲で配合される。ポ
リアリレート樹脂の配合量が20重量部を下回るかポリ
アミド樹脂の配合量が20重量部を下回ると相溶性の改
善効果が低下する。In the present invention, the polyarylate resin (a) and the polyamide resin (b) are (a) :( b) = 8.
0: 20-20: 80 parts by weight, preferably 70: 30-
30:70 parts by weight, more preferably (a) :( b) =
It is mixed in the range of 60:40 to 40:60 parts by weight. If the compounding amount of the polyarylate resin is less than 20 parts by weight or the compounding amount of the polyamide resin is less than 20 parts by weight, the effect of improving the compatibility decreases.
【0011】本発明で用いられる酸化亜鉛又はシリカ及
び/又はアルミナ中に酸化亜鉛を均一に分散させた触
媒は、ポリアリレート樹脂とポリアミド樹脂との反応触
媒の働きをする重要な成分である。本発明で用いられる
酸化亜鉛は、その製法は限定されるものではないが、例
えば金属亜鉛を空気中で 燃焼させる方法あるいは硝酸
亜鉛とアンモニア水又はアンモニアガスから水酸化亜鉛
を得、それを低温で乾燥させる方法などにより得ること
が出来る。上記の製法のうち、硝酸亜鉛とアンモニア水
又はアンモニアガスから水酸化亜鉛を得、それを低温で
乾燥する方法は、高温で処理する他の方法に較べ酸化亜
鉛の活性が大きいため好ましい。又、本発明で用いられ
る酸化亜鉛の特性値は特に限定するものではないが、好
ましくは平均粒子径が0.01〜20μm、比表面積が
5〜100m2 /g、更に好ましくは平均粒子径が0.
01〜2μm、比表面積が10〜100m2 /gのもの
が好適に使用される。The zinc oxide or silica and / or alumina used in the present invention has a uniform dispersion of zinc oxide.
The medium is an important component that acts as a reaction catalyst for the polyarylate resin and the polyamide resin. The production method of zinc oxide used in the present invention is not limited, but for example, a method of burning metallic zinc in air or zinc nitrate obtained from zinc nitrate and aqueous ammonia or ammonia gas, which is prepared at low temperature It can be obtained by a method of drying. Among the above-mentioned production methods, the method of obtaining zinc hydroxide from zinc nitrate and ammonia water or ammonia gas and drying it at a low temperature is preferable because the activity of zinc oxide is larger than that of other methods of treating at a high temperature. The characteristic value of the zinc oxide used in the present invention is not particularly limited, but preferably the average particle size is 0.01 to 20 μm, the specific surface area is 5 to 100 m 2 / g, and more preferably the average particle size is 0.
Those having a surface area of 01 to 2 μm and a specific surface area of 10 to 100 m 2 / g are preferably used.
【0012】本発明で用いられるシリカ及び/又はアル
ミナ中に酸化亜鉛を均一に分散させた触媒は、亜鉛無機
塩類の水溶液にテトラエトキシシラン及び/又はアルミ
ニウムの無機塩類の水溶液を加え、更にアンモニア水を
添加するかアンモニアガスを吹き込むことによりヒドロ
ゲルの格子の中に非常にミクロなレベルで水酸化亜鉛を
均一に分散させた中間体を作り、この中間体を120〜
200℃で乾燥させ、更に300℃〜500℃で焼成す
ることにより得ることが出来る。無機塩類としては、硝
酸塩が得られる触媒の活性が大きいため好ましい。The catalyst used in the present invention, in which zinc oxide is evenly dispersed in silica and / or alumina, is prepared by adding an aqueous solution of tetraethoxysilane and / or an inorganic salt of aluminum to an aqueous solution of zinc inorganic salt, and further adding ammonia water. Is added or ammonia gas is blown into the hydrogel lattice to form an intermediate in which zinc hydroxide is uniformly dispersed at a very micro level.
It can be obtained by drying at 200 ° C. and further baking at 300 ° C. to 500 ° C. Inorganic salts are preferable because the activity of the catalyst for obtaining nitrate is large.
【0013】又、亜鉛無機塩類、テトラエトキシシラ
ン、アルミニウム無機塩類の配合比率としては、Zn原
子のモル数:(Si原子のモル数+Al原子のモル数)
=1:1〜1:0.1の範囲が好ましい。(Si原子の
モル数+Al原子のモル数)が1を上回ると、触媒中の
酸化亜鉛の含有率が低くなり触媒活性が低下し、0.1
を下回ると触媒中での酸化亜鉛の分散が不十分となり、
触媒活性が低下する。The zinc inorganic salt, tetraethoxysilane, and aluminum inorganic salt are mixed in proportions such that the number of moles of Zn atom: (the number of moles of Si atom + the number of moles of Al atom).
= 1: 1 to 1: 0.1 is preferable. When (the number of moles of Si atom + the number of moles of Al atom) is more than 1, the content of zinc oxide in the catalyst is low and the catalytic activity is lowered to 0.1.
When it is below the range, the dispersion of zinc oxide in the catalyst becomes insufficient,
The catalytic activity is reduced.
【0014】ポリアリレート樹脂とポリアミド樹脂とを
所定の割合で配合した樹脂組成物100重量部に対し、
酸化亜鉛又はシリカ及び/又はアルミナ中に酸化亜鉛を
均一に分散させた触媒を0.01〜10重量部、好まし
くは0.1〜3重量部添加し240〜300℃で10〜
120分溶融反応させることによりポリアミド樹脂とポ
リエステル系樹脂の相溶性を顕著に改善する効果を有す
る熱可塑性樹脂組成物を得ることが出来る。反応温度が
240℃を下回ると樹脂が溶融しづらくなり、300℃
を上回ると熱分解が始まる。又、時間が10分を下回る
と樹脂間の反応が不十分となり、240分を越えるとも
はや反応は進行しない。With respect to 100 parts by weight of a resin composition in which a polyarylate resin and a polyamide resin are mixed in a predetermined ratio,
0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight of a catalyst in which zinc oxide is uniformly dispersed in zinc oxide or silica and / or alumina is added, and the catalyst is added at 240 to 300 ° C. for 10 to 10 parts by weight.
By performing a melt reaction for 120 minutes, a thermoplastic resin composition having an effect of remarkably improving the compatibility of the polyamide resin and the polyester resin can be obtained. If the reaction temperature is lower than 240 ° C, it will be difficult for the resin to melt and 300 ° C
When it exceeds the value, thermal decomposition begins. If the time is less than 10 minutes, the reaction between the resins becomes insufficient, and if it exceeds 240 minutes, the reaction no longer proceeds.
【0015】このように本発明の熱可塑性樹脂組成物
は、ポリアミド樹脂とポリエステル系樹脂の相溶性を顕
著に改善する効果を有しているが、その理由としては、
酸化亜鉛又はシリカ及び/又はアルミナ中に酸化亜鉛を
均一に分散させた触媒が反応触媒として働くことにより
ポリアリレート樹脂とポリアミド樹脂との間に反応が生
じ、同一分子内にポリアリレート成分及びポリアミド成
分を有する反応生成物が界面活性剤的な働きをすること
により、ポリアミド樹脂とポリエステル系樹脂との相溶
性を改善し、非相溶ミクロ相分離型海島構造を取ること
が可能になったためと考えられる。As described above, the thermoplastic resin composition of the present invention has an effect of remarkably improving the compatibility between the polyamide resin and the polyester resin. The reason is as follows.
A catalyst in which zinc oxide or zinc oxide is uniformly dispersed in silica and / or alumina acts as a reaction catalyst, whereby a reaction occurs between the polyarylate resin and the polyamide resin, and the polyarylate component and the polyamide component are contained in the same molecule. It is considered that the reaction product having a function of acting as a surfactant improves the compatibility between the polyamide resin and the polyester resin and enables the formation of an incompatible micro phase separation type sea-island structure. Be done.
【0016】ポリアミド樹脂とポリエステル系樹脂に対
する本発明の熱可塑性樹脂組成物の添加量としては、両
樹脂の合計100重量部に0.5〜10重量部の範囲が
好ましい。The addition amount of the thermoplastic resin composition of the present invention to the polyamide resin and the polyester resin is preferably 0.5 to 10 parts by weight based on 100 parts by weight of both resins.
【0017】[0017]
《実施例1》硝酸亜鉛水溶液(0.1mol/l)と硝
酸アルミニウム水溶液(0.1mol/l)とを等量混
合した混合溶液にアンモニアガスを室温で吹き込み、得
られた沈澱物を水洗したのちスプレー乾燥機で乾燥し、
更に350℃で8時間乾燥し酸化亜鉛Aを得た。Example 1 Ammonia gas was blown at room temperature into a mixed solution obtained by mixing equal amounts of an aqueous zinc nitrate solution (0.1 mol / l) and an aqueous aluminum nitrate solution (0.1 mol / l), and the obtained precipitate was washed with water. Then dry with a spray dryer,
Further, it was dried at 350 ° C. for 8 hours to obtain zinc oxide A.
【0018】ポリアリレート樹脂(UポリマーR U−1
060、ユニチカ(株)製)70重量部、ポリアミド樹
脂(UBEナイロン1013FB、宇部興産(株)製)
30重量部、酸化亜鉛A1重量部を熱ニーダーに投入
し、樹脂温が240〜270℃になるような条件で30
分間溶融混練し、その後冷却粉砕して本発明の熱可塑性
樹脂組成物Aを得た。Polyarylate resin (U polymer R U-1
060, Unitika Ltd. 70 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.)
30 parts by weight and 1 part by weight of zinc oxide A were put into a heat kneader, and the resin temperature was adjusted to 240 to 270 ° C.
The mixture was melt-kneaded for a minute and then cooled and pulverized to obtain a thermoplastic resin composition A of the present invention.
【0019】ポリアリレート樹脂(UポリマーR U−1
060、ユニチカ(株)製)60重量部、ポリアミド樹
脂(UBEナイロン1013FB、宇部興産(株)製)
40重量部、熱可塑性樹脂組成物A1重量部をヘンシェ
ルミキサーに投入し、800〜1200rpmで数分間
混合し、これを二軸混練機にて樹脂温が240〜270
℃になるような条件で溶融混練してペレットを作り、そ
の後射出成形を行い、成形性の評価と共に得られた試験
片について熱変形温度、アイゾット衝撃強度、耐薬品
性、溶融粘度の評価を行った。その評価結果を表1に示
す。Polyarylate resin (U polymer R U-1
060, Unitika Ltd. 60 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.)
40 parts by weight and 1 part by weight of the thermoplastic resin composition A are put into a Henschel mixer and mixed at 800 to 1200 rpm for several minutes, and the resin temperature is 240 to 270 with a biaxial kneader.
Melt-kneading to make pellets under the condition of ℃, injection molding is performed, and then the heat distortion temperature, Izod impact strength, chemical resistance and melt viscosity of the obtained test piece are evaluated. It was The evaluation results are shown in Table 1.
【0020】《実施例2》硝酸亜鉛水溶液(0.1mo
l/l)とテトラエトキシシラン(0.02mol/
l)とアンモニア水溶液(0.28mol/l)を各等
量室温で混合し、得られた沈澱物を水洗したのちスプレ
ー乾燥機で乾燥し、更に350℃で8時間乾燥し酸化亜
鉛Bを得た。Example 2 Aqueous zinc nitrate solution (0.1 mo
1 / l) and tetraethoxysilane (0.02 mol /
1) and an aqueous ammonia solution (0.28 mol / l) are mixed in equal amounts at room temperature, the obtained precipitate is washed with water, dried with a spray drier, and further dried at 350 ° C. for 8 hours to obtain zinc oxide B. It was
【0021】ポリアリレート樹脂(UポリマーR U−1
060、ユニチカ(株)製)70重量部、ポリアミド樹
脂(UBEナイロン1013FB、宇部興産(株)製)
30重量部、酸化亜鉛B1重量部を熱ニーダーに投入
し、樹脂温が240〜270℃になるような条件で30
分間溶融混練し、その後冷却粉砕して本発明の熱可塑性
樹脂組成物Bを得た。Polyarylate resin (U polymer R U-1
060, Unitika Ltd. 70 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.)
30 parts by weight and 1 part by weight of zinc oxide B are put into a heat kneader, and the resin temperature is set to 240 to 270 ° C.
The mixture was melt-kneaded for a minute, and then cooled and pulverized to obtain a thermoplastic resin composition B of the present invention.
【0022】芳香族ポリカーボネート樹脂(パンライト
R L−1225、帝人化成(株)製)60重量部、ポリ
アミド樹脂(UBEナイロン1013FB、宇部興産
(株)製)40重量部、熱可塑性樹脂組成物B1重量部
をヘンシェルミキサーに投入し、800〜1200rp
mで数分間混合し、これを二軸混練機にて、樹脂温が2
30〜240℃になるような条件で溶融混練してペレッ
トを作り、その後射出成形を行い、得られた試験片につ
いて熱変形温度、アイゾット衝撃強度、耐薬品性、溶融
粘度の評価を行った。その評価結果を表1に示す。Aromatic polycarbonate resin (Panlite
RL-1225, Teijin Kasei Co., Ltd. 60 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries, Ltd.) 40 parts by weight, thermoplastic resin composition B 1 part by weight is charged into a Henschel mixer, 800 ~ 1200rp
Mix for several minutes at m, and use a twin-screw kneader to increase the resin temperature to 2
Pellets were prepared by melt-kneading under the conditions of 30 to 240 ° C., injection molding was then performed, and the obtained test pieces were evaluated for heat distortion temperature, Izod impact strength, chemical resistance, and melt viscosity. The evaluation results are shown in Table 1.
【0023】《実施例3〜5》表1に示す配合でプリブ
レンドした混合物を実施例1と同様にして溶融混練し、
成形後その特性評価を行った。評価結果も合わせ表1に
示す。<Examples 3 to 5> The mixture preblended with the composition shown in Table 1 was melt-kneaded in the same manner as in Example 1,
After molding, its characteristics were evaluated. The evaluation results are also shown in Table 1.
【0024】《比較例1》ポリアリレート樹脂(Uポリ
マーR U−1060、ユニチカ(株)製)90重量部、
ポリアミド樹脂(UBEナイロン1013FB、宇部興
産(株)製)10重量部、酸化亜鉛B1重量部を熱ニー
ダーに投入し、樹脂温が240〜270℃になるような
条件で50分間溶融混練し、その後冷却、粉砕すること
により熱可塑性樹脂組成物Cを得た。Comparative Example 1 90 parts by weight of polyarylate resin (U polymer R U-1060, manufactured by Unitika Ltd.)
10 parts by weight of polyamide resin (UBE nylon 1013FB, manufactured by Ube Industries, Ltd.) and 1 part by weight of zinc oxide B were put into a thermal kneader, and melt-kneaded for 50 minutes under the condition that the resin temperature was 240 to 270 ° C., and thereafter. A thermoplastic resin composition C was obtained by cooling and pulverizing.
【0025】芳香族ポリカーボネート樹脂(パンライト
R L−1225、帝人化成(株)製)60重量部、ポリ
アミド樹脂(UBEナイロン1013FB、宇部興産
(株)製)40重量部、熱可塑性樹脂組成物C1重量部
をヘンシェルミキサーに投入し、800〜1200rp
mで数分間混合し、これを二軸混練機にて樹脂温が23
0〜250℃になるような条件で溶融混練してペレット
を作り、その後射出成形を行い、成形性の評価と共に得
られた試験片について熱変形温度、アイゾット衝撃強
度、耐薬品性、溶融粘度の評価を行った。その評価結果
を表2に示す。Aromatic polycarbonate resin (Panlite
RL-1225, Teijin Kasei Co., Ltd. 60 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries, Ltd.) 40 parts by weight, thermoplastic resin composition C 1 part by weight was charged into a Henschel mixer, and 800 ~ 1200rp
Mix for several minutes at m, and use a twin-screw kneader to increase the resin temperature to 23
Pellets were prepared by melt-kneading under conditions of 0 to 250 ° C., injection molding was then performed, and heat distortion temperature, Izod impact strength, chemical resistance, and melt viscosity of the obtained test pieces were evaluated. An evaluation was made. The evaluation results are shown in Table 2.
【0026】《比較例2》ポリアリレート樹脂(Uポリ
マーR U−1060、ユニチカ(株)製)70重量部、
ポリアミド樹脂(UBEナイロン1013FB、宇部興
産(株)製)30重量部、酸化亜鉛A15重量部を熱ニ
ーダーに投入し、樹脂温が240〜270℃になるよう
な条件で50分間溶融混練し、その後冷却、粉砕するこ
とにより熱可塑性樹脂組成物Dを得た。Comparative Example 2 70 parts by weight of polyarylate resin (U polymer R U-1060, manufactured by Unitika Ltd.)
30 parts by weight of a polyamide resin (UBE Nylon 1013FB, manufactured by Ube Industries, Ltd.) and 15 parts by weight of zinc oxide A are put into a heat kneader, and melt-kneaded for 50 minutes under the condition that the resin temperature is 240 to 270 ° C., and thereafter. A thermoplastic resin composition D was obtained by cooling and pulverizing.
【0027】ポリアリレート樹脂(UポリマーR U−1
060、ユニチカ(株)製)60重量部、ポリアミド樹
脂(UBEナイロン1013FB、宇部興産(株)製)
40重量部、熱可塑性樹脂組成物D1重量部をヘンシェ
ルミキサーに投入し、800〜1200rpmで数分間
混合し、これを二軸混練機にて、樹脂温が250〜27
0℃になるような条件で溶融混練してペレットを作り、
その後射出成形を行い、得られた試験片について熱変形
温度、アイゾット衝撃強度、耐薬品性、溶融粘度の評価
を行った。その評価結果を表2に示す。Polyarylate resin (U polymer R U-1
060, Unitika Ltd. 60 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.)
40 parts by weight and 1 part by weight of the thermoplastic resin composition D were put into a Henschel mixer and mixed at 800 to 1200 rpm for several minutes, and this was mixed with a twin-screw kneader to obtain a resin temperature of 250 to 27.
Melt and knead under the condition of 0 ℃ to make pellets,
After that, injection molding was performed, and the obtained test pieces were evaluated for heat distortion temperature, Izod impact strength, chemical resistance, and melt viscosity. The evaluation results are shown in Table 2.
【0028】《比較例3〜5》表2に示す配合でプリブ
レンドした混合物を実施例1と同様にして溶融混練し、
成形後その特性評価を行った。評価結果も合わせ表2に
示す。<< Comparative Examples 3 to 5 >> The mixture preblended with the composition shown in Table 2 was melt-kneaded in the same manner as in Example 1,
After molding, its characteristics were evaluated. The evaluation results are also shown in Table 2.
【0029】[0029]
【表1】 [Table 1]
【0030】[0030]
【表2】 [Table 2]
【0031】*1 パンライトR L−1225、帝人
化成(株)製 *2 UポリマーR U−1060 ユニチカ (株)
製 *3 TK−3 鐘紡 (株)製 *4 UBEナイロン1013FB,宇部興産 (株)
製 *5 熱変形温度: 一定速度(2℃/分)で昇温した
時に、試験片が一定加重(18.6Kg/cm2 )を受
けて所定量(0.25mm)だけたわむ時の温度をAS
TM D486に従って測定。 *6 アイゾット衝撃強度: 1/4”幅のノッチ付き
試験片についてASTMD256記載の方法にしたがっ
て測定した。 *7 耐薬品性: 25℃でガソリン中に曲げ試験片を
一昼夜浸漬し、ソルベントクラックが発生する最低応力
値(臨界応力値)を測定した。 表中 ○は臨界応力値が140Kgf/cm2 以上、 △は100〜140Kgf/cm2 未満、 ×は100Kgf/cm2 未満を示す。 *8 溶融粘度: 東洋精機(株)製キャピログラフに
より280℃、ノズル下降スピード100mm/min
にて測定。* 1 Panlite R L-1225 manufactured by Teijin Chemicals Ltd. * 2 U Polymer R U-1060 Unitika Ltd.
* 3 TK-3 Kanebo Co., Ltd. * 4 UBE Nylon 1013FB, Ube Industries Ltd.
Manufacturing * 5 Heat distortion temperature: The temperature at which a test piece receives a constant load (18.6 Kg / cm 2 ) and is bent by a predetermined amount (0.25 mm) when heated at a constant rate (2 ° C./min). AS
Measured according to TM D486. * 6 Izod impact strength: Measured according to the method described in ASTM D256 for a 1/4 "width notched test piece. * 7 Chemical resistance: Solvent cracks were generated by immersing the bending test piece in gasoline at 25 ° C for one day. The minimum stress value (critical stress value) was measured: In the table, ◯ indicates a critical stress value of 140 Kgf / cm 2 or more, Δ indicates 100 to less than 140 Kgf / cm 2 , and × indicates less than 100 Kgf / cm 2. * 8 Melting Viscosity: Toyo Seiki Co., Ltd. Capillograph 280 ° C., nozzle descending speed 100 mm / min
Measured at.
【0032】[0032]
【発明の効果】表1、表2から明らかなように、溶融反
応して得られる本発明の熱可塑性樹脂組成物は、ポリア
ミド樹脂とポリエステル系樹脂との相溶性を顕著に改善
する効果を有しており、これらの樹脂のポリマーアロイ
化に有用である。As is apparent from Tables 1 and 2, the thermoplastic resin composition of the present invention obtained by the melt reaction has the effect of remarkably improving the compatibility between the polyamide resin and the polyester resin. It is useful for polymer alloying these resins.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成4年8月28日[Submission date] August 28, 1992
【手続補正1】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0018[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0018】ポリアリレート樹脂(UポリマーR U−
100、ユニチカ(株)製)70重量部、ポリアミド樹
脂(UBEナイロン1013FB、宇部興産(株)製)
30重量部、酸化亜鉛A1重量部を熱ニーダーに投入
し、樹脂温が240〜270℃になるような条件で30
分間溶融混練し、その後冷却粉砕して本発明の熱可塑性
樹脂組成物Aを得た。Polyarylate resin (U polymer R U-
100 , manufactured by Unitika Ltd., 70 parts by weight, polyamide resin (UBE nylon 1013FB, produced by Ube Industries, Ltd.)
30 parts by weight and 1 part by weight of zinc oxide A were put into a heat kneader, and the resin temperature was adjusted to 240 to 270 ° C.
The mixture was melt-kneaded for a minute and then cooled and pulverized to obtain a thermoplastic resin composition A of the present invention.
【手続補正2】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0019[Name of item to be corrected] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0019】ポリアリレート樹脂(UポリマーR U−
100、ユニチカ(株)製)60重量部、ポリアミド樹
脂(UBEナイロン1013FB、宇部興産(株)製)
40重量部、熱可塑性樹脂組成物A1重量部をヘンシェ
ルミキサーに投入し、800〜1200rpmで数分間
混合し、これを二軸混練機にて樹脂温が240〜270
℃になるような条件で溶融混練してペレットを作り、そ
の後射出成形を行い、成形性の評価と共に得られた試験
片について熱変形温度、アイゾット衝撃強度、耐薬品
性、溶融粘度の評価を行った。その評価結果を表1に示
す。Polyarylate resin (U polymer R U-
100 , manufactured by Unitika Ltd., 60 parts by weight, polyamide resin (UBE nylon 1013FB, produced by Ube Industries, Ltd.)
40 parts by weight and 1 part by weight of the thermoplastic resin composition A are put into a Henschel mixer and mixed at 800 to 1200 rpm for several minutes, and the resin temperature is 240 to 270 with a biaxial kneader.
Melt-kneading to make pellets under the condition of ℃, injection molding is performed, and then the heat distortion temperature, Izod impact strength, chemical resistance and melt viscosity of the obtained test piece are evaluated. It was The evaluation results are shown in Table 1.
【手続補正3】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0021[Correction target item name] 0021
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0021】ポリアリレート樹脂(UポリマーR U−
100、ユニチカ(株)製)70重量部、ポリアミド樹
脂(UBEナイロン1013FB、宇部興産(株)製)
30重量部、酸化亜鉛B1重量部を熱ニーダーに投入
し、樹脂温が240〜270℃になるような条件で30
分間溶融混練し、その後冷却粉砕して本発明の熱可塑性
樹脂組成物Bを得た。Polyarylate resin (U polymer R U-
100 , manufactured by Unitika Ltd., 70 parts by weight, polyamide resin (UBE nylon 1013FB, produced by Ube Industries, Ltd.)
30 parts by weight and 1 part by weight of zinc oxide B are put into a heat kneader, and the resin temperature is set to 240 to 270 ° C.
The mixture was melt-kneaded for a minute, and then cooled and pulverized to obtain a thermoplastic resin composition B of the present invention.
【手続補正4】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0024[Correction target item name] 0024
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0024】《比較例1》ポリアリレート樹脂(Uポリ
マーR U−100、ユニチカ(株)製)90重量部、
ポリアミド樹脂(UBEナイロン1013FB、宇部興
産(株)製)10重量部、酸化亜鉛B1重量部を熱ニー
ダーに投入し、樹脂温が240〜270℃になるような
条件で50分間溶融混練し、その後冷却、粉砕すること
により熱可塑性樹脂組成物Cを得た。Comparative Example 1 90 parts by weight of polyarylate resin (U Polymer RU -100 , manufactured by Unitika Ltd.),
10 parts by weight of polyamide resin (UBE nylon 1013FB, manufactured by Ube Industries, Ltd.) and 1 part by weight of zinc oxide B were put into a thermal kneader, and melt-kneaded for 50 minutes under the condition that the resin temperature was 240 to 270 ° C., and thereafter. A thermoplastic resin composition C was obtained by cooling and pulverizing.
【手続補正5】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0026[Correction target item name] 0026
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0026】《比較例2》ポリアリレート樹脂(Uポリ
マーR U−100、ユニチカ(株)製)70重量部、
ポリアミド樹脂(UBEナイロン1013FB、宇部興
産(株)製)30重量部、酸化亜鉛A15重量部を熱ニ
ーダーに投入し、樹脂温が240〜270℃になるよう
な条件で50分間溶融混練し、その後冷却、粉砕するこ
とにより熱可塑性樹脂組成物Dを得た。Comparative Example 2 70 parts by weight of polyarylate resin (U Polymer RU -100 , manufactured by Unitika Ltd.),
30 parts by weight of a polyamide resin (UBE Nylon 1013FB, manufactured by Ube Industries, Ltd.) and 15 parts by weight of zinc oxide A are put into a heat kneader, and melt-kneaded for 50 minutes under the condition that the resin temperature is 240 to 270 ° C., and thereafter. A thermoplastic resin composition D was obtained by cooling and pulverizing.
【手続補正6】[Procedure Amendment 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0027[Name of item to be corrected] 0027
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0027】ポリアリレート樹脂(UポリマーR U−
100、ユニチカ(株)製)60重量部、ポリアミド樹
脂(UBEナイロン1013FB、宇部興産(株)製)
40重量部、熱可塑性樹脂組成物D1重量部をヘンシェ
ルミキサーに投入し、800〜1200rpmで数分間
混合し、これを二軸混練機にて、樹脂温が250〜27
0℃になるような条件で溶融混練してペレットを作り、
その後射出成形を行い、得られた試験片について熱変形
温度、アイゾット衝撃強度、耐薬品性、溶融粘度の評価
を行った。その評価結果を表2に示す。Polyarylate resin (U polymer R U-
100 , manufactured by Unitika Ltd., 60 parts by weight, polyamide resin (UBE nylon 1013FB, produced by Ube Industries, Ltd.)
40 parts by weight and 1 part by weight of the thermoplastic resin composition D were put into a Henschel mixer and mixed at 800 to 1200 rpm for several minutes, and this was mixed with a twin-screw kneader to obtain a resin temperature of 250 to 27.
Melt and knead under the condition of 0 ℃ to make pellets,
After that, injection molding was performed, and the obtained test pieces were evaluated for heat distortion temperature, Izod impact strength, chemical resistance, and melt viscosity. The evaluation results are shown in Table 2.
【手続補正7】[Procedure Amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0031[Correction target item name] 0031
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0031】*1 パンライトR L−1225、帝人
化成(株)製 *2 UポリマーR U−100 ユニチカ (株)製 *3 TK−3 鐘紡 (株)製 *4 UBEナイロン1013FB,宇部興産 (株)
製 *5 熱変形温度: 一定速度(2℃/分)で昇温した
時に、試験片が一定加重(18.6Kg/cm2 )を受
けて所定量(0.25mm)だけたわむ時の温度をAS
TM D486に従って測定。 *6 アイゾット衝撃強度: 1/4”幅のノッチ付き
試験片についてASTMD256記載の方法にしたがっ
て測定した。 *7 耐薬品性: 25℃でガソリン中に曲げ試験片を
一昼夜浸漬し、ソルベントクラックが発生する最低応力
値(臨界応力値)を測定した。 表中 ○は臨界応力値が140Kgf/cm2 以上、 △は100〜140Kgf/cm2 未満、 ×は100Kgf/cm2 未満を示す。 *8 溶融粘度: 東洋精機(株)製キャピログラフに
より280℃、ノズル下降スピード100mm/min
にて測定。* 1 Panlite RL-1225, Teijin Kasei Co., Ltd. * 2 U Polymer R U-100 Unitika Co., Ltd. * 3 TK-3 Kanebo Co., Ltd. * 4 UBE Nylon 1013FB, Ube Industries ( stock)
Manufacturing * 5 Heat distortion temperature: The temperature at which a test piece receives a constant load (18.6 Kg / cm 2 ) and is bent by a predetermined amount (0.25 mm) when heated at a constant rate (2 ° C./min). AS
Measured according to TM D486. * 6 Izod impact strength: Measured according to the method described in ASTM D256 for a 1/4 "width notched test piece. * 7 Chemical resistance: Solvent cracks were generated by immersing the bending test piece in gasoline at 25 ° C for one day. The minimum stress value (critical stress value) was measured: In the table, ◯ indicates a critical stress value of 140 Kgf / cm 2 or more, Δ indicates 100 to less than 140 Kgf / cm 2 , and × indicates less than 100 Kgf / cm 2. * 8 Melting Viscosity: Toyo Seiki Co., Ltd. Capillograph 280 ° C., nozzle descending speed 100 mm / min
Measured at.
Claims (2)
量部、(b)ポリアミド樹脂20〜80重量部及び
(c)前記ポリアリレート樹脂と前記ポリアミド樹脂の
合計100重量部に対して酸化亜鉛を0.01〜10重
量部添加し、240〜300℃で10〜240分溶融反
応させることにより得られることを特徴とする熱可塑性
樹脂組成物の製造方法。1. Zinc oxide is added to (a) 80 to 20 parts by weight of a polyarylate resin, (b) 20 to 80 parts by weight of a polyamide resin, and (c) a total of 100 parts by weight of the polyarylate resin and the polyamide resin. A method for producing a thermoplastic resin composition, which is obtained by adding 0.01 to 10 parts by weight and performing a melt reaction at 240 to 300 ° C. for 10 to 240 minutes.
部、(b)ポリアミド樹脂20〜80重量部及び(c)
前記ポリアリレート樹脂と前記ポリアミド樹脂の合計1
00重量部に対して、シリカ及び/又はアルミナ中に酸
化亜鉛を均一に分散させた触媒を0.01〜10重量部
添加し、240〜300℃で10分〜240分溶融反応
させることにより得られることを特徴とする熱可塑性樹
脂組成物の製造方法。2. (a) 80 to 20 parts by weight of polyarylate resin, (b) 20 to 80 parts by weight of polyamide resin, and (c).
Total 1 of the polyarylate resin and the polyamide resin
Obtained by adding 0.01 to 10 parts by weight of a catalyst in which zinc oxide is uniformly dispersed in silica and / or alumina to 00 parts by weight and performing a melting reaction at 240 to 300 ° C. for 10 to 240 minutes. A method for producing a thermoplastic resin composition, comprising:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24377291A JPH0578563A (en) | 1991-09-24 | 1991-09-24 | Production of thermoplastic resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24377291A JPH0578563A (en) | 1991-09-24 | 1991-09-24 | Production of thermoplastic resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0578563A true JPH0578563A (en) | 1993-03-30 |
Family
ID=17108747
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP24377291A Pending JPH0578563A (en) | 1991-09-24 | 1991-09-24 | Production of thermoplastic resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0578563A (en) |
-
1991
- 1991-09-24 JP JP24377291A patent/JPH0578563A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2707714B2 (en) | Polyphenylene sulfide resin composition | |
JPH0578563A (en) | Production of thermoplastic resin composition | |
JP3456501B2 (en) | Polyamide resin composition | |
JP3341974B2 (en) | Flame retardant polyamide resin composition | |
JP2002020606A (en) | Thermoplastic resin pellet composition and molded article obtained by injection molding | |
JPH0578566A (en) | Production of thermoplastic resin composition | |
JPH0578561A (en) | Thermoplastic resin composition | |
JPH0578559A (en) | Thermoplastic resin composition | |
JPH0578565A (en) | Thermoplastic resin composition | |
JP3633184B2 (en) | Vibration welding resin composition | |
JPH07173394A (en) | Thermoplastic resin composition | |
JPH0578562A (en) | Thermoplastic resin composition | |
JPH07126516A (en) | Aromatic polyamide resin composition | |
JPH04170433A (en) | Production of polyamide resin masterbatch | |
JPH1017767A (en) | Highly fluid polyamide resin composition | |
JPH06287416A (en) | Thermoplastic resin composition | |
JPH0812865A (en) | Pbt resin molding material | |
JP3237956B2 (en) | Thermoplastic resin composition | |
JPH05132614A (en) | Resin composition | |
JPS5911354A (en) | Resin composition | |
JPH02292359A (en) | Epoxy-modified resin composition | |
JPH10130495A (en) | Polyamide resin composition and injection-molded products using the same | |
JP4061695B2 (en) | Thermoplastic resin composition and molded body | |
JPH05170998A (en) | Resin composition | |
JPH06234914A (en) | Thermoplastic resin composition |