JPH0228250A - Polyamide resin composition - Google Patents
Polyamide resin compositionInfo
- Publication number
- JPH0228250A JPH0228250A JP17659988A JP17659988A JPH0228250A JP H0228250 A JPH0228250 A JP H0228250A JP 17659988 A JP17659988 A JP 17659988A JP 17659988 A JP17659988 A JP 17659988A JP H0228250 A JPH0228250 A JP H0228250A
- Authority
- JP
- Japan
- Prior art keywords
- potassium
- parts
- nylon
- fiber
- potassium titanate
- 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.)
- Granted
Links
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 21
- 239000011342 resin composition Substances 0.000 title claims description 15
- 239000000835 fiber Substances 0.000 claims abstract description 70
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011591 potassium Substances 0.000 claims abstract description 35
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000000465 moulding Methods 0.000 claims description 8
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 abstract description 49
- 229920002292 Nylon 6 Polymers 0.000 abstract description 10
- 229920002302 Nylon 6,6 Polymers 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000012756 surface treatment agent Substances 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- -1 aliphatic diamines Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XYKGWEYJIKCRDF-UHFFFAOYSA-N 3-triethoxysilylsilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)[SiH2]CCCN XYKGWEYJIKCRDF-UHFFFAOYSA-N 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000007 Nylon MXD6 Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 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
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000003503 early effect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 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、精密成形用ポリアミド系樹脂組成物に関する
ものであり、更に詳しくは、広い湿度範囲にわたり、寸
法安定性と高強度、高剛性度が保持され、特に薄肉部品
や精密成形部品に適したポリアミド系樹脂組成物に関す
る。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polyamide resin composition for precision molding, and more specifically, it has dimensional stability, high strength, and high rigidity over a wide humidity range. The present invention relates to a polyamide-based resin composition which is particularly suitable for thin-walled parts and precision molded parts.
［従来の技術］
周知のように、ポリアミド系樹脂としてはナイロン６や
ナイロン６６が比較的低価格であり、機械的強度に優れ
ていることから、エンジニアリングプラスチックとして
広範囲に利用されているが、吸湿による寸法変化及び強
度、剛性度の低下が重大な問題となっている精密部品の
成形材料としての適用は困難であった。[Prior Art] As is well known, polyamide resins such as nylon 6 and nylon 66 are relatively inexpensive and have excellent mechanical strength, so they are widely used as engineering plastics. It has been difficult to apply this material as a molding material for precision parts, where dimensional changes and reductions in strength and rigidity due to molding are serious problems.
即ち、強度を要求される機構部品の用途分野ではガラス
繊維配合組成物が実用化されているが、１つの部品の重
量が１０９以下という小型部品、肉厚がＬ１以下のよう
な薄肉部を含む部品及び歯車のように先端に鋭角部を含
むような部品については、該ガラス繊維を充填したもの
では薄肉部や鋭角部などで長い繊維の流動が不十分で該
繊維の含有量が他の部分に比べて少なくなり、十分な補
強効果が得られず強度不足となる。又該繊維の配向に基
く異方性や反りが生じ、精密成形が困難である。That is, glass fiber blended compositions have been put into practical use in the field of mechanical parts that require strength, but these compositions include small parts with a weight of 109 or less, and thin parts with a wall thickness of L1 or less. For parts and parts with sharp edges such as gears, when filled with glass fibers, the flow of long fibers is insufficient in thin parts or sharp corners, and the fiber content is low in other parts. As a result, a sufficient reinforcing effect cannot be obtained and the strength is insufficient. Furthermore, anisotropy and warpage occur due to the orientation of the fibers, making precision molding difficult.
粉末状無機物を充填した系では、ガラス繊維のような成
形品の箇所による充填物の含有量の差や異方性、反りに
ついては軽微であるが、補強効果が十分ではなく、強度
の小さいものしか得られない。In systems filled with powdered inorganic materials, there are slight differences in the filler content, anisotropy, and warping depending on the location of the molded product, such as glass fiber, but the reinforcing effect is not sufficient and the strength is low. I can only get it.
異方性や反りが軽微であり、かっは内部や鋭角部の末端
まで高い強度を有する樹脂組成物として、チタン酸カリ
ウム繊維配合組成物が開示されている。しかしながら、
ナイロン６やナイロン６６にチタン酸カリウム繊維を充
填した場合、乾燥状態での強度は良好であるが、高湿度
の雰囲気での吸湿状態では大幅に強度が低下し、実用的
な材料にはなり得なかつな。この現東は、従来のチタン
酸カリウム繊維では結晶構造中からの遊術が可能なカリ
ウムが多く、この遊離カリウムが樹脂組成物の特性を劣
化させることが原因であった。A composition containing potassium titanate fibers has been disclosed as a resin composition that exhibits slight anisotropy and warpage and has high strength even inside the frame and at the ends of acute corners. however,
When nylon 6 or nylon 66 is filled with potassium titanate fibers, it has good strength in a dry state, but its strength decreases significantly when it absorbs moisture in a high humidity atmosphere, making it unsuitable for practical use. Nakatsuna. This problem is caused by the fact that conventional potassium titanate fibers contain a large amount of potassium that is free from the crystal structure, and this free potassium deteriorates the properties of the resin composition.
［発明が解決しようとする課題］
このように従来のチタン酸カリウム繊維は、遊離カリウ
ム含有量が多い為に、その存在を嫌うナイロンの補強材
としては好ましいものではなく、新規な補強材の開発が
望まれていた。[Problems to be Solved by the Invention] As described above, conventional potassium titanate fibers have a high free potassium content, so they are not preferable as reinforcing materials for nylon, which does not like the presence of free potassium.Therefore, it is necessary to develop a new reinforcing material. was desired.
本発明は従来のもののような欠点をもたない、異方性や
反りが軽微であって、Ｊ内部や鋭角部の末端まで高強度
、高剛性度を有し、かつ広い湿度範囲にわたり高強度、
高剛性度が保持されるポリアミド系樹脂組成物を提供す
ることを目的とする。The present invention does not have the drawbacks of conventional products, has slight anisotropy and warpage, has high strength and high rigidity up to the inside of the J and the end of the acute angle part, and has high strength over a wide humidity range. ,
An object of the present invention is to provide a polyamide resin composition that maintains high rigidity.
［課題を解決する手段］
本発明者らは上記の課題を解決するため研究を行った結
果、遊離カリウム量が１５ｐｐｍ以下好ましくは５ｐｐ
ｍ以下であるトンネル構造穴チタン酸カリウム繊維をポ
リアミド系樹脂に添加することが効果的であることを見
出し、本発明を完成させた。[Means for Solving the Problems] The present inventors conducted research to solve the above problems and found that the amount of free potassium is 15 ppm or less, preferably 5 ppm.
The present invention was completed based on the discovery that it is effective to add potassium titanate fibers with tunnel structures having a diameter of less than m to polyamide resin.
すなわち、本発明はポリアミド系！Ｄ４ｒＹ１９ｃｓ〜
５０重量部と遊離カリウム量が１５ｐｐｍ以下好ましく
は５１１１１１１以下であるトンネル構造水チタン酸カ
リウム繊維５〜５０重量部を含むｔＩｌ密成形成形用ポ
リアミド系樹脂組成物供するものである。In other words, the present invention is polyamide-based! D4rY19cs~
The present invention provides a polyamide resin composition for dense molding, which contains 50 parts by weight and 5 to 50 parts by weight of tunnel-structure water potassium titanate fibers having a free potassium content of 15 ppm or less, preferably 5,111,111 or less.
上記チタン酸カリウム繊維はトンネル構造内チタン酸カ
リウム繊維中に混入する層状構造四チタン酸カリウムの
含有量を極端に少なくして、結晶構造から遊離するカリ
ウム量を１５ｐｐｎ以下好ましくは５１３９１１以下に
した製品であるが、本発明者らはポリアミド系樹脂に該
チタン酸カリウムｍ維を配合することにより、従来のチ
タン酸カリウム繊維を配合した場合よりも、吸湿時の強
度及び剛性度が著しく改善されることを見出したもので
ある。The above potassium titanate fiber is a product in which the content of layered potassium tetratitanate mixed in the potassium titanate fiber within the tunnel structure is extremely reduced, and the amount of potassium liberated from the crystal structure is 15 ppn or less, preferably 513,911 or less. However, the present inventors have found that by blending the potassium titanate m-fibers into polyamide resin, the strength and rigidity during moisture absorption are significantly improved compared to when conventional potassium titanate fibers are blended. This is what I discovered.
従来のチタン酸カリウム繊維配合樹脂成形物の絶屹時の
強度が、吸湿後再＜ｌｄ５することで復元することから
、ポリアミド系樹脂が遊離カリウムの存在により加水分
解するのではなく、チタン酸カリウム繊維とポリアミド
系樹脂との吸湿時の界面剪断強度に遊離カリウノ、が影
うを及ぼしており、従来のチタン酸カリウム繊維配合組
成物の場合には、！！離カリウムが吸湿時の界面剪断強
度を低下させているもめと推察される。Since the ultimate strength of conventional potassium titanate fiber-containing resin moldings is restored by re-<ld5 after moisture absorption, the polyamide resin is not hydrolyzed due to the presence of free potassium, but potassium titanate Free potassium affects the interfacial shear strength of fibers and polyamide resin when they absorb moisture, and in the case of conventional compositions containing potassium titanate fibers,! ! It is inferred that this is due to potassium release reducing the interfacial shear strength during moisture absorption.
以下、本発明をＪＴＨＥに説明する６本発明のポリアミ
ド系樹脂としては、特に制限はなく様々なものを用いる
ことができる。即ち、■ ナイロン６及びナイロン１２
等の環状脂肪族ラクタムの開環重合によるもの■ ナイ
ロン６６、ナイロン６１０及びナイロンＭＸＤ６等の脂
肪族ジアミンと脂肪族ジカルボン酸または芳香族ジカル
ボン酸の縮重合反応によるもの■ ナイロン１１等のア
ミノ酸の縮重合によるもの、その他各種モノマーの共重
合体がある。これらの中でも、特にナイロン６やナイロ
ン６６を用いることが好ましい。Hereinafter, the present invention will be explained to JTHE.6 The polyamide resin of the present invention is not particularly limited and various resins can be used. That is, ■ Nylon 6 and Nylon 12
■ Condensation polymerization of aliphatic diamines such as nylon 66, nylon 610, and nylon MXD6 with aliphatic dicarboxylic acids or aromatic dicarboxylic acids ■ Condensation of amino acids such as nylon 11 There are polymerization products and copolymers of various other monomers. Among these, it is particularly preferable to use nylon 6 and nylon 66.
本発明のポリアミド系樹脂組成物の強化材として使用さ
れるチタン酸カリウノ、繊維は、遊離カリウム量が５
ｐｐｍ以下であるトン本ル構造六チタン酸カリウム繊維
である。本発明で使用できるトンネル構造穴チタン酸カ
リウム繊維は、代表的には以下の方法で製造される。The potassium titanate fiber used as a reinforcing material for the polyamide resin composition of the present invention has a free potassium content of 5.
It is a potassium hexatitanate fiber with a tonne structure of ppm or less. The tunnel-structured potassium titanate fiber that can be used in the present invention is typically produced by the following method.
すなわち、一般式Ｋ ２０ ・ｎＴ ｉｏ ２（但しｎ
−２〜４）で示される割合で配合されたチタン原料化合
物とカリウム原料化合物との混り物を９００〜１２００
℃で焼成して塊状のチタン酸カリウノ、繊維を生成せし
め、次いで該塊状生成物を水又は温水中に浸漬してチタ
ン酸カリウム繊維を単繊維に解繊した後、該スラリーに
酸を添加してｐＨ９，３〜９．７に調整することにより
、チタン酸カリウムｕ！！維の組成がＴ ｉ Ｏ２／
Ｋ ａ Ｏ（モル比）テ５．９５〜６．００（７）組成
になるように組成変換処理し、更に９５０〜１１５０℃
で１時間以上加熱後、酸洗浄すれば良い。That is, the general formula K 20 ・nT io 2 (where n
- 900 to 1200
The potassium titanate fibers are calcined at ℃ to produce lumpy potassium titanate fibers, and then the lumpy product is immersed in water or hot water to defibrate the potassium titanate fibers into single fibers, and then an acid is added to the slurry. By adjusting the pH to 9.3 to 9.7, potassium titanate u! ! The composition of the fiber is T i O2/
The composition was converted to a composition of K a O (molar ratio) of 5.95 to 6.00 (7), and further heated at 950 to 1150°C.
After heating for 1 hour or more, wash with acid.
このチタン酸カリウム繊維の製造に際し、チタン原料化
合物としては、含水酸化チタン、二酸化チタン及びルチ
ル鉱などを挙げることができ、カリウム原料化合物とし
ては焼成時にに２０を生じる化音物、例えばＫ ２０
、 Ｋ ＯＨ、Ｋ ２ ＣＯ＊及びＫ Ｎ Ｏｓなどを
挙げることができる。In the production of potassium titanate fibers, titanium raw material compounds include hydrous titanium oxide, titanium dioxide, and rutile ore, and potassium raw material compounds include compounds that produce 20 when fired, such as K20.
, K OH, K 2 CO* and K N Os.
また、チタン酸カリウム繊維の形状は、平均繊維長が５
μ【―以上でかつ平均アスペクト比（平均繊維長／平均
繊維径〉１０以上であることが好ましい。In addition, the shape of the potassium titanate fiber has an average fiber length of 5
It is preferable that the average aspect ratio (average fiber length/average fiber diameter) is 10 or more.
得られたチタン酸カリウム繊維中の遊離カリウム量の測
定は以下の方法により行えば良い。The amount of free potassium in the obtained potassium titanate fibers may be measured by the following method.
すなわち、チタン酸カリウム繊維の所定量を水中に分散
した後、煮沸することによって溶出したカリウムを、高
周波誘導結合プラズマ発光分析法、次光分光分析法、原
子吸光分光分析法などにより測定すれば良い、又チタン
酸カリウムの結晶構造から遊離したカリウムは、煮沸後
の水溶液中において水酸化カリウムとして存在する為、
溶液のｐＨを測定し、算出することも可能である。That is, after dispersing a predetermined amount of potassium titanate fibers in water, the potassium eluted by boiling may be measured by high-frequency inductively coupled plasma emission spectrometry, secondary optical spectroscopy, atomic absorption spectroscopy, etc. Also, since potassium liberated from the crystal structure of potassium titanate exists as potassium hydroxide in the aqueous solution after boiling,
It is also possible to measure and calculate the pH of the solution.
本発明において遊離カリウム量とはポリアミド系樹脂と
混合した後の樹脂組成物中における、チタン酸カリウム
繊維に対する遊離カリウム量をいう、混合時にチタン酸
カリウム繊維は折れるため、該組成物中における平均繊
維長は混合前のそれよりも短くなっている。このため組
成物にし、それを成形した場合には、従来のような表面
処理によりカリウムイオンの溶出を防止したものに比較
してはるかに良好な結果を与えるのである。In the present invention, the amount of free potassium refers to the amount of free potassium relative to the potassium titanate fibers in the resin composition after mixing with the polyamide resin.Since the potassium titanate fibers break during mixing, the average fiber in the composition The length is shorter than that before mixing. Therefore, when made into a composition and molded, it gives much better results than conventional surface treatments that prevent the elution of potassium ions.
本発明にかかる組成物の製造に際しては、シランカップ
リング剤等の表面処理剤による処理を施されているチタ
ン酸カリウム繊維を使用する方が、分散性の点で好まし
い、この表面処理されたチタン酸カリウム繊維を利用す
る方法としては、あらかじめ表面処理剤による処理が施
されているものを利用する方法と、チタン酸カリウム繊
維とポリアミド系樹脂とを混練する際に表面処理剤を添
加する方法とがあるが、あらかじめ表面処理剤による処
理が施されたチタン酸カリウム繊維を使用する方が、表
面処理剤の効果がより大きい。When producing the composition according to the present invention, it is preferable to use potassium titanate fibers that have been treated with a surface treatment agent such as a silane coupling agent in terms of dispersibility. There are two ways to use potassium titanate fibers: one that has been treated with a surface treatment agent in advance, and one that adds a surface treatment agent when kneading potassium titanate fibers and polyamide resin. However, the effect of the surface treatment agent is greater when using potassium titanate fibers that have been previously treated with a surface treatment agent.
前記表面処理剤としては、特に、γ−アミノプロピルト
リエトキシシラン、γ−グリシドキシプロピルトリメト
キシシラン及びＮ−（β−アミノエチル）−γ−アミノ
プロピルトリメトキシシラン等が効果的であり、チタン
酸カリウム繊維に対し０．２〜２．０重量％程度の添加
が好ましい。As the surface treatment agent, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, etc. are particularly effective. It is preferably added in an amount of about 0.2 to 2.0% by weight relative to the potassium titanate fiber.
本発明のポリアミド系樹脂組成物の組成については、ポ
リアミド系樹脂は９５〜５０重量部、好すウム繊維は、
５〜５０重量部、好ましくは１０〜４０重量部の範囲で
ある。ポリアミド系樹脂が５０重量部未満では、成形加
工性が悪くなるので好ましくなく、該チタン酸カリウム
繊維が５重量部未満では強度の改良効果が不十分である
。Regarding the composition of the polyamide resin composition of the present invention, the polyamide resin is 95 to 50 parts by weight, and the preferred fiber is:
It ranges from 5 to 50 parts by weight, preferably from 10 to 40 parts by weight. If the amount of the polyamide resin is less than 50 parts by weight, the molding processability will deteriorate, which is undesirable, and if the amount of the potassium titanate fiber is less than 5 parts by weight, the strength improvement effect will be insufficient.
コスト並びに作業性のバランスを考慮すれば、チタン酸
カリウム繊維が１０〜４０重量部の範囲が好ましい。Considering the balance between cost and workability, the amount of potassium titanate fiber is preferably in the range of 10 to 40 parts by weight.
本発明の樹脂組成物には、組成物本来の物性に悪影響を
与えない範囲で、その用途、目的に応じて難燃剤、熱安
定剤、滑剤等の各種添加剤を１種または２種以上を添加
することができる。The resin composition of the present invention may contain one or more of various additives such as flame retardants, heat stabilizers, and lubricants, depending on the use and purpose, within a range that does not adversely affect the original physical properties of the composition. Can be added.
上記のようにして得られた本発明にかかるポリアミド系
樹脂組成物は精密成形部品すなわち、肉厚がｊａｍ以下
のような薄肉部を含む部品、１つの成形重量が１０！Ｆ
程度以下の小型部品や先端に鋭角部を含むような部品、
例えば各種歯車、カム、アーリー及び軸等のようなｌｆ
ｆ械的強度が要求される部品の製造に好適である。The polyamide resin composition according to the present invention obtained as described above can be used for precision molded parts, that is, parts including thin-walled parts with a wall thickness of less than jam, and one molded weight of 10! F
Small parts of the same size or parts with sharp edges,
For example, various gears, cams, earlys, shafts, etc.
f Suitable for manufacturing parts that require mechanical strength.
実施例 以下に実施例をあげて本発明をさらに詳細に説明する。Example The present invention will be explained in more detail with reference to Examples below.
以下の実施例は単に例示のために記すものであり、発明
の範囲がこれらによって制限されるものではない、なお
以下において特に記載のない限り部は重量部を示す。The following examples are given for illustrative purposes only, and the scope of the invention is not limited thereto. In the following, parts refer to parts by weight unless otherwise specified.
実施例１
アナターゼ型酸化チタン１４００．と炭酸カリウム８０
０ｇとを乾式混合した後、アルミナ製ルツボに入れ、電
気炉中で昇温速度２５０℃／時、保持温度１０５０℃、
保持時間３時間の条件で焼成した後、２００℃／時の速
度で降温した。Example 1 Anatase titanium oxide 1400. and potassium carbonate 80
After dry mixing with 0g, the mixture was placed in an alumina crucible, heated at a heating rate of 250°C/hour, and held at 1050°C in an electric furnace.
After firing under conditions of a holding time of 3 hours, the temperature was lowered at a rate of 200° C./hour.
焼成物をステンレス製容器中１ＯＬの温水に投入して５
時間浸漬した後、６００ｒｐ＋ａで撹拌を開始し、浴温
を６０℃に調整する。５Ｎ−塩酸を滴下してｐＨを９．
５に調整する。この後撹拌を更に続けると四チタン酸カ
リウムの層間からカリウムイオンが溶出する為、ｐＨが
高くなるが、塩酸滴下後、３０分間撹拌を続けた場合の
ｐＨの上昇が０．１以下になるまで、３０分間隔で塩酸
を滴下して１）［（を９．５に調整した。Pour the baked product into 1 OL of warm water in a stainless steel container.
After soaking for an hour, stirring is started at 600 rpm+a and the bath temperature is adjusted to 60°C. Add 5N hydrochloric acid dropwise to adjust the pH to 9.
Adjust to 5. If stirring is continued after this, potassium ions will be eluted from between the layers of potassium tetratitanate, resulting in a higher pH.However, if stirring is continued for 30 minutes after adding hydrochloric acid dropwise, the pH will not increase until it becomes 0.1 or less. , 1) was adjusted to 9.5 by adding hydrochloric acid dropwise at 30 minute intervals.
ろ通接、１０００℃で３時間焼成した。該焼成物を１Ｏ
Ｌの温水中に分散した後、ＩＮ−塩酸を滴下して、ｐＨ
を４に調整した。ろ過、屹燥してチタン酸カリウム繊維
を得た。The mixture was passed through a filter and fired at 1000°C for 3 hours. 1O of the fired product
After dispersing in L of warm water, IN-hydrochloric acid was added dropwise to adjust the pH.
was adjusted to 4. It was filtered and dried to obtain potassium titanate fibers.
この繊維をＸ線回折により同定したところ、トンネル構
造・六チタン酸カリウムの単一相であった。又、走査型
電子顕微鏡により繊維を観察したところ、平均繊維長は
８０μ−で、平均繊維径は１．２μ蹟であった。This fiber was identified by X-ray diffraction and was found to have a tunnel structure and a single phase of potassium hexatitanate. Further, when the fibers were observed using a scanning electron microscope, the average fiber length was 80 .mu.m and the average fiber diameter was 1.2 .mu.m.
得られたチタン酸カリウム１！維２０部とナイロン６６
樹脂（宇部興産製、商品名：ＵＢＥナイロン２０２０Ｂ
）８０部とを、ナカタニｖ１械製２軸押出機ＡＳ−３０
により２８０℃の温度で溶融、混練してベレットとした
。Obtained potassium titanate 1! 20 parts of fiber and nylon 66
Resin (manufactured by Ube Industries, product name: UBE Nylon 2020B)
) 80 parts using a twin-screw extruder AS-30 manufactured by Nakatani V1 Machinery.
The mixture was melted and kneaded at a temperature of 280°C to form pellets.
実施例２
実施ｒ！Ａ１と同一のナイロン６６樹脂７０部と、実施
例１で使用したチタン酸カリウム繊維表面に０．８重量
％のγ−アミノプロピルトリエトキジシランを処理した
試料３０部とを、実施例１と同様な条件で溶融、混練し
てペレット化した。Example 2 Implementation r! 70 parts of the same nylon 66 resin as A1 and 30 parts of the sample in which the surface of the potassium titanate fiber used in Example 1 was treated with 0.8% by weight of γ-aminopropyltriethoxydisilane were added in the same manner as in Example 1. It was melted and kneaded under the following conditions to form pellets.
比較例１
Ｒを行い、トンネル構造・六チタン酸カリウムの単一相
を得た。走査型電子ｉ微鏡により繊維を観察したところ
、平均繊維長は８０μ＋ａで、平均繊維径は１．２μ輪
であった。Comparative Example 1 R was carried out to obtain a tunnel structure/single phase of potassium hexatitanate. When the fibers were observed using a scanning electronic i-microscope, the average fiber length was 80μ+a, and the average fiber diameter was 1.2μ.
得られたチタン酸カリウム繊維２０部と実施例１と同一
のナイロン６６樹脂８０部とを、実施例１と同様な条件
でペレット化した。20 parts of the obtained potassium titanate fibers and 80 parts of the same nylon 66 resin as in Example 1 were pelletized under the same conditions as in Example 1.
実施例１で得られたチタン酸カリウムｍ維と比較例１で
得られたチタン酸カリウム繊維について以下の方法によ
りそれぞれの遊離カリウム量を測定した。The amount of free potassium of each of the potassium titanate m fibers obtained in Example 1 and the potassium titanate fibers obtained in Comparative Example 1 was measured by the following method.
実施例１、及び比較例１、のベレットの所定量を採取し
て水中に分散後、１０分間煮沸し、水中に溶出しカリウ
ム量を日本ジャーレルアッシュ製ＩＣＡＰ−５０５型高
周波誘導結合プラズマ発光分析装置により分析し、又水
溶液中の塩素イオン量を日立製作所製分光光度計１００
−０１０１により分析した。A predetermined amount of the pellets of Example 1 and Comparative Example 1 were collected, dispersed in water, boiled for 10 minutes, eluted into the water, and the amount of potassium was determined by high-frequency inductively coupled plasma emission spectrometry using ICAP-505 model manufactured by Nippon Jarel Ash. The amount of chlorine ions in the aqueous solution was analyzed using a Hitachi spectrophotometer 100.
-0101.
これにより塩化カリウムとして含まれるカリウムを除去
してチタン酸カリウムの結晶構造がら溶出した遊離カリ
ウム量を算出した。Thereby, potassium contained as potassium chloride was removed and the amount of free potassium eluted from the crystal structure of potassium titanate was calculated.
実施例１の場き、チタン酸カリウム繊維に対し１．５ｐ
ｐｍ 、比較例１の場合は２３ｐ１１Ｍであった。実施
例及び比較例の試験片中のチタン酸カリウム繊維の平均
繊維長は共に２５μ（イ）程度であったことがら、遊離
カリウム量が吸湿時の強度及び剛性度の低下に関係して
いると判断される。In the case of Example 1, 1.5p for potassium titanate fiber
pm, and in the case of Comparative Example 1, it was 23p11M. Since the average fiber length of the potassium titanate fibers in the test pieces of Examples and Comparative Examples were both approximately 25 μ(A), it is believed that the amount of free potassium is related to the decrease in strength and rigidity upon moisture absorption. be judged.
比較［２
実施例１と同一のナイロン６６ｖＪ４脂７０部と、比較
例１で使用したチタン酸カリウム１！維表面に０．８重
量％のγ−アミノプロピルトリエトキシシランを処理し
た試料３０部とを、実施例１と同様な条件でペレット化
した。Comparison [2 70 parts of the same nylon 66vJ4 fat as in Example 1 and 1! of potassium titanate used in Comparative Example 1! 30 parts of a sample whose fiber surface had been treated with 0.8% by weight of γ-aminopropyltriethoxysilane was pelletized under the same conditions as in Example 1.
比較例３
実施例と同一のナイロン６６樹脂８０部とチタン酸カリ
ウム繊１ｆｔ（天理化学製、商品名：ティスモＤ）２０
部とを、実施例１と同様な条件でペレット化した。Comparative Example 3 80 parts of the same nylon 66 resin as in Example and 1 ft of potassium titanate fiber (manufactured by Tenri Kagaku, trade name: Tismo D) 20
were pelletized under the same conditions as in Example 1.
実施例１．２及び比較例１〜３で得られたベレットを真
空乾燥機を使用して、１２０℃で１２時間屹燻した後、
山域精機製作断裂５ＡＶ−３０３０型射出成形機により
、射出成形〈シリンダー温度２６０〜２８０℃、金型温
度８０℃）し、引張強度及び曲げ強度測定用試験片を得
た。絶乾時及び甜脂に対し２．５％吸湿時の強度測定結
果を第１表に示す。尚この表には比較の為、ナイロン６
６ｔＭ脂単独の場合の物性値も示した。（比較例４）（
第１表）
第１表に明らかなように、遊離カリウム量が１５部９ｍ
以下であるトンネル構造穴チタン酸カリウム繊維を配合
したナイロン６６ｇ４脂組成物は、吸湿時においても高
強度、高剛性度を有している。After smoking the pellets obtained in Example 1.2 and Comparative Examples 1 to 3 at 120°C for 12 hours using a vacuum dryer,
Injection molding (cylinder temperature 260-280°C, mold temperature 80°C) was carried out using a 5AV-3030 injection molding machine manufactured by Yamagen Seiki Co., Ltd. to obtain a test piece for measuring tensile strength and bending strength. Table 1 shows the strength measurement results when completely dry and when 2.5% moisture absorption with respect to sugar beet. For comparison, this table shows nylon 6
Physical property values for 6tM fat alone are also shown. (Comparative example 4) (
Table 1) As shown in Table 1, the amount of free potassium is 15 parts 9m
The following nylon 66g4 resin composition containing tunnel-structured potassium titanate fibers has high strength and high rigidity even when absorbing moisture.
実施例３
ナイロン６樹脂（宇部興産製、商品名：ＵＢＥナイロン
１０１３Ｂ）７０部と実施例２と同一のチタン酸カリウ
ム繊維３０部とを、ナカタニ機械製２軸押出機ＡＳ−３
０により２６０℃の温度で溶融、混練してペレット化し
た。Example 3 70 parts of nylon 6 resin (manufactured by Ube Industries, trade name: UBE Nylon 1013B) and 30 parts of the same potassium titanate fiber as in Example 2 were mixed in a twin-screw extruder AS-3 manufactured by Nakatani Kikai.
The mixture was melted and kneaded at a temperature of 260° C. to form pellets.
比較例５
実施例３と同一のナイロン６樹脂７０部と、比較例２と
同一のチタン酸カリウム繊維３０部とを、実施例３と同
様な条件でペレット化した。Comparative Example 5 70 parts of the same nylon 6 resin as in Example 3 and 30 parts of the same potassium titanate fiber as in Comparative Example 2 were pelletized under the same conditions as in Example 3.
実施例３と比較例５で得られたペレットを、真空乾燥機
を使用して１１０℃１５時間乾燥後、山域精機製作新製
５ＡＶ−３０−３０型射出成形機により射出成形（シリ
ンダー温度２２０〜２４０℃、金型温度８０℃）し、強
度測定用試験片を得た。The pellets obtained in Example 3 and Comparative Example 5 were dried at 110°C for 15 hours using a vacuum dryer, and then injection molded using a 5AV-30-30 injection molding machine (cylinder temperature 220 ~240°C, mold temperature 80°C) to obtain a test piece for strength measurement.
絶乾時及び樹脂に対し３．５％吸湿時の物性測定結果を
第２表に示す、尚この表には比較の為、ナイロン６樹脂
単独の場合の物性値を示した。（比較例６）
（第２表）
第２表より明らかなように、遊離カリウム量が５ ｐｐ
ｍ以下であるトンネル構造力チタン酸カリウム繊維を配
合したナイロン６樹脂組成物は、吸湿時でも、高強度、
高剛性度を有している。Table 2 shows the physical property measurement results when completely dry and when the resin absorbs 3.5% moisture.For comparison, this table also shows the physical property values for nylon 6 resin alone. (Comparative Example 6) (Table 2) As is clear from Table 2, the amount of free potassium is 5 pp
The nylon 6 resin composition blended with potassium titanate fiber has a tunnel structure strength of less than m, and even when moisture is absorbed, it has high strength and
It has high rigidity.
［発明の効果］
本発明の組成物を成形して得られる成形品は、吸湿時に
おいて高強度、高剛性度を有しており、歯車、カム、プ
ーリー及び軸等高い機械的強度が要求される精密機械部
品用途で有効性を特徴する特許出願人 チタン工業株
式会社
（外４名）[Effects of the Invention] Molded products obtained by molding the composition of the present invention have high strength and high rigidity when moisture is absorbed, and can be used in gears, cams, pulleys, shafts, etc. that require high mechanical strength. Patent applicant: Titanium Industry Co., Ltd. (4 others)
Claims (1)
量が１５ｐｐｍ以下であるトンネル構造六チタン酸カリ
ウム繊維５〜５０重量部を含む精密成形用ポリアミド系
樹脂組成物。 ２、請求項第一項記載の組成物から作られた精密機械部
品。[Scope of Claims] 1. A polyamide resin composition for precision molding, comprising 95 to 50 parts by weight of a polyamide resin and 5 to 50 parts by weight of tunnel structure potassium hexatitanate fibers having a free potassium content of 15 ppm or less. 2. Precision mechanical parts made from the composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17659988A JPH0668073B2 (en) | 1988-07-15 | 1988-07-15 | Polyamide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17659988A JPH0668073B2 (en) | 1988-07-15 | 1988-07-15 | Polyamide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0228250A true JPH0228250A (en) | 1990-01-30 |
| JPH0668073B2 JPH0668073B2 (en) | 1994-08-31 |
Family
ID=16016388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17659988A Expired - Fee Related JPH0668073B2 (en) | 1988-07-15 | 1988-07-15 | Polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0668073B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5407754A (en) * | 1991-06-20 | 1995-04-18 | Titan Kogyo Kabushiki Kaisha | Potassium hexatitanate fibers for use as reinforcement |
| US5665620A (en) * | 1994-08-01 | 1997-09-09 | Motorola, Inc. | Method for forming concurrent top oxides using reoxidized silicon in an EPROM |
| US5712177A (en) * | 1994-08-01 | 1998-01-27 | Motorola, Inc. | Method for forming a reverse dielectric stack |
| CN105050958A (en) * | 2013-03-18 | 2015-11-11 | 东邦钛株式会社 | Method for producing potassium titanate |
-
1988
- 1988-07-15 JP JP17659988A patent/JPH0668073B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5407754A (en) * | 1991-06-20 | 1995-04-18 | Titan Kogyo Kabushiki Kaisha | Potassium hexatitanate fibers for use as reinforcement |
| US5665620A (en) * | 1994-08-01 | 1997-09-09 | Motorola, Inc. | Method for forming concurrent top oxides using reoxidized silicon in an EPROM |
| US5712177A (en) * | 1994-08-01 | 1998-01-27 | Motorola, Inc. | Method for forming a reverse dielectric stack |
| CN105050958A (en) * | 2013-03-18 | 2015-11-11 | 东邦钛株式会社 | Method for producing potassium titanate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0668073B2 (en) | 1994-08-31 |
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