[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

JP2502631B2 - Resin composition - Google Patents

Resin composition

Info

Publication number
JP2502631B2
JP2502631B2 JP27849987A JP27849987A JP2502631B2 JP 2502631 B2 JP2502631 B2 JP 2502631B2 JP 27849987 A JP27849987 A JP 27849987A JP 27849987 A JP27849987 A JP 27849987A JP 2502631 B2 JP2502631 B2 JP 2502631B2
Authority
JP
Japan
Prior art keywords
nylon
acid
resin composition
present
boron nitride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP27849987A
Other languages
Japanese (ja)
Other versions
JPH01121361A (en
Inventor
健治 安江
洋 伊吹
孝 井田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unitika Ltd
Original Assignee
Unitika Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unitika Ltd filed Critical Unitika Ltd
Priority to JP27849987A priority Critical patent/JP2502631B2/en
Publication of JPH01121361A publication Critical patent/JPH01121361A/en
Application granted granted Critical
Publication of JP2502631B2 publication Critical patent/JP2502631B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Landscapes

  • Compositions Of Macromolecular Compounds (AREA)

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は,優れた機械特性と耐熱性をあわせ持つ新規
なポリアミド樹脂組成物に関する。
TECHNICAL FIELD The present invention relates to a novel polyamide resin composition having excellent mechanical properties and heat resistance.

(従来の技術) ナイロン46はすでに高知のポリアミドである。たとえ
ば,特公昭60−8248号公報および特公昭60−28843号公
報にはナイロン46の製造方法が開示されている。またナ
イロン46がエンジニアリングプラスチックスとして優れ
た特性,特に卓越した耐熱性を有することも知られてい
る。
(Prior Art) Nylon 46 is already a high-tech polyamide. For example, JP-B-60-8248 and JP-B-60-28843 disclose a method for producing nylon 46. Nylon 46 is also known to have excellent properties as engineering plastics, especially excellent heat resistance.

たとえばその融点は295℃であり,これはナイロン6
の220℃,ナイロン66の260℃よりも高いばがりでなく,
ポリフェニレンスルフィドの285℃をも上回るものであ
る。このようにナイロン46は融点が高いため,熱変形温
度であらわされる耐熱性や耐ハンダ性に優れる。また結
晶化速度が大きく,到達結晶化度も高いために成形サイ
クルが短く,流動性も良いため成形性が良好である。
For example, its melting point is 295 ° C, which is nylon 6
The flash is higher than 220 ℃ of 260 ℃ and 260 ℃ of nylon 66,
It is higher than 285 ℃ of polyphenylene sulfide. Since nylon 46 has a high melting point in this way, it has excellent heat resistance and solder resistance, which are represented by the heat distortion temperature. In addition, the molding cycle is short because the crystallization speed is high and the ultimate degree of crystallinity is high, and the flowability is good, so the moldability is good.

しかし,特に電気部品や自動車部品などの用途におい
ては,ナイロン46の特徴である耐熱性,耐薬品性,成形
性などを維持しながら,さらに高い力学特性を有する材
料が要求されている。
However, especially for applications such as electric parts and automobile parts, materials having higher mechanical properties while maintaining the heat resistance, chemical resistance, moldability, etc., which are the characteristics of nylon 46, are required.

従来,ポリアミドにガラス繊維,炭素繊維などの繊維
状強化剤を配合することにより,強度,剛性,耐熱性な
どが改良されることが知られている。
Conventionally, it is known that strength, rigidity, heat resistance, etc. are improved by blending polyamide with a fibrous reinforcing agent such as glass fiber or carbon fiber.

またポリアミドにタルク,マイカ,炭酸カルシウム,
ガラスビーズなどの粉末状もしくは薄片状の充填剤を配
合すると,成形収縮率および線膨張率が低下し,寸法安
定性が改良されることが知られている。
In addition, polyamide, talc, mica, calcium carbonate,
It is known that when a powdery or flaky filler such as glass beads is blended, the molding shrinkage rate and the linear expansion rate are reduced, and the dimensional stability is improved.

(発明が解決しようとする問題点) しかし,繊維状強化剤を配合した組成物は、異方性が
大きい。表面が荒れ外観が悪い,加工機,金型を摩耗さ
せるなどの欠点がある。
(Problems to be Solved by the Invention) However, the composition containing the fibrous reinforcing agent has large anisotropy. There are drawbacks such as rough surface and poor appearance and abrasion of processing machines and molds.

また粉末状,薄片状の充填剤を配合した場合には,剛
性の改良が十分でない衝撃強度が低下し脆弱となるなど
の欠点が生じる。
In addition, when a powdery or flaky filler is blended, the rigidity is not sufficiently improved, and the impact strength is lowered and the material becomes fragile.

(問題点を解決するための手段および作用) 本発明者らは,優れた力学特性,耐熱性を有し,成形
品外観(表面平滑性)が良好でかつ成形収縮率の小さい
ナイロン46樹脂組成物を開発するため鋭意研究を重ねた
結果,ナイロン46と窒化ホウ素とからなる樹脂組成物が
この目的を満たすことを見いだし,本発明に至った。
(Means and Actions for Solving Problems) The inventors of the present invention have a nylon 46 resin composition having excellent mechanical properties, heat resistance, a good appearance (surface smoothness) of a molded product, and a small molding shrinkage ratio. As a result of intensive studies to develop a product, a resin composition comprising nylon 46 and boron nitride was found to satisfy this purpose, and the present invention was accomplished.

すなわち,本発明はナイロン46 50〜99重量%と窒化
ホウ素1〜50重量%とからなる樹脂組成物に関するもの
である。
That is, the present invention relates to a resin composition containing 50 to 99% by weight of nylon 46 and 1 to 50% by weight of boron nitride.

本発明において用いられるナイロン46とは酸成分とし
てアジピン酸またはその機能誘導体を用い,アミン成分
としてテトラメチレンジアミンまたはその機能誘導体を
用いて,縮合反応により得られるポリアミドを主な構成
単位とするポリアミドおよびポリアミド混合物を対象と
するが,そのアジピン酸成分またはテトラメチレンジア
ミン成分の一部を他の共重合成分で置き換えたものでも
よい。
Nylon 46 used in the present invention is a polyamide whose main constituent unit is a polyamide obtained by a condensation reaction using adipic acid or its functional derivative as an acid component and tetramethylenediamine or its functional derivative as an amine component. The target is a polyamide mixture, but it may be one in which a part of the adipic acid component or tetramethylenediamine component is replaced with another copolymerization component.

共重合成分あるいは混合成分は特に制限がなく,公知
のアミド基形成成分を用いることができる。
The copolymerization component or the mixing component is not particularly limited, and a known amide group-forming component can be used.

共重合成分の代表例として,6−アミノカプロン酸,11
−アミノウンデカン酸,12−アミノドデカン酸,パラア
ミノメチル安息香酸などのアミノ酸,ε−カプロラクタ
ム,ω−ラウリルラクタムなどのラクタム,ヘキサメチ
レンジアミン,ウンデカメチレンジアミン,ドデカメチ
レンジアミン,2,2,4/2,2,4−トリメチルヘキサメチレン
ジアミン,5−メチルノナメチレンジアミン,メタキシリ
レンジアミン,パラキシリレンジアミン,1,3−ビス(ア
ミノメチル)シクロヘキサン,1,4−ビス(アミノメチ
ル)シクロヘキサン,1−アミノ−3−アミノメチル−3,
5,5−トリメチルシクロヘキサン,ビス(3−メチル−
4−アミノシクロヘキシル)メタン,2,2−ビス(4−ア
ミノシクロヘキシル)プロパン,ビス(アミノプロピ
ル)ピペラジン,アミノエチルピペラジンなどのジアミ
ンとアジピン酸,スペリン酸,アゼライン酸,セバシン
酸,ドデカン2酸,テレフタル酸,イソフタル酸,2−ク
ロロテレフタル酸,2−メチルテレフタル酸,5−メチルイ
ソフタル酸,5−ナトリウムスルホイソフタル酸,ヘキサ
ヒドロテレフタル酸,ヘキサヒドロイソフタル酸,ジグ
リコール酸などのジカルボン酸などを挙げることがで
き,また混合ポリアミドはこれらの成分からなるポリア
ミドを挙げることができる。
As a typical example of the copolymerization component, 6-aminocaproic acid, 11
Amino acids such as -aminoundecanoic acid, 12-aminododecanoic acid and para-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryllactam, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4 / 2,2,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,
5,5-Trimethylcyclohexane, bis (3-methyl-
4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine and other diamines and adipic acid, speric acid, azelaic acid, sebacic acid, dodecane diacid, Dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, diglycolic acid, etc. The mixed polyamide may be a polyamide composed of these components.

本発明で用いられるナイロン46の製造方法は任意であ
る。たとえば特公昭60−28843号公報,特公昭60−8248
号公報,特開昭58,83029号公報および特開昭61−43631
号公報などで開示された方法,つまりまず環状末端基量
が少ないプレポリマーを特定の条件下で製造したのち,
これを水蒸気雰囲気などで固相重合して高粘度ナイロン
46を調製する方法で得たもの,あるいは2−ピロリドや
N−メチルピロリドンなどの極性有機溶媒中で加熱する
方法で得たものの利用が特に好ましい。
The method for producing nylon 46 used in the present invention is optional. For example, Japanese Patent Publication No. 60-28843 and Japanese Patent Publication No. 60-8248.
JP-A-58,83029 and JP-A-61-43631
The method disclosed in Japanese Unexamined Patent Application Publication No. 2003-107242, that is, after preparing a prepolymer having a small amount of cyclic end groups under specific conditions,
This is a high-viscosity nylon that is solid-phase polymerized in a steam atmosphere.
It is particularly preferable to use those obtained by the method of preparing 46 or those obtained by the method of heating in a polar organic solvent such as 2-pyrrolid or N-methylpyrrolidone.

本発明で用いられるナイロン46の重合度について特に
制限はないが,相対粘度を96%硫酸を用い濃度1g/dl,25
℃で測定した時,1.5〜5,5さらには2.0〜4.5の範囲にあ
るナイロン46が好ましい。5.5を越える相対粘度のナイ
ロン46を用いる場合には組成物の流動性が悪くなるだけ
でなく,その機械的,熱的性質のばらつきが大きくなる
ので好ましくない。一方1.5よりも低い相対粘度では組
成物の機械的強度が小さくなるという欠点を生じる。
The degree of polymerization of nylon 46 used in the present invention is not particularly limited, but the relative viscosity is 96% sulfuric acid and the concentration is 1 g / dl, 25
Nylon 46 in the range of 1.5-5,5 and even 2.0-4.5 as measured at ° C is preferred. When nylon 46 having a relative viscosity exceeding 5.5 is used, not only the fluidity of the composition deteriorates, but also the dispersion of mechanical and thermal properties becomes large, which is not preferable. On the other hand, if the relative viscosity is lower than 1.5, the mechanical strength of the composition will be reduced.

本発明で用いられる窒化ホウ素は,黒鉛(グラファイ
ト)と同様の層状構造を持ち,空気中では950℃,窒素
中では2,200℃まて安定な化合物である。
The boron nitride used in the present invention has a layered structure similar to that of graphite and is a stable compound up to 950 ° C. in air and 2,200 ° C. in nitrogen.

本発明で用いられる窒化ホウ素の平均粒径は20μm以
下,特に1〜15μmのものが好ましい。
The average particle size of the boron nitride used in the present invention is preferably 20 μm or less, more preferably 1 to 15 μm.

本発明で用いられる窒化ホウ素の製造法には,窒素と
ホウ素を高温(1,500℃)で反応させる方法,ホウ砂と
塩化アンモニウムとを加熱する方法などが知られている
が,特に制限はない。
As a method for producing boron nitride used in the present invention, a method of reacting nitrogen and boron at high temperature (1,500 ° C.), a method of heating borax and ammonium chloride, etc. are known, but there is no particular limitation.

本発明の樹脂組成物における各構成成分の配合割合
は,ナイロン46と窒化ホウ素の合計量に対して,ナイロ
ン46 50〜96重量%,窒化ホウ素1〜50重量%である。
好ましくはナイロン46 70〜97重量%,窒化ホウ素3〜3
0重量%である。窒化ホウ素が1重量%未満の場合に
は,剛性などの力学特性や外観(表面平滑性)の改良が
不十分であり,また窒化ホウ素が50重量%を越える場合
には,溶融混合機での分散が不十分であり,また溶融粘
度の上昇が著しいため,流動性が低下し,通常の条件に
よる成形が困難となり好ましくない。
The blending ratio of each component in the resin composition of the present invention is 50 to 96% by weight of nylon 46 and 1 to 50% by weight of boron nitride with respect to the total amount of nylon 46 and boron nitride.
Nylon 46 70-97% by weight, boron nitride 3-3
It is 0% by weight. When the content of boron nitride is less than 1% by weight, the mechanical properties such as rigidity and the appearance (surface smoothness) are not sufficiently improved. Since the dispersion is insufficient and the melt viscosity increases remarkably, the fluidity decreases and molding under normal conditions becomes difficult, which is not preferable.

本発明の樹脂組成物には,さらに,熱安定剤,光安定
剤,酸化防止剤,可塑剤,滑剤,着色剤,離型剤,離燃
剤,離燃助剤,帯電防止剤などの通常の添加剤を一種以
上添加してもよい。
The resin composition of the present invention is further provided with a usual stabilizer such as a heat stabilizer, a light stabilizer, an antioxidant, a plasticizer, a lubricant, a colorant, a release agent, a flame retardant, a flame retardant aid, an antistatic agent, and the like. One or more additives may be added.

本発明の樹脂組成物は,粉末,ペレットその他の形成
とし,このものを用いてプレス成形,射出成形,押出成
形など一般に知られているプラスチック成形法により各
種の有用な製品を作ることができる。
The resin composition of the present invention can be formed into powder, pellets, or the like, and various useful products can be produced by the generally known plastic molding methods such as press molding, injection molding, and extrusion molding.

以下実施例をあげて本発明をさらに具体的に説明する
が,本発明はこれらに限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

(実施例) 実施例,比較例における評価方法を次に示す。(Example) The evaluation methods in Examples and Comparative Examples are shown below.

成形収縮率 曲げ試験片(1/8インチ×1/2インチ×5インチ)を射
出成形し,長手方向の寸法変化を測定し,金型寸法から
の減少割合を求めた。
Mold shrinkage Bending test pieces (1/8 inch x 1/2 inch x 5 inch) were injection-molded, the dimensional change in the longitudinal direction was measured, and the reduction rate from the die size was obtained.

成形品外観 曲げ試験片を射出成形し、成形品表面の肌荒れ,気
泡,色などをみた。結果を次の記号で示した。
Appearance of molded products Bending test pieces were injection-molded, and the surface of the molded products was observed for roughness, bubbles, and color. The results are shown by the following symbols.

○:良好 △:やや悪い ×:悪い 灰分 成形した試験片を電気炉中で燃焼し(600℃,12hr),
残存分の重量割合を求めた。
○: Good △: Slightly Bad ×: Bad Ash Formed test pieces were burned in an electric furnace (600 ° C, 12hr),
The weight ratio of the residual component was determined.

実施例1〜3 相対粘度3.5のナイロン46と,窒化ホウ素(電気化学工
業(株)製,テンカボロンナイロライドGP,粒度1〜5
μm)とを表1の組成で配合した。この混合物を290℃
にて2軸押出機を用いて押出し,ペレットを得た。
Examples 1 to 3 Nylon 46 having a relative viscosity of 3.5 and boron nitride (manufactured by Denki Kagaku Kogyo KK, Tencaborone Nylolide GP, particle sizes 1 to 5)
μm) and the composition shown in Table 1. 290 ℃ this mixture
Was extruded using a twin-screw extruder to obtain pellets.

このペレットを用いてシリンダ温度300℃,射出時間
6秒,冷却時間6秒で射出成形を行い,厚み1/8インチ
の試験片を得た。これらの試験片を用いて物性試験を行
った。結果を表1に示す。
Using this pellet, injection molding was performed at a cylinder temperature of 300 ° C., an injection time of 6 seconds, and a cooling time of 6 seconds to obtain a test piece having a thickness of 1/8 inch. A physical property test was performed using these test pieces. The results are shown in Table 1.

比較例1,2 実施例で用いたナイロン46に,ガラス繊維(平均繊維
径13μm,平均繊維長3mm)を表1に示す比率で配合し,
実施例と同様に処理してペレットおよび試験片を作製
し,物性試験を行った。結果を表1に示す。
Comparative Examples 1 and 2 Nylon 46 used in Examples was mixed with glass fibers (average fiber diameter: 13 μm, average fiber length: 3 mm) at a ratio shown in Table 1,
Pellets and test pieces were prepared in the same manner as in the example, and the physical properties were tested. The results are shown in Table 1.

比較例3,4 実施例で用いたナイロン46に,種々の強化剤,充填剤
を表1に示す比率で配合し,実施例と同様に処理してペ
レットおよび試験片を作製し、物性試験を行った。結果
を表1に示す。
Comparative Examples 3 and 4 Nylon 46 used in Examples was mixed with various reinforcing agents and fillers in the ratios shown in Table 1, and treated in the same manner as in Examples to prepare pellets and test pieces, and subjected to physical property tests. went. The results are shown in Table 1.

(発明の効果) これらより,ナイロン46と窒化ホウ素とからなる樹脂
組成物は,ナイロン46本来の特性を損なうことなく力学
特性や耐熱性が向上し,しかも他の強化剤を配合した場
合と比較して,外観(表面平滑性)が改良され,また成
形収縮率が著しく小さくなっていることがわかる。
(Effects of the Invention) From these, the resin composition comprising nylon 46 and boron nitride has improved mechanical properties and heat resistance without impairing the original properties of nylon 46, and is compared with the case where other reinforcing agents are blended. It can be seen that the appearance (surface smoothness) is improved and the molding shrinkage is significantly reduced.

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−95953(JP,A) 特開 昭61−197288(JP,A) 特開 昭62−63628(JP,A) 特開 昭62−257967(JP,A) ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP 61-95953 (JP, A) JP 61-197288 (JP, A) JP 62-63628 (JP, A) JP 62- 257967 (JP, A)

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】ナイロン46 50〜99重量%と窒化ホウ素1
〜50重量%とからなる樹脂組成物。
1. Nylon 46 50 to 99% by weight and boron nitride 1
A resin composition comprising 50 wt%.
JP27849987A 1987-11-04 1987-11-04 Resin composition Expired - Lifetime JP2502631B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP27849987A JP2502631B2 (en) 1987-11-04 1987-11-04 Resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP27849987A JP2502631B2 (en) 1987-11-04 1987-11-04 Resin composition

Publications (2)

Publication Number Publication Date
JPH01121361A JPH01121361A (en) 1989-05-15
JP2502631B2 true JP2502631B2 (en) 1996-05-29

Family

ID=17598166

Family Applications (1)

Application Number Title Priority Date Filing Date
JP27849987A Expired - Lifetime JP2502631B2 (en) 1987-11-04 1987-11-04 Resin composition

Country Status (1)

Country Link
JP (1) JP2502631B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009167358A (en) * 2008-01-18 2009-07-30 Techno Polymer Co Ltd Heat-dissipating resin composition

Also Published As

Publication number Publication date
JPH01121361A (en) 1989-05-15

Similar Documents

Publication Publication Date Title
EP0203136B1 (en) Polyamide resin compositions
JP2763348B2 (en) Polyamide resin composition
US6414064B1 (en) Polyamide resin composition
WO2012093722A1 (en) Copolymer polyamide
JP5526031B2 (en) Thermoplastic polymer composition containing polyamide
JP5371683B2 (en) Manufacturing method of polyamide resin composition pellets
JP6174707B2 (en) Polyamide resin composition and molded product
JP2502631B2 (en) Resin composition
JP3159896B2 (en) Polyarylene sulfide resin composition
CN111225942B (en) Improved polyamide stabilizers
JP3456501B2 (en) Polyamide resin composition
JPS6164751A (en) Nylon resin composition
JP2010254822A (en) Thermoplastic resin composition and molding formed thereof
JPH09241505A (en) Polyamide resin composition
JP3331639B2 (en) Polytetramethylene adipamide resin composition
JP7514449B2 (en) Carbon fiber reinforced polyamide resin composition and molded article thereof
JP4235878B2 (en) Method for producing heat-resistant polyamide resin composition
JPH0782474A (en) Polyamide resin composition
JP2604462B2 (en) Resin composition
JPH01121360A (en) Resin composition
JPH02150449A (en) Molding material
JPH0463864A (en) Resin composition
JP2952923B2 (en) Resin composition for circuit board
JP2023001647A (en) Waterproof component and electronic apparatus including the same, waterproofing method using insert molding and waterproofing method for electronic apparatus
JP3045303B2 (en) Damping material