JPH0782474A - Polyamide resin composition - Google Patents
Polyamide resin compositionInfo
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- JPH0782474A JPH0782474A JP24975393A JP24975393A JPH0782474A JP H0782474 A JPH0782474 A JP H0782474A JP 24975393 A JP24975393 A JP 24975393A JP 24975393 A JP24975393 A JP 24975393A JP H0782474 A JPH0782474 A JP H0782474A
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- polyamide resin
- resin composition
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、成形加工性に優れたポ
リアミド樹脂組成物に関する。更に詳しくは射出成形時
に於いて、優れた生産性を与えると同時に、優れた成形
品特性を得ることが可能なポリアミド樹脂組成物に関す
るものである。FIELD OF THE INVENTION The present invention relates to a polyamide resin composition excellent in molding processability. More specifically, the present invention relates to a polyamide resin composition capable of giving excellent productivity at the same time as giving excellent productivity during injection molding.
【０００２】[0002]
【従来の技術】ポリアミド樹脂は優れた機械的特性、耐
熱性、耐油性等を有することで、エンジニアリング樹脂
として広く使用されている。このポリアミド樹脂は、通
常は容易に射出成形等で成形加工されるが、生産性及び
経済性の観点から、成形サイクルを短縮することがで
き、高生産の達成が可能なポリアミド樹脂が求められて
いる。これに応えて、これまで数々の技術的な改良が試
みられて来た。例えば、ステアリン酸バリウム、ラウリ
ン酸バリウム、ステアリン酸アルミニウム等よりなる群
より選ばれた１種以上の化合物を添加してなるポリアミ
ド樹脂組成物（特公昭４１−８９５４号公報）、ポリシ
ロキサンと周期律表Ｉ族、ＩＩ族、およびＩＩＩ族の金
属から選ばれた金属の高級脂肪酸塩を添加してなるポリ
アミド樹脂組成物（特開昭５１−３４２５７号公報）、
炭素数１０〜２０の脂肪族カルボン酸の塩および炭素数
２２以上の脂肪族カルボン酸またはその誘導体を含有し
てなるポリアミド樹脂組成物（特開昭５２−４２５４９
号）、等が知られている。Polyamide resins are widely used as engineering resins because they have excellent mechanical properties, heat resistance and oil resistance. This polyamide resin is usually easily molded by injection molding or the like, but from the viewpoint of productivity and economical efficiency, a polyamide resin capable of shortening the molding cycle and achieving high production is demanded. There is. In response to this, many technical improvements have been attempted so far. For example, a polyamide resin composition (Japanese Patent Publication No. Sho 41-8954) obtained by adding one or more compounds selected from the group consisting of barium stearate, barium laurate, aluminum stearate, etc., polysiloxane and periodic A polyamide resin composition obtained by adding a higher fatty acid salt of a metal selected from Group I, II, and III metals (JP-A-51-34257).
A polyamide resin composition containing a salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms and an aliphatic carboxylic acid having 22 or more carbon atoms or a derivative thereof (JP-A-52-42549).
No.), etc. are known.
【０００３】しかしながら、これらの方法で得られたポ
リアミド樹脂組成物は、可塑化時間が短縮されること
と、離型性が改善されることで、見かけ上は成形サイク
ルタイムが短縮されるが、成形サイクルタイムを短縮し
て成形した場合は、得られる成形品の反り変形量が大き
くなり、寸法精度が厳しい用途向けの成形品を得る為に
は、成形サイクルタイムを延ばして成形する必要があっ
た。また、ポリアミド樹脂成形品が吸水する事で靭性が
増す特徴を利用して、ヒンジ部が付いた成形品を一体成
形するケースが増えてきている。しかしながら、ポリア
ミド樹脂成形品の厚みが薄いヒンジ部は、吸水してない
絶乾状態に於いて、曲げ折れが生じ易い為に、調湿して
強制的に吸水させているのが現状であった。However, although the polyamide resin composition obtained by these methods has a shortened plasticizing time and improved releasability, the molding cycle time is apparently shortened. When molding is performed with a short molding cycle time, the amount of warpage deformation of the resulting molded product increases, and it is necessary to extend the molding cycle time to obtain a molded product for applications with strict dimensional accuracy. It was Further, by utilizing the characteristic that the polyamide resin molded product absorbs water to increase its toughness, the number of cases in which a molded product with a hinge portion is integrally molded is increasing. However, in the thin hinge portion of the polyamide resin molded product, bending is likely to occur in an absolutely dry state where water is not absorbed, so that it is the current situation that the humidity is controlled and the water is forcibly absorbed. .
【０００４】[0004]
【発明が解決しようとする課題】かかる事情に鑑み、本
発明の課題は、ポリアミド樹脂の可塑化時間の短縮と離
型性を改善し、成形サイクルタイムの短縮を可能とし、
更に成形サイクルタイムを短縮して成形した場合に於い
ても反り変形が少ないポリアミド樹脂組成物を提供刷る
ものであり、同時に、絶乾状態に於いても成形品ヒンジ
部の曲げ折れ性が改善されたポリアミド樹脂組成物を提
供することにある。In view of such circumstances, an object of the present invention is to shorten the plasticizing time of the polyamide resin and improve the releasability, and to shorten the molding cycle time.
Further, the present invention provides a polyamide resin composition that is less warped and deformed even when the molding cycle time is shortened, and at the same time, the bendability of the hinge part of the molded product is improved even in an absolutely dry state. Another object of the present invention is to provide a polyamide resin composition.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意検討を重ねた結果、窒化ホウ素粉末
と脂肪族カルボン酸の誘導体を含有してなるポリアミド
樹脂組成物が、上記課題をすべて解決できることを見出
し、本発明を完成するに到った。すなわち、本発明は、
（Ａ）ポリアミド樹脂１００重量部に、（Ｂ）粉末粒径
が１０μ以下である窒化ホウ素の粉末を０．０００１〜
１重量部と、（Ｃ）炭素数１５以上の脂肪族カルボン酸
の誘導体を０．００５〜０．５重量部とを含有させてな
るポリアミド樹脂組成物。を要旨とするものである。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, a polyamide resin composition containing a boron nitride powder and a derivative of an aliphatic carboxylic acid has They have found that they can solve all the problems, and have completed the present invention. That is, the present invention is
0.0001 to 100 parts by weight of (A) polyamide resin, (B) powder of boron nitride having a particle size of 10 μm or less.
A polyamide resin composition comprising 1 part by weight and 0.005 to 0.5 part by weight of a derivative of an aliphatic carboxylic acid having 15 or more carbon atoms (C). Is the gist.
【０００６】以下、本発明の内容を詳細に説明すると、
本発明に用いられるポリアミド樹脂とは、公知のポリア
ミド樹脂であれば特に制限はなく、５０００以上の分子
量を有するナイロンと称せられているものを包含してい
る。具体的には、ラクタムの重縮合物、ジアミン化合物
とジカルボン酸化合物との重縮合物、ω−アミノカルボ
ン酸の重縮合物等の各種タイプのポリアミド樹脂、又は
それ等の共重合ポリアミド樹脂やブレンド物等であり、
例えば、ナイロン６、６６、６１０、６１２、１１、１
２、４６等のホモポリマー、ナイロン６６／６、６６／
６１０、６６／６１２、６６／６Ｔ、６６／６Ｉ、６６
／６Ｔ／６Ｉ等のコポリマー及びこれ等の相互ブレンド
物が挙げられる。ここで６Ｔとは、ヘキサメチレンジア
ミンとテレフタル酸、６Ｉとはヘキサメチレンジアミン
とイソフタル酸を原料とする縮合物であり、他は公知の
原料を用いたポリアミド樹脂である。The details of the present invention will be described below.
The polyamide resin used in the present invention is not particularly limited as long as it is a known polyamide resin, and includes what is called nylon having a molecular weight of 5000 or more. Specifically, various types of polyamide resins such as lactam polycondensates, polycondensates of diamine compounds and dicarboxylic acid compounds, polycondensates of ω-aminocarboxylic acids, or copolymerized polyamide resins or blends thereof. Things etc.,
For example, nylon 6, 66, 610, 612, 11, 1
Homopolymer such as 2, 46, nylon 66/6, 66 /
610, 66/612, 66 / 6T, 66 / 6I, 66
/ 6T / 6I and like copolymers and their mutual blends. Here, 6T is a condensation product of hexamethylenediamine and terephthalic acid, 6I is a condensation product of hexamethylenediamine and isophthalic acid, and the other is a polyamide resin using a known raw material.
【０００７】本発明で用いられる窒化ホウ素とは、化学
式：ＢＮで表わされるものであり、ホウ素を窒素気流中
で高温加熱するか、またはアンモニアと酸化ホウ素ある
いは、塩化アンモニウムとホウ砂を加熱して得られる粉
末であり、粉末の粒径が大きいと構造欠陥を生じてヒン
ジ特性の改善効果が得られない為に粒径が１０μ以下の
粉末を用いるのが好ましい。窒化ホウ素の添加量は、そ
の作用効果に関連して限定されたものであり、ポリアミ
ド樹脂１００重量部に対して０．０００１重量部よりも
少ないとそれが目的とする効果が小さく、１重量部を越
えても目的とする効果が得られないので０．０００１〜
１重量部の範囲で含有させることが必要であり、好まし
くは０．０００５〜０．５重量部の範囲である。 窒化
ホウ素はポリマーの重合時に添加してもよく、また押出
機内でポリアミドに配合する、ペレット表面にブレンド
添加する、高濃度のマスターバッチとして添加する等の
公知の方法で配合する事ができる。The boron nitride used in the present invention is represented by the chemical formula: BN, which is obtained by heating boron at a high temperature in a nitrogen stream or by heating ammonia and boron oxide or ammonium chloride and borax. It is preferable to use a powder having a particle size of 10 μm or less because it is a powder obtained, and if the particle size of the powder is large, structural defects occur and the effect of improving the hinge characteristics cannot be obtained. The amount of boron nitride added is limited in relation to its function and effect, and if it is less than 0.0001 parts by weight with respect to 100 parts by weight of polyamide resin, the desired effect is small and 1 part by weight. 0.0001-
It is necessary to contain it in the range of 1 part by weight, preferably 0.0005 to 0.5 part by weight. Boron nitride may be added at the time of polymerizing the polymer, or may be added by a known method such as addition to the polyamide in the extruder, blend addition to the pellet surface, addition as a high-concentration masterbatch, and the like.
【０００８】本発明に用いられる炭素数１５以上の脂肪
族カルボン酸の誘導体としては、パルミチン酸、ステア
リン酸、ベヘニン酸、セロチン酸、モンタン酸、メリシ
ン酸、セロプラスチン酸、オレイン酸、エルカ酸、等の
金属塩及びエステル等が包含される。炭素数１５以上の
脂肪族カルボン酸の誘導体の添加量はその作用効果に関
連して限定される、即ち、ポリアミド樹脂１００重量部
に対して０．００５重量部よりも少ないとそれが目的と
する効果が小さく、０．５重量部を越えても更なる効果
は望めないので０．００５〜０．５重量部の範囲であ含
有させることが必要である。炭素数１５以上の脂肪族カ
ルボン酸の誘導体は押出機内でポリアミドに配合する、
ペレット表面にブレンド添加する、高濃度のマスターバ
ッチとして添加する等の公知の方法で配合することがで
きる。なお、本発明のポリアミド樹脂組成物には、本発
明の効果を著しく損なわない程度の範囲内において他の
添加剤、即ち展着剤、帯電防止剤、着色剤、充填剤、補
強剤、安定剤等を任意の段階で添加することができる。As the derivative of the aliphatic carboxylic acid having 15 or more carbon atoms used in the present invention, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid, melissic acid, ceroplastic acid, oleic acid, erucic acid, etc. And metal salts and esters thereof are included. The amount of addition of the derivative of the aliphatic carboxylic acid having 15 or more carbon atoms is limited in relation to its action and effect, that is, the amount is less than 0.005 parts by weight based on 100 parts by weight of the polyamide resin. The effect is small, and further effect cannot be expected even if it exceeds 0.5 parts by weight. Therefore, it is necessary to contain it in the range of 0.005 to 0.5 part by weight. The derivative of the aliphatic carboxylic acid having 15 or more carbon atoms is blended with the polyamide in the extruder,
It can be compounded by a known method such as blending addition to the pellet surface or addition as a high-concentration master batch. In the polyamide resin composition of the present invention, other additives, that is, a spreading agent, an antistatic agent, a colorant, a filler, a reinforcing agent, and a stabilizer are added to the extent that the effects of the present invention are not significantly impaired. Etc. can be added at any stage.
【０００９】[0009]
【実施例】次に、実施例及び比較例によって本発明を更
に詳細に説明するが、本発明はこの実施例に限定される
ものではない。実施例及び比較例に於いて、可塑化時
間、離型可能な成形サイクルタイム、反り変形量、ヒン
ジ特性は以下の方法で測定した。 （１）可塑化時間 （成形条件） 射出成形機 ：日精樹脂工業（株）製 ＰＳ４
０Ｅ 金 型 ：１ケ取りボックス（図１参照） シリンダー温度 ：ノズル部２８０℃、前部２８０
℃、中部２８０℃、後部２８０℃ 型 温 度 ：８０℃ 可塑化ストローク ：１２ｍｍ スクリュー回転数 ：２５０ｒｐｍ 背 圧 ：１０％ 射出速度 ：４０％ 射出圧力 ：３０％ 成形サイクルタイム ：射出２ｓｅｃ、冷却１３ｓｅ
ｃ、休止０．３ｓｅｃ（トータル１８．３ｓｅｃ） （測定方法）成形開始より３１ショットから４０ショッ
トまでの可塑化時間の平均値を求めた。EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In Examples and Comparative Examples, the plasticizing time, the mold cycle time at which the mold can be released, the amount of warp deformation, and the hinge characteristics were measured by the following methods. (1) Plasticization time (molding conditions) Injection molding machine: PS4 manufactured by Nissei Plastic Industry Co., Ltd.
OE mold: 1 box (see Fig. 1) Cylinder temperature: Nozzle part 280 ° C, front part 280
℃, middle 280 ℃, rear 280 ℃ Mold temperature: 80 ℃ Plasticizing stroke: 12mm Screw rotation speed: 250rpm Back pressure: 10% Injection speed: 40% Injection pressure: 30% Molding cycle time: Injection 2sec, cooling 13se
c, rest 0.3 sec (total 18.3 sec) (Measurement method) The average value of the plasticizing time from 31 shots to 40 shots from the start of molding was determined.
【００１０】（２）離型可能な成形サイクルタイム （測定方法）可塑化時間の測定と同一条件で成形し、冷
却時間のみを短縮しながら５０ショット連続成形した時
に離型不良がない限界のトータル成形サイクルタイムを
求めた。 （３）反り変形量 （測定方法）可塑化時間の測定と同一条件で、冷却時間
のみを変化させて、トータル成形サイクルタイムが１
２．３ｓｅｃと２０．３ｓｅｃの成形品の反りを測定し
た。尚、測定部位は図１に記した部位である。(2) Molding cycle time at which mold release is possible (Measurement method) Molding is performed under the same conditions as the measurement of the plasticizing time, and when the 50-shot continuous molding is carried out while shortening only the cooling time, there is no total mold release defect. The molding cycle time was determined. (3) Warp deformation amount (Measurement method) Under the same conditions as the measurement of plasticization time, only the cooling time was changed so that the total molding cycle time was 1
The warpage of the molded product was measured for 2.3 seconds and 20.3 seconds. The measurement site is the site shown in FIG.
【００１１】（４）ヒンジ特性 （成形条件） 射出成形機 ：日精樹脂工業（株）製 ＰＳ４
０Ｅ 金 型 ：ヒンジ付き成形品（図２参照） シリンダー温度 ：ノズル部２８０℃、前部２８０
℃、中部２８０℃、後部２８０℃ 型 温 度 ：８０℃ 可塑化ストローク ：１５ｍｍ スクリュー回転数 ：２００ｒｐｍ 背 圧 ：１０％ 射出速度 ：４０％ 射出圧力 ：２３％ 成形サイクルタイム ：射出７ｓｅｃ、冷却７ｓｅｃ、
休止１ｓｅｃ （測定方法）上記成形条件で成形した図２のヒンジ付き
成形品を絶乾状態で１８０°折り曲げて、破壊した時の
折り曲げ回数を測定した。実施例及び比較例のポリアミ
ド樹脂組成物は以下の様にして得た。分子量１６，００
０のナイロン６６を１００重量部に対して、表１に記し
た配合物の配合量をヘンシェルミキサーで３分間混合し
て得た。これらのポリアミド樹脂組成物を前記した条件
で成形及び測定し、表１に示す物性を得た。(4) Hinge characteristics (molding conditions) Injection molding machine: PS4 manufactured by Nissei Plastic Industry Co., Ltd.
OE mold: Molded product with hinge (see Fig. 2) Cylinder temperature: Nozzle part 280 ° C, front part 280
℃, middle 280 ℃, rear 280 ℃ Mold temperature: 80 ℃ Plasticization stroke: 15mm Screw rotation speed: 200rpm Back pressure: 10% Injection speed: 40% Injection pressure: 23% Molding cycle time: Injection 7sec, Cooling 7sec,
Pause 1 sec (Measurement method) The hinged molded article of Fig. 2 molded under the above-mentioned molding conditions was bent 180 ° in an absolutely dry state, and the number of times of bending when it was broken was measured. The polyamide resin compositions of Examples and Comparative Examples were obtained as follows. Molecular weight 16,000
100 parts by weight of Nylon 66 of No. 0 were mixed with the Henschel mixer for 3 minutes to obtain the compounding amounts of the compounds shown in Table 1. These polyamide resin compositions were molded and measured under the conditions described above, and the physical properties shown in Table 1 were obtained.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【発明の効果】本発明により、従来技術が抱えていた課
題、即ち、ポリアミド樹脂の可塑化時間の短縮と離型性
を改善し、成形サイクルタイムの短縮を可能とした、更
に成形サイクルタイムを短縮した場合に於いても反り変
形が少ないことで、生産性を向上する為に成形サイクル
タイムを短縮した場合に於いても、寸法精度が厳しい用
途向けの成形品を得る事が可能となった。更に、成形品
の厚みが薄いヒンジ部の絶乾状態における曲げ折れに関
しても、本発明で改善されたことで、調湿工程が不要と
なり、生産性向上に寄与できた。EFFECTS OF THE INVENTION According to the present invention, the problems faced by the prior art, namely, the shortening of the plasticizing time and the releasability of the polyamide resin, and the shortening of the molding cycle time. Even if the molding cycle time is shortened, the warp deformation is small, so even if the molding cycle time is shortened to improve productivity, it is possible to obtain molded products for applications with strict dimensional accuracy. . Further, regarding the bending and bending of the hinge part having a small thickness of the molded product in the absolutely dry state, the improvement of the present invention eliminates the need for the humidity control step and contributes to the improvement of productivity.
【図１】本発明で成形品の反り変形量を測定するため
の、１ケ取りボックス成形品の図であり、（Ａ）は平面
図、（Ｂ）は断面図、（Ｃ）は反り変形を生じた側面図
である。1A and 1B are views of a single-piece box molded product for measuring the amount of warped deformation of a molded product according to the present invention, in which FIG. 1A is a plan view, FIG. 1B is a sectional view, and FIG. It is the side view which produced.
【図２】本発明でヒンジ部の曲げ折れ回数の測定に用い
た成形品の図であり、（Ａ）は平面図、（Ｂ）は断面
図、（Ｃ）は１８０゜折り曲げ時の断面図である。2A and 2B are views of a molded product used for measuring the number of times the hinge portion is bent and bent according to the present invention. FIG. 2A is a plan view, FIG. 2B is a sectional view, and FIG. Is.
Claims (1)
（Ｂ）粉末粒径が１０μ以下である窒化ホウ素の粉末を
０．０００１〜１重量部と、（Ｃ）炭素数１５以上の脂
肪族カルボン酸の誘導体を０．００５〜０．５重量部と
を含有させてなるポリアミド樹脂組成物。1. To 100 parts by weight of (A) polyamide resin,
(B) 0.0001 to 1 part by weight of boron nitride powder having a particle size of 10 μm or less, and (C) 0.005 to 0.5 part by weight of derivative of aliphatic carboxylic acid having 15 or more carbon atoms. A polyamide resin composition containing:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24975393A JP3380008B2 (en) | 1993-09-13 | 1993-09-13 | Polyamide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24975393A JP3380008B2 (en) | 1993-09-13 | 1993-09-13 | Polyamide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0782474A true JPH0782474A (en) | 1995-03-28 |
| JP3380008B2 JP3380008B2 (en) | 2003-02-24 |
Family
ID=17197715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24975393A Expired - Lifetime JP3380008B2 (en) | 1993-09-13 | 1993-09-13 | Polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3380008B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005343979A (en) * | 2004-06-02 | 2005-12-15 | Mitsubishi Engineering Plastics Corp | Polyamide resin composition |
| JP2007297463A (en) * | 2006-04-28 | 2007-11-15 | Teijin Ltd | Reinforced resin composition and its manufacturing method |
| JP2008214398A (en) * | 2007-02-28 | 2008-09-18 | Nippon Polypenco Ltd | Thermoconductive monomer-cast nylon-molded article |
| JP2010173739A (en) * | 2010-03-19 | 2010-08-12 | Mitsubishi Engineering Plastics Corp | Binding band and molded object having hinge structure |
| US8362191B2 (en) | 2004-05-21 | 2013-01-29 | Mitsubishi Chemical Corporation | Polyamide resin and hinged molded product |
-
1993
- 1993-09-13 JP JP24975393A patent/JP3380008B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8362191B2 (en) | 2004-05-21 | 2013-01-29 | Mitsubishi Chemical Corporation | Polyamide resin and hinged molded product |
| JP2005343979A (en) * | 2004-06-02 | 2005-12-15 | Mitsubishi Engineering Plastics Corp | Polyamide resin composition |
| JP2007297463A (en) * | 2006-04-28 | 2007-11-15 | Teijin Ltd | Reinforced resin composition and its manufacturing method |
| JP2008214398A (en) * | 2007-02-28 | 2008-09-18 | Nippon Polypenco Ltd | Thermoconductive monomer-cast nylon-molded article |
| JP2010173739A (en) * | 2010-03-19 | 2010-08-12 | Mitsubishi Engineering Plastics Corp | Binding band and molded object having hinge structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3380008B2 (en) | 2003-02-24 |
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