JPH078916B2 - Heat-resistant additives and heat-resistant polyamide moldings - Google Patents
Heat-resistant additives and heat-resistant polyamide moldingsInfo
- Publication number
- JPH078916B2 JPH078916B2 JP12867987A JP12867987A JPH078916B2 JP H078916 B2 JPH078916 B2 JP H078916B2 JP 12867987 A JP12867987 A JP 12867987A JP 12867987 A JP12867987 A JP 12867987A JP H078916 B2 JPH078916 B2 JP H078916B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- polyamide
- copper compound
- resistant
- porous
- 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
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- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はポリアミド樹脂添加用耐熱剤に関するものであ
る。TECHNICAL FIELD The present invention relates to a heat-resistant agent for adding a polyamide resin.
（従来の技術） ポリアミド材料はその優れた性質よりタイヤコード，ベ
ルト用補強材，自動車部品などの産業資材に広く利用さ
れている。ポリアミド材料は用途によりかなりの耐熱性
が要求されるが、この要求を満たすために、従来銅化合
物が耐熱助剤としてポリアミド樹脂に配合されている。(Prior Art) Due to its excellent properties, polyamide materials are widely used in industrial materials such as tire cords, belt reinforcing materials, and automobile parts. A polyamide material is required to have a considerable heat resistance depending on its use, and in order to satisfy this requirement, a copper compound has conventionally been blended with a polyamide resin as a heat resistance aid.
（発明が解決しようとする問題点） しかしながら耐熱性は満足するものの、最終製品の着色
の原因となるばかりでなく、ポリアミド材料の製造中、
例えば重合時に添加する方法であれば重合装置を銅及び
ハロゲンが汚染、浸食する問題が残る。また混練によっ
て銅化合物を添加する方法或いは銅化合物の粒径を機械
的に微細にする方法（特公昭56−54337号公報）を用い
ても、フィルム，シートなどの薄い成形品や繊維におい
て銅化合物が凝集した塊として散在し、外観不良及び物
性低下を伴うという問題が残る。(Problems to be solved by the invention) However, although heat resistance is satisfied, it not only causes coloring of the final product, but also during production of the polyamide material,
For example, if it is added during the polymerization, the problem remains that the polymerization equipment is contaminated and eroded by copper and halogen. Further, even if a method of adding a copper compound by kneading or a method of mechanically reducing the particle size of the copper compound (Japanese Patent Publication No. 56-54337) is used, the copper compound in a thin molded product such as a film or a sheet or a fiber is used. Are scattered as agglomerated lumps, and there remains a problem of poor appearance and deterioration of physical properties.
かかる問題点を解決すべく鋭意検討した結果、ポリアミ
ド樹脂にドライブレンド後成型することにより、極めて
優れた耐熱性と銅化合物の分散性を有し、しかも製造工
程が容易で、耐熱性の要求レベルに応じて銅化合物の添
加量を小ロットで変えられるポリアミド用耐熱添加剤を
発明した。As a result of diligent studies to solve such problems, by dry blending with a polyamide resin, it has excellent heat resistance and dispersibility of a copper compound, and the manufacturing process is easy, and the required level of heat resistance is obtained. Inventing a heat-resistant additive for polyamide in which the addition amount of a copper compound can be changed in a small lot according to the above.
（問題点を解決するための手段） すなわち本発明は、多孔性ポリアミド粉末の少なくとも
孔部に銅化合物の微結晶を含有せしめた耐熱添加剤であ
る。また本発明の耐熱性ポリアミド成形品は、多孔性ポ
リアミド粉末の少なくとも孔部に銅化合物の微結晶を含
有せしめた耐熱添加剤をポリアミド樹脂に添加して溶融
成形した耐熱性ポリアミド成形品である。(Means for Solving Problems) That is, the present invention is a heat-resistant additive in which at least pores of porous polyamide powder contain fine crystals of a copper compound. Further, the heat-resistant polyamide molded article of the present invention is a heat-resistant polyamide molded article obtained by adding a heat-resistant additive containing microcrystals of a copper compound in at least the pores of a porous polyamide powder to a polyamide resin for melt molding.
本発明の多孔性ポリアミド粉末とは、ナイロン6,ナイロ
ン66,ナイロン12,ナイロン610,ナイロン11などのポリア
ミドからなる粉末で、多孔性粉末に加工したものを言
う。本発明においては粒径は500μ以下が好ましく、100
μ以下がより好ましい。また孔径は20μ以下が好まし
く、５μ以下がより好ましく、最も好ましくは１μ以下
である。粒径が500μ以上であれば、ポリアミド樹脂の
粉末又はペレットにドライブレンド添加する際に樹脂表
面に均一に分散し難く、銅化合物の分散性が悪くなる。
また孔径が20μ以上であると、銅化合物の結晶が20μ以
上となりフィルムや繊維などの成形品に異物として析出
し、外観と物性低下の原因となるばかりでなく、最終製
品の着色も問題となる。The porous polyamide powder of the present invention is a powder made of polyamide such as nylon 6, nylon 66, nylon 12, nylon 610, nylon 11, etc., which is processed into a porous powder. In the present invention, the particle size is preferably 500μ or less, 100
It is more preferably μ or less. The pore size is preferably 20 μm or less, more preferably 5 μm or less, and most preferably 1 μm or less. When the particle size is 500 μm or more, it is difficult to uniformly disperse on the resin surface when dry blending the powder or pellets of the polyamide resin, and the dispersibility of the copper compound deteriorates.
In addition, if the pore size is 20μ or more, the copper compound crystals will be 20μ or more and will be deposited as foreign matter on molded products such as films and fibers, which not only causes the appearance and physical properties to deteriorate, but also causes coloring of the final product. .
本発明の銅化合物としては特に限定されないが、好まし
くは銅化合物の錯体であり、特にハロゲン化銅が好まし
い。ハロゲン化銅としてはCuCl,CuI,CuCl2,CuI2が挙げ
られ、そのうちCuIが最も有効である。また銅錯体とし
てはハロゲン化アンモニウム，アンモニア水とのアンモ
ニウム錯体,2−メルカプトベンゾイミダゾールを代表と
するメルカプト化合物との錯体，メラミンなどの含窒素
化合物との錯体などが挙げられる。The copper compound of the present invention is not particularly limited, but it is preferably a copper compound complex, and copper halide is particularly preferable. Examples of copper halides include CuCl, CuI, CuCl 2 and CuI 2 , of which CuI is most effective. Examples of the copper complex include ammonium halides, ammonium complexes with aqueous ammonia, complexes with mercapto compounds represented by 2-mercaptobenzimidazole, and complexes with nitrogen-containing compounds such as melamine.
多孔性ポリアミド粉末の孔に銅化合物を含有させる方法
は特に限定されるものではないが、例えば多孔性ポリア
ミド粉末の細孔容積以下の銅化合物溶液量を含浸させ或
いは多孔性ポリアミド粉末を銅化合物溶液に浸漬させ、
次いで溶媒を除去することにより含有させる方法、もし
くは銅化合物の比重を計り、多孔性ポリアミド粉末の細
孔容積以下の容積の銅化合物を計量し銅化合物溶液とし
たのち、所定のポリアミド粉末と混合してスラリー化
し、約１時間攪拌後徐々に溶媒を除去することにより、
ポリアミド粉末の孔の中で結晶させ含有させる方法が良
い。ただし、いずれも銅化合物を溶液にする必要があ
り、例えばCuIのような難溶性のものはヨウ化カリウム
などのハロゲン化アルカリ金属を併用して溶解し易くす
ることが望ましい。銅化合物の含有量は、均一分散させ
るためには比較的低い0.1〜10重量％が好ましい。The method of containing the copper compound in the pores of the porous polyamide powder is not particularly limited, for example, impregnated with a copper compound solution amount not more than the pore volume of the porous polyamide powder or the porous polyamide powder is a copper compound solution. Soak in
Then, a method of containing the solvent by removing the solvent, or by measuring the specific gravity of the copper compound, after measuring the copper compound volume of the copper compound less than the pore volume of the porous polyamide powder to prepare a copper compound solution, mixed with a predetermined polyamide powder To make a slurry, and gradually remove the solvent after stirring for about 1 hour,
A method in which the polyamide powder is crystallized in the pores and contained therein is preferable. However, it is necessary to make the copper compound into a solution in both cases, and it is desirable to use a hardly soluble substance such as CuI in combination with an alkali metal halide such as potassium iodide to facilitate dissolution. The content of the copper compound is preferably 0.1 to 10% by weight, which is relatively low for uniform dispersion.
本発明の耐熱添加剤のポリアミド樹脂への配合方法は、
特に限定されるものではないが、ポリアミド樹脂にドラ
イブレンドする、更に必要により溶融混練する方法が好
ましい。ポリアミド樹脂としては、融点が多孔性ポリア
ミドの融点以下であることが好ましく、また主たる構成
単位が多孔性ポリアミドと同一であることが好ましい。
滑剤及び核剤、可塑剤、安定剤など他の添加剤といっし
ょにドライブレンドする場合には、他の添加剤とボール
ミルやスーパーミキサーで混合処理する方法が有効であ
る。The method for blending the heat-resistant additive of the present invention with the polyamide resin is
Although not particularly limited, a method of dry blending with a polyamide resin and, if necessary, melt kneading is preferable. The polyamide resin preferably has a melting point not higher than the melting point of the porous polyamide, and the main constituent unit is preferably the same as that of the porous polyamide.
When dry blending with other additives such as a lubricant, a nucleating agent, a plasticizer, and a stabilizer, a method of mixing with other additives in a ball mill or a super mixer is effective.
本発明における成形品は、溶融成形されたものであれば
特に限定されない（尚、溶融成形により多孔性ポリアミ
ド粉末は溶融してポリアミド樹脂中に分散される）。ま
た銅化合物の添加量は銅原子として10〜1000ppmが好ま
しい。10ppm以下であると耐熱性改善の効果が顕著でな
くなり、一方1000ppm以上含有しても耐熱性は飽和に達
し、また最終製品の外観が悪くなる。The molded article in the present invention is not particularly limited as long as it is melt-molded (the porous polyamide powder is melted and dispersed in the polyamide resin by melt-molding). Further, the addition amount of the copper compound is preferably 10 to 1000 ppm as a copper atom. If it is 10 ppm or less, the effect of improving heat resistance is not remarkable, while if it is 1000 ppm or more, heat resistance reaches saturation and the appearance of the final product deteriorates.
（本発明の効果） 本発明による効果は次の通りである。(Effect of the present invention) The effect of the present invention is as follows.
本発明の耐熱添加剤は、銅化合物が微結晶となるた
めドライブレンドにおいても分散性が良く、フィルムや
繊維などの製品においても銅化合物の凝集塊が発生する
ことはなく、優れた外観及び耐熱性を示す。The heat-resistant additive of the present invention has good dispersibility even in dry blending because the copper compound becomes fine crystals, and does not generate agglomerates of the copper compound in products such as films and fibers, and has an excellent appearance and heat resistance. Shows sex.
重合時に添加する必要はないので銅及びハロゲンに
起因する重合装置の汚染、腐食などのトラブルがない。Since it is not necessary to add it at the time of polymerization, there is no trouble such as contamination and corrosion of the polymerization apparatus due to copper and halogen.
従来の重合、混練方式では不可能であった押出グレ
ード、例えば相対粘度4.5以上の高粘度ナイロン６の耐
熱品を生産することが可能になり、ガラス，ミネラルフ
ィラー強化品，共重合品など、あらゆる製品への応用が
可能となる。It is now possible to produce extruded grades that could not be achieved by conventional polymerization and kneading methods, such as high-viscosity nylon 6 heat-resistant products with a relative viscosity of 4.5 or higher, such as glass, mineral filler reinforced products, and copolymer products. It can be applied to products.
耐熱性の要求に応じて銅化合物の添加量の変更が簡
単で、多品種小ロットへの対応が容易である。It is easy to change the amount of copper compound added according to the heat resistance requirement, and it is easy to handle a wide variety of small lots.
本発明の耐熱添加剤を添加したポリアミド成形品は
極めて耐熱性が優れている。The polyamide molded product containing the heat-resistant additive of the present invention has extremely excellent heat resistance.
外観の美麗な最終製品が得られる。加えて、従来経
時的な色の変化はさけられなかったが、本発明の成形品
は色の経時変化が無い。A finished product with a beautiful appearance is obtained. In addition, although the color change with time was unavoidable in the past, the molded article of the present invention has no color change with time.
本発明の耐熱添加剤を製造するのに特別な装置を必
要としない。No special equipment is required to produce the heat resistant additive of the present invention.
（実施例） 以下、本発明を実施例により具体的に説明する。(Examples) Hereinafter, the present invention will be specifically described with reference to Examples.
実施例１ ヨウ化第１銅2gとヨウ化カリウム2gをアセトン50mlに加
熱溶解する。室温に冷却後、多孔性ナイロン６粉末（平
均粒径19μ、平均孔径0.24μ）を10g混合する。数分間
攪拌すると、吸着しスラリー状になる。次いでこのスラ
リーを加熱し、アセトンを徐々に除去した後、真空乾燥
機で乾燥する。Example 1 2 g of cuprous iodide and 2 g of potassium iodide are dissolved by heating in 50 ml of acetone. After cooling to room temperature, 10 g of porous nylon 6 powder (average particle size 19μ, average pore size 0.24μ) is mixed. After stirring for a few minutes, it adsorbs and becomes a slurry. Next, this slurry is heated to gradually remove acetone and then dried in a vacuum dryer.
得られた粉末を電子顕微鏡で観察すると、第１図のよう
に孔の中に銅化合物が含有していることがわかる。また
この粉末の銅原子を定量したところ3.5重量％であっ
た。When the obtained powder is observed with an electron microscope, it is found that the copper compound is contained in the pores as shown in FIG. The amount of copper atoms in this powder was determined to be 3.5% by weight.
次に、この粉末3.4gをナイロン６樹脂のペレツト2,000g
とタンブラーでドライブレンドし、これを溶融成型した
ところ、成型品の外観及び機械物性は無添加品と同等で
あった。なお成型品の銅含有率は59ppmであった。Next, add 3.4 g of this powder to 2,000 g of nylon 6 resin pellets.
When dry-blended with a tumbler and melt-molded, the appearance and mechanical properties of the molded product were the same as those of the additive-free product. The copper content of the molded product was 59 ppm.
次に、150℃の熱風乾燥機で168時間加熱し、引張強度，
曲げ強度の変化で耐熱性を評価した結果を第１表に示
す。Next, heat for 168 hours in a hot air dryer at 150 ° C to obtain tensile strength,
Table 1 shows the results of evaluation of heat resistance based on changes in bending strength.
比較例として本発明の添加剤を使用しないときの結果も
第１表に併せて示す。As a comparative example, the results when the additive of the present invention is not used are also shown in Table 1.
第１表より明らかな様に、本発明品使用のポリアミド樹
脂より得られる成型品は耐熱性が極めて良好である。 As is clear from Table 1, the molded product obtained from the polyamide resin used in the product of the present invention has extremely good heat resistance.
実施例２ 実施例１において銅化合物の種類を変える以外同様にし
て成形後、耐熱テスト（150℃×168時間）を行った。耐
熱性は加熱前後における引張強度及び曲げ強度の保持率
で評価し、第２表に示す。Example 2 After molding in the same manner as in Example 1 except that the kind of the copper compound was changed, a heat resistance test (150 ° C. × 168 hours) was performed. The heat resistance was evaluated by the retention of tensile strength and bending strength before and after heating, and is shown in Table 2.
第１図は本発明のポリアミド樹脂用耐熱添加剤の粒子構
造の一例を示す電子顕微鏡写真であり、多孔性ポリアミ
ド粉末の孔に銅化合物の微結晶（１μ程度のやや白色の
粒子）が散在している。第２図は銅化合物を含有する前
の多孔性ポリアミド粉末の粒子構造を示す写真である。FIG. 1 is an electron micrograph showing an example of the particle structure of the heat-resistant additive for polyamide resin of the present invention, in which the fine particles of copper compound (about 1 μm white particles) are scattered in the pores of the porous polyamide powder. ing. FIG. 2 is a photograph showing the particle structure of the porous polyamide powder before containing the copper compound.
Claims (7)
銅化合物の微結晶を含有せしめたことを特徴とする耐熱
添加剤。1. A heat-resistant additive characterized in that at least pores of a porous polyamide powder contain fine crystals of a copper compound.
ある特許請求の範囲第１項記載の添加剤。2. The additive according to claim 1, wherein the pore diameter of the porous polyamide powder is 20 μm or less.
である特許請求の範囲第１項記載の添加剤。3. The additive according to claim 1, wherein the particle diameter of the porous polyamide powder is 500 μm or less.
される錯体化合物である特許請求の範囲第１項記載の添
加剤。4. The additive according to claim 1, wherein the copper compound is copper halide and a complex compound derived therefrom.
銅化合物の微結晶を含有せしめた耐熱添加剤をポリアミ
ド樹脂に添加して溶融成形した耐熱性ポリアミド成形
品。5. A heat-resistant polyamide molded product obtained by adding a heat-resistant additive containing fine crystals of a copper compound in at least the pores of a porous polyamide powder to a polyamide resin and performing melt molding.
たる構成単位を同一とするポリアミドである特許請求の
範囲第５項記載の組成物。6. The composition according to claim 5, wherein the porous polyamide and the polyamide resin are polyamides whose main constituent units are the same.
の融点以下である特許請求の範囲第５項記載の組成物。7. The composition according to claim 5, wherein the melting point of the porous polyamide is equal to or lower than the melting point of the polyamide resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12867987A JPH078916B2 (en) | 1987-05-26 | 1987-05-26 | Heat-resistant additives and heat-resistant polyamide moldings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12867987A JPH078916B2 (en) | 1987-05-26 | 1987-05-26 | Heat-resistant additives and heat-resistant polyamide moldings |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63291928A JPS63291928A (en) | 1988-11-29 |
| JPH078916B2 true JPH078916B2 (en) | 1995-02-01 |
Family
ID=14990759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12867987A Expired - Lifetime JPH078916B2 (en) | 1987-05-26 | 1987-05-26 | Heat-resistant additives and heat-resistant polyamide moldings |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH078916B2 (en) |
-
1987
- 1987-05-26 JP JP12867987A patent/JPH078916B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63291928A (en) | 1988-11-29 |
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