JPS6042823B2 - Light and heat resistant agent for polyamide resin - Google Patents

Description

【発明の詳細な説明】 本発明は新規なポリアミド系樹脂の耐光耐熱剤に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel light and heat resistant agent for polyamide resins.

従来、合成重合体からなる繊維、フィルム、プラスチ
ックなどの各種成形品は耐光性に乏しく、この耐光性を
改良するために各種の耐光剤が配合されているのが普通
である。Conventionally, various molded articles such as fibers, films, and plastics made of synthetic polymers have poor light resistance, and in order to improve this light resistance, various light stabilizers are usually added.

これらの合成重合体の中でも繊維原料、プラスチック製
品として大量に使用されているポリアミドは、ポリエス
テルあるいはポリ塩化ビニルなどにくらべて耐光性がか
なり低く、産業用途ではもちろんのこと各種衣料、イン
テリア製品あるいは人工芝などの繊維製品、特に染色さ
れた繊維製品の染色堅牢性の点で問題であつた。また、
ポリアミドは長時間高温に加熱すると劣化する傾向が大
きく、産業用繊維において特にその向上が望まれて来た
。 これらの合成重合体、特に前記ポリアミドの耐光・
耐熱剤としては、銅化合物がすぐれた性能を有する代表
的なものの一つとして知られているが、この銅化合物は
成形時、たとえば溶融紡糸時に変性したり、ポリマ中か
ら析出して装置内のポリマ流路、特に紡糸口金孔に蓄積
して安定した紡糸又は製糸性及び操業性を妨げ、長時間
に亘つて運転すると得られる繊維の品質、性能の低下を
もたらすことが知られている。Among these synthetic polymers, polyamide, which is used in large quantities as a textile raw material and plastic products, has considerably lower light resistance than polyester or polyvinyl chloride, and is used not only for industrial purposes but also for various clothing, interior products, and artificial materials. This has been a problem in terms of color fastness of textile products such as grass, especially dyed textile products. Also,
Polyamides have a strong tendency to deteriorate when heated to high temperatures for long periods of time, and improvements in this quality have been particularly desired for industrial fibers. The light resistance and
Copper compounds are known as one of the typical heat-resistant agents with excellent performance, but these copper compounds can be denatured during molding, for example during melt spinning, or precipitate from the polymer and cause problems inside the equipment. It is known that it accumulates in the polymer flow path, especially in the spinneret holes, impeding stable spinning or reeling properties and operability, and deteriorating the quality and performance of the resulting fibers when operated for a long time.

したがつて、このポリアミドの紡糸においては紡糸装置
の解体、洗浄、口金面の修正などを定期的に行う回数が
増大し、生産性の面でも問題であつた。さらに銅化合物
以外の紫外線吸収剤や耐熱安定剤も種々の化合物が提案
されているが、これらの多くは効果が十分でなく溶融成
形時に熱分解したり、ポリマを着色させるなど必ずしも
実用上満足すべきものではない。 本発明者らは上記合
成重合体、特にポリアミドの耐光・耐熱剤について鋭意
検討を進めて本発明の新規なポリアミド系樹脂の耐光・
耐熱剤を見出すに至つたものである。Therefore, in spinning this polyamide, the number of times that the spinning device must be dismantled, cleaned, and the spinneret surface modified periodically increases, which also poses a problem in terms of productivity. Furthermore, various compounds have been proposed for ultraviolet absorbers and heat-resistant stabilizers other than copper compounds, but many of these are not sufficiently effective and may cause thermal decomposition during melt molding or color the polymer, resulting in problems that are not always satisfactory for practical purposes. It's not a kimono. The present inventors have conducted extensive studies on the light and heat resistance agents for the above synthetic polymers, especially polyamides, and have developed the light and heat resistance of the novel polyamide resin of the present invention.
This led to the discovery of a heat resistant agent.

すなわち、本発明の目的とするところは、前述したポリ
マの成形工程の操業上のトラブルが少なく、ポリマ固有
の物性、たとえば強度的性質、光沢、透明性、染色鮮明
性などを損うことがない優れたポリアミド系樹脂の耐光
・耐熱性を付与する耐光・耐熱剤を提供するにある。That is, the object of the present invention is to reduce operational troubles in the above-mentioned polymer molding process, and to avoid impairing the physical properties inherent to the polymer, such as strength, gloss, transparency, and color clarity. An object of the present invention is to provide a light and heat resistant agent that imparts excellent light and heat resistance to polyamide resins.

他の目的はこのような耐光・耐熱剤を配合した耐光性、
特に耐光染色堅牢度および耐熱性が格段にすぐれたポリ
アミド系成形品特に繊維を提供するにある。Other purposes include light resistance, which is formulated with light and heat resistance agents,
In particular, it is an object of the present invention to provide a polyamide molded product, particularly a fiber, which is particularly excellent in color fastness to light and heat resistance.

このような本発明の目的は、約１０〜５唾量％のアクリ
ロニトリルと約９０〜５鍾量％の少なくとも１種のアク
リロニトリルとは異なるビニル系化合物とからなる共重
合体に第一銅化合物を銅分として、約０．０２〜２５重
量％、好ましくは０．０３〜２鍾量％の範囲量配合して
なる重合体組成物を耐光耐熱剤としてポリアミド系樹脂
に用いることによつて達成することができる。The object of the present invention is to add a cuprous compound to a copolymer consisting of about 10 to 5% by weight of acrylonitrile and about 90 to 5% by weight of at least one vinyl compound different from acrylonitrile. This is achieved by using a polymer composition containing copper in a range of about 0.02 to 25% by weight, preferably 0.03 to 2% by weight, as a light and heat resistant agent in a polyamide resin. be able to.

本発明において上記共重合体の共重合成分である駅とは
異種のビニル系化合物としてはスチレンｖα−メチルス
チレン、ビニルトルエン、アクリル酸メチル、メタクリ
ル酸メチル、アクリル酸、などがあり、これらの中でア
クリロニトリル（以下Ａと略す）とスチレン（以下ＳＴ
と略する）との共重合体、ＡＮとａ−メチルスチレン（
以下ａ−ＭＳＴと略す）とＳＴとの共重合体、書とＳＴ
とメタクリル酸メチル（以下ＭＭＡと略す）との共重合
体などが好ましい。In the present invention, vinyl compounds different from the station which are the copolymerization components of the above copolymer include styrene vα-methylstyrene, vinyltoluene, methyl acrylate, methyl methacrylate, and acrylic acid. Acrylonitrile (hereinafter abbreviated as A) and styrene (hereinafter ST
copolymer of AN and a-methylstyrene (abbreviated as
A copolymer of ST (hereinafter abbreviated as a-MST) and ST, calligraphy and ST
A copolymer of and methyl methacrylate (hereinafter abbreviated as MMA) is preferred.

しかしながら、これらの共重合体はその共重合組成とし
て、書を約１０〜５０重量％、ビニル系化合物を９０〜
５鍾量％の範囲内で共重合するのがよく、ＡＮの共重合
割合が約１０重量％以下になると後述するように第一銅
化合物を配合した際に第一銅化合物が該共重合体中に安
定に分散、保持され難くなるし、他方ＡＮの共重合割合
が５０重量％を越えると、得られる重合体組成物の着色
が著しくなるので好ましくない。However, these copolymers have a copolymer composition of approximately 10 to 50% by weight of carbon and 90 to 90% by weight of vinyl compounds.
It is preferable to copolymerize within the range of 5% by weight, and if the copolymerization ratio of AN is about 10% by weight or less, as will be described later, when the cuprous compound is blended, the copolymerization will be On the other hand, if the copolymerization ratio of AN exceeds 50% by weight, the resulting polymer composition will become significantly colored, which is not preferable.

また、第一銅化合物としては従来耐光・耐熱性を有する
ものとして知られている無機銅塩、有機銅塩あるいは無
機又は有機の銅錯体又は複塩など、さらに具体的には、
沃化第一銅、塩化第一銅、沃化第一銅、臭化第一銅と２
−メルカプトベンゾイミダゾールとからなる錯体、など
を挙げることができる。In addition, the cuprous compounds include inorganic copper salts, organic copper salts, inorganic or organic copper complexes or double salts, which are conventionally known to have light resistance and heat resistance, and more specifically,
Cuprous iodide, cuprous chloride, cuprous iodide, cuprous bromide and 2
- mercaptobenzimidazole, and the like.

これらの第一銅化合物は前記共重合体に対して銅分とし
て約０．０２〜２５重量％、好ましくは０．０３〜２唾
量％の範囲内で均一、かつ安定に配合することができる
。These cuprous compounds can be uniformly and stably blended in the copolymer in a copper content of about 0.02 to 25% by weight, preferably 0.03 to 2% by weight. .

そして、これらの第一銅化合物は単なる混合物として配
合されているのではなく、少なくともその一部が前記共
重合体と錯体を形成していると推定される。すなわち、
本発明の重合体組成物はエレクトロン●スペクトロスコ
ピイ●フォー●ケミカル●アナリシス（以下ＥＳＣＡと
略称する）による測定では、共重合体と第一銅化合物と
の間に相互作用の存在が認められる。It is presumed that these cuprous compounds are not simply blended as a mixture, but that at least a part of them forms a complex with the copolymer. That is,
When the polymer composition of the present invention is measured by electron spectroscopy for chemical analysis (hereinafter abbreviated as ESCA), the presence of interaction between the copolymer and the cuprous compound is observed.

また、第一銅化合物の配合により、重合体組成物の溶融
粘度が増大し、曳糸性が向上する。In addition, the blending of the cuprous compound increases the melt viscosity of the polymer composition and improves the spinnability.

以上のことから前記推定が事実として裏付けられる。し
かしながら、該第１銅化合物の配合割合は前記共重合体
に対して銅分として約０．０２〜２５重量％、好ましく
は０．０３〜２鍾量％の範囲内がよく、０．０種量％よ
りも少ない配合割合になると組成物として耐光・耐熱性
が十分でないし、２５重量％を越えると錯体を形成し難
くなるためか未反応物が多くなるので好ましくない。From the above, the above estimation is supported as a fact. However, the proportion of the cuprous compound in the copolymer is preferably about 0.02 to 25% by weight as copper content, preferably 0.03 to 2% by weight, and 0.0 to 25% by weight, preferably 0.03 to 2% by weight. If the blending ratio is less than % by weight, the composition will not have sufficient light resistance and heat resistance, and if it exceeds 25% by weight, unreacted substances will increase, probably because it becomes difficult to form a complex, which is not preferred.

かくして第一銅化合物を配合した本発明の重合体組成物
はポリアミド用耐光・耐熱剤として極めて有用である。
すなわち、該重合体組成物はポリアミドに対する混和性
にすぐれており、ポリアミド中に均一、かつ安定に配合
することができ、ポリアミドの有する優れた性質を損う
ことがない。アクリル繊維の染色に１価の銅イオンを利
用する方法があるが、本発明のように溶融可能なアクリ
ロニトリル共重合体と第一銅化合物との組成物ならびに
それをポリアミドに溶融混合してすぐれた耐光・耐熱効
果を得ることは知られていない。Thus, the polymer composition of the present invention containing a cuprous compound is extremely useful as a light and heat resistant agent for polyamide.
That is, the polymer composition has excellent miscibility with polyamide, can be uniformly and stably blended into polyamide, and does not impair the excellent properties of polyamide. There is a method of using monovalent copper ions for dyeing acrylic fibers, but as in the present invention, a composition of a meltable acrylonitrile copolymer and a cuprous compound and melt-mixing it with polyamide are excellent methods. It is not known to have light or heat resistance effects.

本発明により、第一銅を種々の融点のポリアミド中に容
易に、多量に混合することができ、通常１の方法で行な
つた場合に起こりやすい成型時の障害を著しく少なくす
ることができる。また、本発明で得られたポリアミド成
型品を電子顕微鏡的に観察するとアクリロニトリル共重
合体がポリアミド中に不均一相を形成していることが認
められるが、このような構造においてもポリアミドの全
体にわたつて著しい耐光・耐熱化が達せられることは驚
くべきことである。According to the present invention, it is possible to easily mix large quantities of cuprous into polyamides having various melting points, and it is possible to significantly reduce the problems that occur during molding, which usually occur when method 1 is used. Furthermore, when the polyamide molded product obtained in the present invention is observed under an electron microscope, it is observed that the acrylonitrile copolymer forms a heterogeneous phase in the polyamide, but even in such a structure, the entire polyamide is It is surprising that remarkable light and heat resistance can be achieved over time.

しかも、通常第一銅化合物単独ではポリアミドに対する
配合割合が銅分として約０．０１重量％を越えると、前
述したように溶融成形時に銅化合物又はその変性物が析
出し、短時間のうちに成形が困難になつたり、ポリマが
着色したりするが、本発明の重合体組成物は第１銅化合
物の銅分に換算して約０．３重量％まで配合してもこの
ようなトラブルを生じることがないのである。Moreover, if the copper content alone exceeds approximately 0.01% by weight of copper in the polyamide, the copper compound or its modified product will precipitate during melt molding as described above, and the molding will be completed within a short period of time. However, the polymer composition of the present invention causes such troubles even if it is incorporated up to about 0.3% by weight in terms of the copper content of the cuprous compound. There is no such thing.

しかしながら、ポリアミドの優れた特性を保有し、十分
な耐光・耐熱性を付与するためには第一銅化合物は銅分
として約０．００３〜０．２重量％、好ましくは０．０
０５〜０．１重量％の範囲で配合するのがよい。However, in order to retain the excellent properties of polyamide and provide sufficient light and heat resistance, the cuprous compound should be used in an amount of approximately 0.003 to 0.2% by weight as copper, preferably 0.0% by weight.
It is preferable to mix it in a range of 0.05 to 0.1% by weight.

本発明になる重合体組成物を耐光・耐熱剤として配合し
たポリアミド成型物は、従来のポリアミドと同様に成形
することができる。A polyamide molded product containing the polymer composition of the present invention as a light and heat resistant agent can be molded in the same manner as conventional polyamides.

たとえば繊維の場合ポリアミドチップに重合体組成物を
添加混合し、常法により溶融紡糸される。重合体組成物
の形状は、粉末、フレーク、チップいずれでも良い。ま
た、予めポリアミドと溶融混練して重合体組成物含有ポ
リアミドチップ（以下マスターチツプ）とし、これを常
法により混合して溶融紡糸し−ても良い。ポリアミドに
は耐光・耐熱剤として通常用いられる紫外線吸収剤、耐
熱剤を含有していても良い。該重合体組成物は、溶融状
態で、紡糸機装置の口金バック内に添加してポリアミド
と混合し紡糸ｊすることも出来るし、ポリアミドの重合
装置内に添加することも出来る。For example, in the case of fibers, a polymer composition is added to and mixed with polyamide chips, and then melt-spun by a conventional method. The shape of the polymer composition may be powder, flake, or chip. Alternatively, the polyamide chips may be melt-kneaded with polyamide in advance to form polyamide chips containing a polymer composition (hereinafter referred to as master chips), which may be mixed in a conventional manner and melt-spun. The polyamide may contain ultraviolet absorbers and heat resistant agents that are commonly used as light and heat resistant agents. The polymer composition can be added in a molten state into a spinneret bag of a spinning machine device, mixed with polyamide, and spun, or can be added into a polyamide polymerization device.

ポリアミドとしては、各種溶融紡糸可能なポリマが用い
られる。As the polyamide, various melt-spun polymers can be used.

たとえばナイロン４、５、６６、６１０などを挙げるこ
とが出来る。またポリアミド．は１種のみならず２種以
上の混合物であつても良いし、シンーサヤ方式や側面は
り合せ方式の複合糸であつても良い。溶融条件としては
、温度２３０〜３００℃、紡糸速度３００〜２５００７
ＴＬ，Ｉｍｉｎで引取り、油剤処理後巻取る。For example, nylon 4, 5, 66, 610, etc. can be mentioned. Also polyamide. may be not only one type but also a mixture of two or more types, or may be a composite yarn of a thin-saya type or a side seam type. Melting conditions include temperature 230-300°C, spinning speed 300-25007
Taken off at TL and Imin, treated with oil and then rolled up.

・得られた未延伸糸は伸度が高く、口金バック内の戸圧
の変動が小さく安定し、紡糸口金面の汚染が改善され、
紡出糸の収率が高い上に、該未延伸糸は延伸性にも優れ
、高倍率延伸が可能で毛羽発生などのトラブルも少なく
、収率良好な延伸糸が得られる。延伸方法は、熱延伸、
冷延伸いずれでも良く、５０〜１０００ｍＩｍｉｎの速
度で行い得る。・The obtained undrawn yarn has high elongation, the fluctuation in door pressure inside the spinneret bag is small and stable, and contamination on the spinneret surface is improved.
In addition to the high yield of the spun yarn, the undrawn yarn has excellent drawability and can be drawn at a high magnification, with fewer problems such as occurrence of fuzz, and a drawn yarn with a good yield can be obtained. The stretching method is hot stretching,
Any cold stretching may be used, and it can be carried out at a speed of 50 to 1000 mImin.

得られた延伸糸は常法により編地、織物紡績糸、電気植
毛品などに加工され、染色される。か）くして得られた
重合体組成物含有ポリアミド繊維は優れた耐光堅牢性と
耐熱性を有する。以下実施例により本発明の効果をさら
に具体的に説明する。なお、実施例において、耐光染色
堅牢性は、・ＪＩＳ染色堅ろう度試験用「変退色用グレ
ースケール」を基準にしたグレースケールで示した。The obtained drawn yarn is processed into knitted fabrics, textile spun yarns, electro-flocked products, etc., and dyed by conventional methods. (c) The polyamide fiber containing the polymer composition thus obtained has excellent light fastness and heat resistance. The effects of the present invention will be explained in more detail with reference to Examples below. In addition, in the examples, the light fastness to dyeing is shown in gray scale based on the "gray scale for discoloration and fading" for JIS dye fastness test.

すなわち、グレースケールとは染色繊維が光照射を受け
変退色する度合を表わすものであり、１級は変退色の度
合が最も著しいことを示し、次いで、１″〜２級、２級
・・・・ ・・と変退色が少ないものを示し、最後の５
級は全く変退色がない（耐光効果最大）ことを示す。ま
た、耐光強力保持率は、染色繊維の光照射前後の糸質（
強力）から求めた強力保持率を示すものである。実施例
１ ＡＮ／ＳＴ／α−ＭＳＴ（重量比組成＝２７／１１／６
２、クロロホルム溶媒による３０℃の固有粘度０．４５
）の共重合体粉末１０娼にＣｕＩの粉末１娼を加え、こ
れにメタノール２０（１）部を加えて攪拌しながら６０
℃に加熱した。In other words, gray scale refers to the degree to which dyed fibers change color and fade when exposed to light, and grade 1 indicates the degree of discoloration and fading that is most significant, followed by grade 1'' to grade 2, grade 2, etc.・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・
Grade indicates that there is no discoloration or fading at all (maximum light resistance effect). In addition, the light resistance strength retention rate is the yarn quality of dyed fibers before and after light irradiation (
This shows the strength retention rate calculated from the strength (strength). Example 1 AN/ST/α-MST (weight ratio composition=27/11/6
2. Intrinsic viscosity at 30°C with chloroform solvent 0.45
) to 10 parts of copolymer powder, add 1 part of CuI powder, add 20 (1) parts of methanol to this, and mix 60 parts with stirring.
heated to ℃.

ＣｕＩは、メタノールに微量しか溶解せず、残りは懸濁
状で存在しているが、溶解した微量のＣｕＩが共重合体
と反応するため、ＣｕＩのメタノールへの溶解が次々と
進行し、約１ｈｒ後、懸濁物は消滅し清澄な液となつた
。Only a small amount of CuI dissolves in methanol, and the rest exists in a suspended form. However, as the small amount of dissolved CuI reacts with the copolymer, the dissolution of CuI in methanol progresses one after another, and approximately After 1 hr, the suspended matter disappeared and a clear liquid was obtained.

共重合体とＣｕＩの反応物は沈澱物として得られ、この
重合体組成物を枦別後乾燥して、ＥＳＣＡ測定を行なつ
た。ＥＳＣＡ測定の結果、重合体組成物には、Ｃｕ、Ｉ
の強い信号が得られ、ＣｕＩが共重合体の表面付近に吸
着しているものとみられる。The reaction product of the copolymer and CuI was obtained as a precipitate, and this polymer composition was separated, dried, and subjected to ESCA measurement. As a result of ESCA measurement, the polymer composition contained Cu, I
A strong signal was obtained, indicating that CuI was adsorbed near the surface of the copolymer.

ＣＵＩｌ重合体組成物の主要ピークを第１表に示す。こ
こで注目されるのは、重合体組成物ではＩのピークはシ
フトしていないが、Ｃｕのピークが〜１．６ｅ′Ｖ低Ｋ
．Ｅ方向へシフトしていることである。The major peaks of the CUIl polymer composition are shown in Table 1. It is noteworthy here that in the polymer composition, the I peak is not shifted, but the Cu peak is ~1.6e′V low K
．． This is a shift in the E direction.

これはＣｕ＋に対するＩ−の影響が減少し、別のリガン
ト（−ＣＮ）が近付き、その相互作用によつて引き起ご
されたシフトであると考えられる。これに対応して、−
ＣＮ（７）ＮｌＳもプロードになり〜（イ）．３）ＥＶ
シフトしている。以上の結果から、重合体組成物はＣＬ
ｌｌと共重合体との間の錯体であると考えられる。This is considered to be a shift caused by the reduced influence of I- on Cu+ and the approach of another ligand (-CN) and their interaction. Correspondingly, −
CN (7) NlS also becomes prod ~ (a). 3) EV
It's shifting. From the above results, the polymer composition is CL
It is believed to be a complex between ll and the copolymer.

実施例２ ＡＮ／ＳＴ／α−ＭＳＴ（重量比組成＝２７／１１／６
２、クロロホルム溶媒による３０℃の固有粘度０．４１
）の共重合体１０Ｇ■に、ＣｕＩと２−メルカプトベン
ゾイミダゾールとからなる錯体１５部（ＣｕＩとして８
．３８部）を添加してこの混合物を温度２６００Ｃで１
紛間溶融混練した。Example 2 AN/ST/α-MST (weight ratio composition=27/11/6
2. Intrinsic viscosity at 30°C with chloroform solvent 0.41
) copolymer 10G■, 15 parts of a complex consisting of CuI and 2-mercaptobenzimidazole (8 parts as CuI)
．． 38 parts) was added and the mixture was heated at a temperature of 2600C.
The powder was melted and kneaded.

冷却後、得られた重合体組成物について、Ｗ−■ＩＳ吸
光分析およびＥＳＣＡ測定を行なつた。測定方法 （１）ＵＶ−ＶＩＳ測定 粉末を両面接着テープ上に塗布して、反射法によつて測
定した。After cooling, the obtained polymer composition was subjected to W-IS absorption analysis and ESCA measurement. Measurement method (1) UV-VIS measurement The powder was applied onto a double-sided adhesive tape and measured by a reflection method.

（２）ＥＳＣＡ測定 粉末を両面接着テープ上に塗布して、測定した。(2) ESCA measurement The powder was applied onto double-sided adhesive tape and measured.

測定結果 （１）ＵＶ−■ＩＳ 重合体組成物は共重合体に比べて、３３０〜４００ｒ１
７７１．付近に吸収を示す。Measurement results (1) UV-■IS The polymer composition has 330 to 400r1 compared to the copolymer.
771. It shows absorption in the vicinity.

なお、この吸収はＣｕＩと２−メルカプトベンゾイミダ
ゾールとからの錯体には寮在しない。（２）ＥＳＣＡ ＡＣｕＩと２−メルカプトベンゾイミダゾールとからの
錯体からは、Ｃ．．Ｎ．．Ｓ．．ＣＵ，．ｌが検出され
、Ｃｕ＋とＩ−とのＥＳＣＡスペクトルの相対強度比が
０．３９であるのに対し、重合体組成物はこの値より小
さい。Note that this absorption does not occur in the complex of CuI and 2-mercaptobenzimidazole. (2) From the complex of ESCA ACuI and 2-mercaptobenzimidazole, C. ．． N. ．． S. ．． CU,. l is detected and the relative intensity ratio of the ESCA spectra of Cu+ and I- is 0.39, whereas the polymer composition is smaller than this value.

このことは、ＣｕＩと２−メルカプトベンゾイミダゾー
ルとからの錯体とは異なつた沃素が存在していることを
示唆している。This suggests that iodine different from the complex from CuI and 2-mercaptobenzimidazole is present.

Ｂ重合体組成物のＣｕの存在状態はＣｕ＋が主成分であ
り、Ｃ伊やＣｕ＋＋がわずかに検出されるにすぎない。Regarding the presence of Cu in the B polymer composition, Cu+ is the main component, and only a small amount of Cu and Cu++ are detected.

以上のＷ−■ＩＳ測定結果および、ＥＳＣＡ測定結果か
ら重合体組成物は、共重合体と第一銅化合物との間の錯
体であると考えられる。実施例３ ＡＮ／ＳＴ／ＭＭＡ．．ＡＮ／ビニルトルエン、．ＡＮ
／ＭＭＡ，．ＡＮ／ＳＴの各共重合体１（１）部にそれ
ぞれｗ部のＣｕＩを添加し、スクリユタイプエクストル
ダーにより温度２６０℃、加熱滞留時間２０５３−間溶
融混練した。From the above W-■IS measurement results and ESCA measurement results, the polymer composition is considered to be a complex between a copolymer and a cuprous compound. Example 3 AN/ST/MMA. ．． AN/vinyltoluene,. AN
/MMA,. W parts of CuI were added to 1 (1) part of each AN/ST copolymer, and the mixture was melt-kneaded using a screw type extruder at a temperature of 260° C. for a heating residence time of 2053 minutes.

得られた重合体組成物の２６０′Ｃにおける溶融粘度（
島津製、高化式フローテスタによる）および曵糸性を測
定し、第２表に示した。共重合体の駅成分とＣｕＩとの
錯体形成により、重合体組成物は溶融粘度が上昇し、か
つ曳糸性の向上も認められた。ハ成分が４％の共重合体
からの重合体組成物ては溶融粘度の上昇、曳糸性の向上
は殆ど認められなかつた。一方、共重合体のＡＮ成分が
７５％からの重合体組成物は、重合体の一部が分解し、
色調も黒褐色に変色した。実施例４ナイロン６チップ（
硫酸相対粘度２．氏ＴｉＯ２Ｏ．３％含有）に実施例１
に示した重合体組成物の粉末０．４％を添加し、ブレン
ダーで３扮間混合したのち紡糸原料とした。The melt viscosity at 260'C of the obtained polymer composition (
The results are shown in Table 2. The results are shown in Table 2. Due to the complex formation between the station component of the copolymer and CuI, the melt viscosity of the polymer composition increased, and improvement in stringability was also observed. In the case of a polymer composition made from a copolymer containing 4% component (iii), almost no increase in melt viscosity or improvement in stringiness was observed. On the other hand, in a polymer composition in which the AN component of the copolymer is 75%, part of the polymer decomposes,
The color also changed to blackish brown. Example 4 Nylon 6 chip (
Sulfuric acid relative viscosity2. Mr. TiO2O. Example 1
0.4% of the powder of the polymer composition shown in 1 was added and mixed in a blender for 3 minutes to prepare a spinning raw material.

温度２６５℃、０．３？φ−２＋ＦＬ，の口金を通して
紡糸し、油剤処理後９００ｒｒＬ，Ｉｍｉｎの紡速で巻
取り、次いで４５０ｒｒＬ．Ｉｍｉｎの延伸速度で冷延
伸した。上記と同様の方法で、前述の重合体組成物をブ
レンドしないナイロン６のみの紡糸延伸を行ないブラン
ク糸とした。なお比較例１として、実施例１の重合体組
成物のうち、ＣｕＩを残し共重合体のみを上記ナイロン
６チップにかえて用いる以外は同一組成として溶一融混
合し、マスターチツプを作つた。Temperature 265℃, 0.3? The yarn was spun through a φ-2+FL spinneret, and after oil treatment, it was wound at a spinning speed of 900 rrL, Imin, and then 450 rrL. Cold stretching was carried out at a stretching speed of Imin. In the same manner as above, only nylon 6 without blending the above-mentioned polymer composition was spun and drawn to obtain a blank yarn. As Comparative Example 1, a master chip was prepared by melt-mixing the polymer composition of Example 1 with the same composition except that CuI was left and only the copolymer was used instead of the nylon 6 chip.

このマスターチツプを上記実施例４と同様にナイロン６
に添加混合して紡糸原料とし、同一条件で製糸した。ま
た、比較例２として、前記ナイロン６チップにＡＮ／Ｓ
Ｔ（重量比２５／７＼クロロホルム溶媒に二よる固有粘
度０．５１）１．轍量％を添加して溶融混合したものを
紡糸原料とし、上記実施例４と同一条件で製糸した。こ
れらの未延伸糸、延伸糸の糸質を第３表、第４表に示し
た。This master chip was coated with nylon 6 in the same manner as in Example 4 above.
A spinning raw material was prepared by adding and mixing the mixture to the following, and spinning was performed under the same conditions. In addition, as Comparative Example 2, AN/S was added to the nylon 6 chip.
T (weight ratio 25/7\intrinsic viscosity 0.51 due to chloroform solvent)1. A material obtained by adding % of the rutting amount and melt-mixing was used as a spinning raw material, and yarn was spun under the same conditions as in Example 4 above. The yarn qualities of these undrawn yarns and drawn yarns are shown in Tables 3 and 4.

一これらの延伸糸
を用いて編地を作り精練後染色工程に移した。編地条件 針本数１２００本 ｍ／ｃ回転数１２．５ｒｐｍ 糸速５６〜６７７Ｔ！．１Ｍｉｎ 給糸本数６本 張力５（ダ／本） 染色条件 染 料 イルガランプラツクＧＢＬ 染料濃度０．１％０ｗｆ 浴 比５皓 助 剤 硫安（１ｆ′ｅ） 温 度９８℃ 時 間６０ｒｒ１ｉｎ 得られた染色編地を紫外線スタンダードウエザーメータ
に取付け、６３℃の温度で３００ｈｒ紫外線照射を行な
つた。- A knitted fabric was made using these drawn yarns, and after scouring, it was transferred to a dyeing process. Knitting fabric conditions Number of needles 1200 m/c rotation speed 12.5 rpm Yarn speed 56-677T! ．． 1 Min Number of yarns fed: 6 Tension: 5 (da/strand) Dyeing conditions Dye: Irgaran Plak GBL Dye concentration: 0.1% 0wf Bath ratio: 5 auxiliary agent: Ammonium sulfate (1f'e) Temperature: 98°C Time: 60rr1in Obtained The dyed knitted fabric was attached to an ultraviolet standard weather meter and irradiated with ultraviolet light for 300 hours at a temperature of 63°C.

この染色編地の変退色の度合（グレースケールによる）
を測定し、次いで編地をほぐし、紫外線照射面の糸質を
測定した。Degree of discoloration of this dyed knitted fabric (based on gray scale)
The knitted fabric was then loosened and the yarn quality on the ultraviolet irradiated surface was measured.

同一資料の紫外線未照射面と比較してその結果を第５表
に示した。本発明糸は顕著な耐光性を示した。実施例５ ナイロン６チップ（硫酸相対粘度２．６）に実施例１に
示した重合体組成物を、０．３３％、０．６６％、１．
１０％、３．３０％の種々の割合で添加し、良く混合し
たのち紡糸原料とした。Table 5 shows the results of comparison with the surface of the same material that was not irradiated with ultraviolet rays. The yarn of the invention exhibited remarkable light resistance. Example 5 Nylon 6 chips (relative viscosity of sulfuric acid 2.6) were coated with the polymer composition shown in Example 1 at 0.33%, 0.66%, 1.
They were added in various proportions of 10% and 3.30%, mixed well, and then used as spinning raw materials.

また上記ナイロン６チップにＣｕＩ，．ＫＩをそれぞれ
０．０３％（比較試料１）、およびそれぞれ０．１％（
比較試料２）添加混合したものを比較試料として紡糸原
料とした。紡糸、延伸方法は実施例４によつた。ＣｕＩ
．ＫＩを添加した比較試料は紡糸性が悪いほか、特に比
較試料２は延伸工程における毛羽発生が多く、製糸収率
の低いものが得られた。一方、重合体組成物を添加した
本発明糸は紡糸、延伸性に優れ、高い製糸収率が得られ
た。In addition, CuI, . KI at 0.03% (comparative sample 1) and 0.1% (
Comparative sample 2) The added and mixed material was used as a comparative sample as a spinning raw material. The spinning and drawing methods were as in Example 4. CuI
．． The comparative sample containing KI had poor spinnability, and in particular, comparative sample 2 had a lot of fuzz during the drawing process, resulting in a low spinning yield. On the other hand, the yarn of the present invention to which the polymer composition was added had excellent spinning and drawing properties, and a high spinning yield was obtained.

延伸糸の糸質を第６表に示した。得られた延伸糸から編
地を作成し、精練後、染色した。The yarn quality of the drawn yarn is shown in Table 6. A knitted fabric was prepared from the obtained drawn yarn, and after scouring, it was dyed.

染色条件染 料 イルガランボルドＥＬ 染料濃度０．１％０ｗｆ 浴 比５Ｃ＠ 助 剤 硫安（１ｇＩｅ） 温 度９８安Ｃ 時 間６０ｎ１１ｎ 染色後湯洗して、染色編地を実施例４の紫外線照射装置
を使つて６３℃、３（１）時間露光したあと染色編地の
グレースケールおよびナイロン繊維の強力保持率を求め
た。Dyeing condition dye Irgalanbord EL Dye concentration 0.1% 0wf Bath ratio 5C @ Auxiliary agent Ammonium sulfate (1gIe) Temperature 98am C Time 60n11n After dyeing, wash with hot water and irradiate the dyed knitted fabric with ultraviolet rays as in Example 4 After being exposed to light for 3 (1) hours at 63°C using an apparatus, the gray scale of the dyed knitted fabric and the tenacity retention rate of the nylon fibers were determined.

第７表に示すごとく、本発明糸は顕著な耐光堅牢性を示
した。実施例６ ＡＮ／ＳＴ（重量比組成＝３０／７０．．ＭＥＫ溶媒に
よる３０℃固有粘度０．４１）の共重合体にＣｕＩを銅
分として０．０踵量％から２５重量％まで種々の割合で
添加混合し、エクストルーダにより２７０℃、１５分間
溶融混練して種々の重合体組成物を得た。As shown in Table 7, the yarn of the present invention exhibited remarkable light fastness. Example 6 A copolymer of AN/ST (weight ratio composition = 30/70..Intrinsic viscosity 0.41 at 30°C with MEK solvent) was mixed with various amounts of CuI as copper content from 0.0% to 25% by weight. They were added and mixed in the same proportions and melt-kneaded using an extruder at 270° C. for 15 minutes to obtain various polymer compositions.

得られた重合体組成物をナイロン６チップ（硫酸相対粘
度２．６）に０．１重量％から１５重量％添加混合し、
紡温２．６５℃で溶融紡糸し、０．３Ｔｎφ−２４孔の
口金により、紡糸９００ｍ′Ｍｉｎで巻取り、その後冷
延伸した。延伸糸から編地を作り、実施例４と同一の方
法により精練、染色後耐光堅牢性を測定した。第８表に
示した。実施例７ ８０％Ｅ−カプロラクタム水溶液から、２５ｒｃ１１５
１１ｒの重合後、モノマー、オリゴマー（以下ＭＯ）含
有率１２．２％、硫酸相対粘度２．６５のナイロン６ポ
リマを得た。The obtained polymer composition was mixed with nylon 6 chips (sulfuric acid relative viscosity 2.6) by adding 0.1% to 15% by weight,
It was melt-spun at a spinning temperature of 2.65°C, wound up at a spinning speed of 900 m'min using a 0.3Tnφ-24-hole spinneret, and then cold-stretched. A knitted fabric was made from the drawn yarn, and the light fastness after scouring and dyeing was measured in the same manner as in Example 4. It is shown in Table 8. Example 7 From 80% E-caprolactam aqueous solution, 25rc115
After polymerization of 11r, a nylon 6 polymer having a monomer/oligomer (hereinafter referred to as MO) content of 12.2% and a sulfuric acid relative viscosity of 2.65 was obtained.

該ＭＯ含有ポリマを吐出するに際し、ＡＮ／ＳＴ（重量
比組成３０／７０、ＭＥＫ溶媒３０℃の固有粘度０．４
１）１（４）部とＣＵＩｌ娼からなる重合体組成物をナ
イロン６ポリマに対し、０．５％の割合でポリマ吐出口
金バック内に溶融状態で供給して混練し、０．３ＴＷＬ
φ−１００１Ｌ，の口金孔から該混合ポリマを紡糸し、
８００ＴＴＬ１ｍｉｎの紡速で引取つた。得られた未延
伸糸を６０℃の温水中２紛間処理してＭＯを除去した。
次いで９０℃のスチーム加熱下、３．５倍に延伸した。
重合体組成物を含有しないナイロン６の製糸も上記と同
一の方法で行ない、ブランク糸とした。これらの延伸糸
を用いて、実施例４に示した条件により編地を作り染色
を行なつた。When discharging the MO-containing polymer, AN/ST (weight ratio composition 30/70, MEK solvent intrinsic viscosity 0.4 at 30°C)
1) A polymer composition consisting of 1 (4) part and CUIl fluid was supplied in a molten state into a polymer discharge spout bag at a ratio of 0.5% to nylon 6 polymer, and kneaded to form a 0.3TWL
Spinning the mixed polymer from the spinneret hole of φ-1001L,
The spinning speed was 800 TTL/min. The obtained undrawn yarn was treated with two powders in hot water at 60° C. to remove MO.
Then, it was stretched 3.5 times under steam heating at 90°C.
Nylon 6 containing no polymer composition was also spun in the same manner as described above to obtain a blank yarn. Using these drawn yarns, knitted fabrics were made and dyed under the conditions shown in Example 4.

次いで、紫外線スタンダードウエザメータに取付け、６
３℃の温度で５０叫間の紫外線照射を行ない繊維の強力
保持率、グレースケールを測定し。Next, attach it to the ultraviolet standard weather meter, and
The fibers were exposed to ultraviolet light for 50 hours at a temperature of 3 degrees Celsius, and the strength retention rate and gray scale of the fibers were measured.

た。また、該延伸糸を用いて１８０℃の熱風乾燥器にお
ける３時間の熱処理を行ない、繊維の強力保持率を測定
し、これらの結果を第９表に示した。Ta. Further, the drawn yarn was heat treated in a hot air dryer at 180° C. for 3 hours, and the tenacity retention of the fiber was measured. The results are shown in Table 9.

実施例８ＡＮ／ＳＴ（重量比組成＝２５／７５、ＭＥＸ
３Ｏ℃の固有粘度０．３５）１（１）部とＣＵＩｌ娼か
ら溶融混練によつて重合体組成物を得て、該重合体組成
物をＯおよび０．３％含有する７０Ｄ−２４ｆのナイロ
ン６延伸糸を得た。Example 8 AN/ST (weight ratio composition = 25/75, MEX
A polymer composition was obtained by melt kneading from 1 (1) part of CUIl fluid with an intrinsic viscosity of 0.35) at 3O<0>C, and the polymer composition was made of 70D-24F nylon containing O and 0.3%. 6 drawn yarns were obtained.

これらの延伸糸を用いて仮ヨリ加工を施した。加工条件 スピンドル回転数（Ｒｐｍ） ２２４４００仮
ヨリ数（Ｔ／Ｍ） ３０００加
工温度 １８０゜Ｃ得られた
加工糸の特性を第１咳に示す。A temporary twisting process was performed using these drawn yarns. Processing conditions Spindle rotation speed (Rpm) 224,400 Tentative twist number (T/M) 3,000 Processing temperature 180°C The characteristics of the obtained processed yarn are shown in the first example.

該加工糸から編地を編成し、次いで実施例４に示した染
色条件により染色し、その後、６３℃×５０ＣＢ！間の
紫外線照射を行つた。A knitted fabric is knitted from the processed yarn, then dyed according to the dyeing conditions shown in Example 4, and then dyed at 63°C x 50CB! UV irradiation was performed between the two.

耐光堅牢度の結果を第１１表に示した。本発明の仮ヨリ
加工糸は顕著な耐光性を示した。（１）処理後ＣＲは、
６０℃×２０分の処理後測定した。実施例９ ナイロン６６チップ（ＴｉＯ２Ｏ．Ｏ３％含有、硫酸相
対粘度２．７）に実施例２に示した重合体組成物を１．
０％ブレンドしたものをサヤ成分とし、重合体組成物を
ブレンドしない上記ナイロン６６チップをシン成分とし
た、シンーサヤ型の複合繊維をシンーサヤの重量比が１
：１の割合になるよう紡糸温度２８０℃、紡速９００ｗ
１，１ｍｉｎで紡糸した。The light fastness results are shown in Table 11. The temporarily twisted yarn of the present invention exhibited remarkable light resistance. (1) CR after treatment is
Measurement was carried out after treatment at 60°C for 20 minutes. Example 9 The polymer composition shown in Example 2 was applied to a nylon 66 chip (containing TiO2O.O3%, sulfuric acid relative viscosity 2.7).
A thin sheath type composite fiber with a thin sheath type composite fiber in which a 0% blend is used as a sheath component and the above-mentioned nylon 66 chips that are not blended with the polymer composition are used as a thin component.
: Spinning temperature: 280℃, spinning speed: 900W to achieve a ratio of 1
Spinning was performed for 1.1 min.

３ゐ倍に延伸後、実施例４に示した条件により編成、染
色を施し、６３℃×５００１１ｒの紫外線照射を行なつ
た。After stretching 3 times, it was knitted and dyed according to the conditions shown in Example 4, and was irradiated with ultraviolet light at 63°C x 50011r.

実施例のグレースケールは４級を示し優れた耐光性を示
した。一方、重合体組成物を含有しないナイロン６６の
ノみからなる比較繊維は、グレースケール１級であつた
。The gray scale of the example was 4th grade, indicating excellent light resistance. On the other hand, a comparative fiber made of nylon 66 without the polymer composition had a grade 1 gray scale.

Claims (1)

【特許請求の範囲】[Claims] １ アクリロニトリル約１０〜５０重量％および前記ア
クリロニトリルとは異る少なくとも１種のビニル系化合
物約５０〜９０重量％とからなる共重合体に、第一銅化
合物を銅分として該共重合体重量当り０．０２〜２５重
量％配合してなるポリアミド系樹脂の耐光耐熱剤。1 A copolymer consisting of about 10 to 50% by weight of acrylonitrile and about 50 to 90% by weight of at least one vinyl compound different from the acrylonitrile, with a cuprous compound as the copper content per weight of the copolymer. A light and heat resistant agent for polyamide resin containing 0.02 to 25% by weight.