JPS59163481A - Production of water and oil repellent acrylic fiber - Google Patents
Production of water and oil repellent acrylic fiberInfo
- Publication number
- JPS59163481A JPS59163481A JP3554983A JP3554983A JPS59163481A JP S59163481 A JPS59163481 A JP S59163481A JP 3554983 A JP3554983 A JP 3554983A JP 3554983 A JP3554983 A JP 3554983A JP S59163481 A JPS59163481 A JP S59163481A
- Authority
- JP
- Japan
- Prior art keywords
- water
- oil
- repellent
- polyamine
- treatment
- 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.)
- Pending
Links
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は撥水雨油性乞有するアクリル繊維の製造方法に
関する。 ”
従来、繊維製品に撥水撥油性を付与する方法はフルオロ
化合物を主体とする加工剤を編織物等の二次製品か又は
外衣や帽子などになった最終製品に対してスプレ一方式
やパッディング/ドラ1方式によって処理し この製品
の表面に加工剤の被膜を形成させ表面張力を低下せしめ
ることが一般的であった。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a water-repellent, rain-oil-repellent acrylic fiber. ” Conventionally, the method of imparting water and oil repellency to textile products is to apply a finishing agent mainly containing fluoro compounds to secondary products such as knitted fabrics or final products such as outerwear and hats by spraying or patching. It was common practice to process the product using the Ding/Drag 1 method to form a film of a processing agent on the surface of the product to lower the surface tension.
このような方法で得られた製品の性能は初期め段階では
一応すぐれた撥水1峻油性能を有するものの例えば耐洗
層性に劣るなど耐久性が不十分な物であり、且つ風合的
にもゴワゴワとしてかなり剛直性の高いものであった。Although the products obtained by this method have excellent water and oil repellency in the initial stage, their durability is insufficient, for example, their wash resistance is poor, and their texture is poor. It was also stiff and quite rigid.
その理由は上記の方法で処理された物2例えは織物の場
合、その織物の表面部分には該加工剤が付着しているが
、織物の組織内部を構成している糸の内部迄付着させる
ことは不可能で2このことが充分な耐久性を付与できな
い犬ぎな理由の一つである。The reason for this is that in the case of a fabric treated by the above method, for example, the processing agent is attached to the surface of the fabric, but it also adheres to the inside of the threads that make up the inside of the fabric. This is one of the reasons why sufficient durability cannot be imparted.
そのために原綿、原糸段階迄さかのほってこのような撥
水性を有する化合物で処理する方法が従来から試みられ
てきたが、このような化合物で処理した繊維はゴワゴワ
として剛直性が高くなると同時に、単繊維間の接着も起
こり、又対金属並びに対繊維間の平滑性が極めて低下す
ることと、更に又撥水性能を有するため静電気の発生と
その帯電量が大きくなり、紡績や編織物加工などの製品
加工工程通過性が非常に悪いものしか得られず全く実用
化されていないのが現状である。To this end, attempts have been made to treat the raw cotton and yarn stages with such water-repellent compounds, but fibers treated with such compounds become stiff and stiff, and at the same time Adhesion between single fibers also occurs, and the smoothness between metal and fibers is extremely reduced.Furthermore, due to water repellency, static electricity is generated and the amount of charge increases, making it difficult to process spinning and knitting fabrics. At present, only products with very poor passability through the product processing process, such as 100% polyester, have been obtained and have not been put to practical use at all.
そこで本発明@等は面1久性にすぐれた撥水撥油性能を
有1−るアクリル繊維製品を得るために鋭意検討した結
果2本発明を完成するに至った。Therefore, the inventors of the present invention have conducted intensive studies to obtain an acrylic fiber product having excellent surface durability and water- and oil-repellent properties, and as a result, they have completed the present invention.
即ち本発明の要旨とするところ(は、染色したアクリル
繊維をフルオロアルキル基含有撥油剤体)と下記一般式
で示すポリアミン系カチオン活性剤(Blを固形分換算
比率がA:B=1:0.2〜0.6.更((必要に応じ
て高分子カチオン系帯電防止剤(C1をA:B:C=1
:0.2〜0.6:0.2〜0.4で且つ固形分総和濃
度が繊維重量比率で0.2%以上含有するような溶液に
て40〜80℃で少なくとも20分以上浸漬処理した後
。That is, the gist of the present invention is to combine a dyed acrylic fiber with a fluoroalkyl group-containing oil repellent and a polyamine-based cationic activator represented by the following general formula (with a Bl solid content ratio of A:B=1:0). .2 to 0.6. Further ((If necessary, add a polymeric cationic antistatic agent (C1 to
: 0.2-0.6: Immersion treatment at 40-80°C for at least 20 minutes or more in a solution containing 0.2-0.4 and a total solid content concentration of 0.2% or more in terms of fiber weight ratio. After.
100〜130°Cの乾熱で熱処理して得られたアクリ
ル繊維に紡績する直前に融点が10℃以下で沸点が28
0°C以下であるパラフィンとポリアミン系カチオン活
性剤とを主成分とする油剤を固形分換算で0.2〜2.
0重量係付与することを特徴とする撥水撥油性を有づ−
るアクリル繊維の製造方法である。Immediately before spinning, the acrylic fiber obtained by dry heat treatment at 100 to 130°C has a melting point of 10°C or lower and a boiling point of 28°C.
An oil agent whose main components are paraffin and a polyamine-based cation activator whose temperature is 0°C or less is 0.2 to 2.
It has water and oil repellency characterized by imparting zero weight coefficient.
This is a method for producing acrylic fiber.
式中、Rはアルキル基CnH,,n+1でnは15〜2
52mは5〜20の整数である。In the formula, R is an alkyl group CnH,,n+1 and n is 15-2
52m is an integer from 5 to 20.
本発明は前述の如(、紡績ヤ編織性などの加工工程を通
過するに際して全く問題点はなく。The present invention has no problems at all when passing through processing steps such as spinning, knitting, and weaving as described above.
且つすぐれた撥水撥油性能を有するアクリル繊維を製造
する方法であり、以下本発明の同各(Cついて説明づ−
る。This is a method for producing acrylic fibers having excellent water and oil repellency.
Ru.
本発明で使用する撥水撥油胛[としては従来からよく知
られているフルオロアルキル
するものであり,特に限定するものではない。The water- and oil-repellent film used in the present invention is a well-known fluoroalkyl film, and is not particularly limited.
例えはその中で王な物の一例を挙げるとCF3(CF2
)7(CH2)II OCOCH = CH2, CF
s (CF2,)、 CH2ococ(CH3)−CH
2, (CH3)2CF(CF2)、O (CH2)3
0COCH=CH2。For example, to give an example of the most important one, CF3 (CF2
)7(CH2)II OCOCH = CH2, CF
s (CF2,), CH2ococ(CH3)-CH
2, (CH3)2CF(CF2), O (CH2)3
0COCH=CH2.
( CFs) CF( CF2)a CHz CH (
OCOCH3) OCOC ( ’−Hs )二CH2
の如さ炭素数3〜20,好ましくは4〜】5のフルオロ
アルキル基を含むアクリレート又はメタアクリレートで
代表される不飽和エステル類の重合体あるいはかかる不
飽和エステル類とフルオロアルキル類を含まない重合し
得る化合物1種又は2種以上との共重合体などがあけら
れる。( CFs) CF ( CF2)a CHz CH (
OCOCH3) OCOC ('-Hs)2CH2
Polymers of unsaturated esters represented by acrylates or methacrylates containing 3 to 20 carbon atoms, preferably 4 to 5 fluoroalkyl groups, or polymers containing such unsaturated esters and fluoroalkyl groups. Examples include copolymers with one or more compounds that can be used.
この場合,フルオロアルキル基を含まな(・重合し得る
化合物としては多くのものがあるカーその甲で王な例を
挙げると,エチレン、酢酸ビニル、弗化ビニル、塩化ビ
ニル、))コゲ/ビニリデン、アクリロニトリル、スチ
レン、α−メチルスチレン、p−メチルスチレン、−r
y+)ルeトソのアルキルエステル、メタアクリル酸と
そのアルキルエステル、アクリルアミド、メタアクリル
アミド、ジアセトンアクリルアミドなどである。In this case, koge/vinylidene that does not contain a fluoroalkyl group (there are many polymerizable compounds, ethylene, vinyl acetate, vinyl fluoride, vinyl chloride, etc.) , acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, -r
y+) alkyl esters of methacrylic acid and its alkyl esters, acrylamide, methacrylamide, diacetone acrylamide, etc.
本発明は上記したようなフルオロアルキル基を含有する
撥水撥油剤を単にアクリル繊維を染色した後に含浸乾燥
するので(はなくポリアミン系カチオ/・活性剤を一定
量添加した溶液ある(・は更に高分子カチオン系帯電防
止剤を添加した40〜80°Gの溶液中で少なくとも2
0分以上浸漬処理して、所定の温度で乾燥並びに熱処理
した後、紡績する直前に融点が10℃以下で沸点が28
0℃以下であるパラフィンとポリアミン系カチオン活性
剤とを主成分とする油剤を固形分換算で0.2〜2,0
重量係付与することによって初めて満足する撥水撥油性
能と加工工程通過性が得られるのである。In the present invention, acrylic fibers are simply dyed with a water and oil repellent containing a fluoroalkyl group as described above, and then impregnated and dried (instead of a solution containing a certain amount of a polyamine-based cation/activator). At least 2% in a solution at 40-80°G with addition of a polymeric cationic antistatic agent.
After immersion treatment for 0 minutes or more, drying and heat treatment at a predetermined temperature, and immediately before spinning, the material has a melting point of 10°C or less and a boiling point of 28°C.
An oil agent whose main components are paraffin and a polyamine-based cationic activator that have a temperature of 0°C or lower, with a solid content of 0.2 to 2.0
Satisfactory water and oil repellency and processing process passability can only be achieved by adding a weight factor.
本発明において染色したアクリル繊維にM述の撥水土酸
油剤にポリアミン系カチオン活性剤を添加した溶液、更
に又高分子カチオン糸帯電防止剤を添加した溶液で浸漬
処理して所定の熱処理をしたものは、かな9すぐれた撥
水撥油性能を有している。しかし紡績等での加工通過性
において静電気等のトラブルが若干発生するという問題
点があるので、前述の主成分からなる特定の油剤を紡績
の直前に付与することにより。Acrylic fibers dyed in the present invention are immersed in a solution prepared by adding a polyamine cationic activator to the water-repellent earth-acid oil described in M, and further added with a polymer cationic yarn antistatic agent, and then subjected to a prescribed heat treatment. Kana 9 has excellent water and oil repellency. However, there is a problem in that some troubles such as static electricity occur in processing properties such as spinning, so a specific oil agent consisting of the above-mentioned main components is applied immediately before spinning.
この加工通過性、特に紡績に於ける平滑性向上と静電気
の発生量は激減し、且つ撥水撥油性能の維持が同時に達
成されるのであり、このような効果の得られる本発明は
極めて画期的な方法といえるのである。本発明でフルオ
ロアルキル基含有の撥水撥油剤(Alにポリアミン系カ
チオン活性剤(Blあるいは更に高分子カチオン糸帯電
防止剤(C1を添加した処理液で処理する理由は本来ア
クリル繊維の染着座席として知られるスルホン酸やカル
ボッ酸などのような酸性基に対して該処理液中のカチオ
ン基を結合させ、その瀧合力によってフルオロアルキル
化合物のアクリル繊維に対する耐久性付与を図ったもの
である。The processability, especially the smoothness during spinning, is improved, the amount of static electricity generated is drastically reduced, and the water and oil repellency is maintained at the same time. This can be said to be a temporary method. In the present invention, the reason for treating acrylic fibers with a treatment solution containing a water and oil repellent (Al) containing a fluoroalkyl group-containing water and oil repellent (Al and a polyamine cationic activator (Bl) or a polymeric cationic yarn antistatic agent (C1) is originally The cationic group in the treatment liquid is bonded to an acidic group such as sulfonic acid or carboxylic acid, which is known as fluoroalkyl compound, and the cationic group in the treatment liquid is used to impart durability to the acrylic fiber of the fluoroalkyl compound.
そして本発明で用いられるポリアミン系カチオン活性剤
は前述(1)式の如<、疎水性成分と親水性成分のバラ
ンスが重要であって同じポリアミン系カチオン活性剤で
あってもこのバランスがとれていないと本発明の目的と
する効果は得られない。即ち2本発明で使用するポリア
ミン系カチオン活性剤は前述(1)式におけるR即ち疎
水性成分であるアルキル基は一般式CnH2n+1で示
され、nが15〜25で、親水性成分の量を示すmが5
〜20である。As shown in formula (1) above, the polyamine cation activator used in the present invention must have a balance between hydrophobic components and hydrophilic components, and even the same polyamine cation activator cannot maintain this balance. Otherwise, the desired effect of the present invention cannot be obtained. That is, in the polyamine-based cationic activator used in the present invention, R in the above formula (1), that is, the alkyl group that is the hydrophobic component, is represented by the general formula CnH2n+1, where n is 15 to 25 and represents the amount of the hydrophilic component. m is 5
~20.
撥水加工された繊維製品は吸水、吸湿性が一般に低下し
摩擦による静電気の発生量と帯電量が増加するので加工
工程通過性は悪化する。Textile products that have been treated to be water repellent generally have lower water absorption and hygroscopicity, and the amount of static electricity generated and electrostatic charge due to friction increases, resulting in poor passability through processing steps.
その対策として静電気障害を除去するために通常のポリ
エチレンオキサイドやアルキルフォスンエートなどを生
成分とする帯電防止剤を処理液の中に添加すれば一応そ
の効果は認められるが多くの場合目的とする撥水撥油性
能も失うことが非常に多い。そこで本発明では目的とす
る撥水撥油性能と加工通過性両方の性fiヒを同時に満
足するために高分子カチオン系の帯電防止剤を一定の比
率で添加することによってこれらの問題を解決している
。その添加比率はフルオロアルキル基含有の撥水撥油剤
(AJ及びポリアミ/系カチオン活性MIJ (B+の
場合A:B =1:0,2〜0.6であることが必要で
あって、高分子カチオン系帯電防止剤(C1を併用する
場合A:B:C=1:0.2〜0.6:0.2〜0.4
であることが必要である。その理由は該撥水撥油剤(A
lに対して添加比率が小さくなると当然ながら柔軟平滑
性又は訓電効果が低下し、文通に犬ぎくなると撥水撥油
性、特に撥油性能の低下が発生する。従って目的とする
性能と良好な加工性を得るためにこの添加比率は重要で
ある。As a countermeasure, adding an antistatic agent containing ordinary polyethylene oxide or alkyl phosunate to the processing solution to remove static electricity may have some effect, but in many cases this is the intended purpose. Water and oil repellency properties are also often lost. Therefore, in the present invention, these problems are solved by adding a polymeric cationic antistatic agent at a certain ratio in order to simultaneously satisfy the desired properties of water and oil repellency and processability. ing. The addition ratio of water and oil repellents containing fluoroalkyl groups (AJ and polyamide/based cationic active MIJ (in the case of B+, A:B = 1:0, 2 to 0.6, and Cationic antistatic agent (when used together with C1 A:B:C=1:0.2-0.6:0.2-0.4
It is necessary that The reason is that the water and oil repellent (A
Naturally, if the addition ratio to 1 is small, the softness and smoothness or the electric shock effect will decrease, and if correspondence becomes too difficult, water and oil repellency, especially oil repellency, will decrease. Therefore, this addition ratio is important in order to obtain the desired performance and good processability.
本発明の処理工程でもう一つの重要な点は該処理剤の繊
維に対する付着率であって、繊維重量比率が0.2%以
上の固形分換y総和濃度が必要である。この濃度かあま
りにも少ないと本発明が目的とする性能が得られないは
が9が、加工工程通過性も低下する。Another important point in the treatment process of the present invention is the adhesion rate of the treatment agent to the fibers, and it is necessary to have a total solid content concentration of 0.2% or more by weight of the fibers. If this concentration is too low, the performance aimed at by the present invention cannot be obtained9, and the passability through processing steps will also be reduced.
一方、極端に濃度が高くなると単繊維間の接着が生じて
平滑性の低下つまり加工性の低下が発生するので0.3
〜0.6%範囲が通常よく用いられる水準である。以上
のような処理を施すために本発明(は40〜80℃の処
理液に浴比1:10〜50の適当な条件で浸漬し、少な
くとも20分以上処理するものである。On the other hand, if the concentration is extremely high, adhesion between single fibers will occur, resulting in a decrease in smoothness, that is, a decrease in workability, so 0.3
A range of 0.6% to 0.6% is a commonly used level. In order to carry out the above-mentioned treatment, according to the present invention, the substrate is immersed in a treatment solution at a temperature of 40 to 80° C. under suitable conditions at a bath ratio of 1:10 to 50, and treated for at least 20 minutes.
その理由は、繊維と該処理剤の親和力を高めるには低温
浴で短時間浸漬するよりも、処理浴の温度を高くして処
理時間を長くする方が有利である。The reason for this is that in order to increase the affinity between fibers and the treatment agent, it is more advantageous to increase the temperature of the treatment bath and lengthen the treatment time than to immerse the fibers in a low-temperature bath for a short time.
しかしあまり高温になると処理剤の乳化安定性が低下す
るので、工業的灸件として40〜80℃で20分程度の
処理が最も好ましく、均一な処理効果を得るために通常
、循環ボンダ等で強制的に攪拌などが行なわれている。However, if the temperature is too high, the emulsification stability of the treatment agent will decrease, so for industrial moxibustion, treatment at 40 to 80℃ for about 20 minutes is most preferable, and in order to obtain a uniform treatment effect, it is usually forced using a circulation bonder etc. Stirring etc. are carried out separately.
処理後、脱水した後に100〜130℃で乾燥並びに熱
処理を行ない本発明で必要な水準の性能を有する撥水撥
油剤処理を完結するが、この温度が低いと長時間処理が
必要であり、又高温になると黄変等の問題があワ2通常
130°Cで5〜10分必要である。After the treatment, dehydration is performed, followed by drying and heat treatment at 100 to 130°C to complete the water and oil repellent treatment that has the level of performance required by the present invention, but if this temperature is low, a long treatment is required, and At high temperatures, problems such as yellowing occur.2 Usually, 5 to 10 minutes at 130°C is required.
本発明の最も重要なポイントは以上のような方法で処理
された撥水撥油性を有するアクリル繊維を紡績直前に特
定の油剤を付与することである。The most important point of the present invention is to apply a specific oil agent to the water- and oil-repellent acrylic fiber treated by the method described above immediately before spinning.
以下、この特定の油剤処理方法について説明する。This specific oil treatment method will be explained below.
従来、紡績に於げる紡毛方式やセミ梳毛方式の場合は通
常のアクリル繊維の集綿でも工程通過性改良のため紡績
直前に油剤(以下追油剤とイウ)ラスプレー処理づ−る
ことがある。Conventionally, in the case of wool spinning or semi-worsting methods in spinning, even the collection of ordinary acrylic fibers is sometimes treated with an oil spray (hereinafter referred to as lubricant) immediately before spinning in order to improve process passability.
ところが撥水撥油性を付与されたこのような繊維は従来
処理されているよ5な紡績追油方式をそのまま実施する
ことは不可能である。However, such fibers that have been given water and oil repellency cannot be subjected to the conventional spinning and oil addition method as they are.
つま9撥水撥油性能が付与されているのであるから、従
来繊維のように均一な付着処理がまず困難であることと
、更には従来よく用いられている追油剤は殆どの物が撥
水撥油性能を低下せしめるので目的とする性能を有する
最終製品を得ることができないのである。そこで本発明
者等は撥水撥油性能を低下させないで紡績性を中心とし
た工程通過性改良を鋭意検討した結果融点が10℃以下
で沸点が280°C以下であるパラフィン例えは炭素数
15以上のノくラフインを含んでいても良いが主として
デカンないしはペンタデカ/の如く炭素数10〜150
ノぐラフインを主体とする物とポリアミン系カチオン活
性剤を主成分とする追油剤を固形分換算で0.2〜2.
0重量受付与する方法を見い出した。本発明で用いる追
油剤は融点が10°C以下で沸点が280℃以下のパラ
フィンとポリアミン系のカチオン活性剤が主成分となっ
ているが、このパラフィンは常温では液状を示し、且つ
低沸点型で流動パラフィンの範ちゅうに入9.パラフィ
ンとポリアミン系カチオン活性剤その他の比率は処理さ
れた繊維の解繊性や平滑性等によって任意に変えること
が必要である。Tsume 9 Since it is endowed with water and oil repellency, it is difficult to apply it uniformly like with conventional fibers, and most of the oil repellents commonly used in the past are water repellent. Since the oil repellency is reduced, it is not possible to obtain a final product with the desired performance. Therefore, the present inventors conducted intensive studies to improve process passability, mainly spinnability, without reducing water and oil repellency, and found that paraffin, which has a melting point of 10°C or less and a boiling point of 280°C or less, has a carbon number of 15. It may contain the above-mentioned rough-in, but mainly has 10 to 15 carbon atoms, such as decane or pentadeca.
The amount of oil refueling agent mainly composed of Nogurafuin and polyamine cation activator is 0.2 to 2.0% in solid content.
We have found a way to give zero weight. The main components of the refueling agent used in the present invention are paraffin with a melting point of 10°C or lower and a boiling point of 280°C or lower, and a polyamine-based cationic activator. 9. It falls into the category of liquid paraffin. It is necessary to arbitrarily change the ratio of paraffin, polyamine-based cationic activator, etc. depending on the fibrillation properties, smoothness, etc. of the treated fibers.
通常は平滑性同上を重視してパラフィンの比率を高くし
た7:3位のものが多(用いられる。Usually, a material with a high paraffin ratio of 7:3 is often used, with emphasis on smoothness.
次にこの追油剤の付着量は固形分換算で0.2〜2,0
重量%以内に付着しなけ扛ばならないが付着量が少ない
と紡績性の向上が期待でざないし、あまり多いと撥水撥
油性能の低下が生じるので、好ましくは0.4〜0.6
重量%と規制することが必要である。Next, the adhesion amount of this refueling agent is 0.2 to 2.0 in terms of solid content.
It must be adhered within a weight percent range, but if the amount is too small, the spinnability cannot be expected to improve, and if it is too large, the water and oil repellency performance will be reduced, so it is preferably 0.4 to 0.6.
It is necessary to regulate the amount by weight%.
第1図(は代表的なフルオロアルキル化合物仄)にアサ
ヒガードAG−310(開成化学)に対して先述のポリ
アミン系カチオン活性剤(Blを添加比率A:B=1:
0.4の処理液で染色後のアクリル繊維10dに対して
約0.3%付着し、所定の熱処理を行った繊維へ前述の
本発明で使用可能な追油剤の付着量を変化させた時の撥
水撥油性能を示したもので、第2図は同じく加工工程通
過性に対する一つの特性値であるね繊維間の平滑性を約
101’/m のスライバーによる引抜き強力で示し
たものである。追油剤の付着率は撥水撥油性と平滑性に
対して極めて重要な影響を与えるのであり、第1図及び
第2図は目的とする撥水撥油性能を低下させない範囲で
平滑性の向上つまり引抜き強力を小さくするためには0
.2〜2.0%の付着率が必要であることを示している
。In Figure 1 (representative fluoroalkyl compounds), the aforementioned polyamine-based cationic activator (Bl) is added to Asahi Guard AG-310 (Kaisei Kagaku) at a ratio of A:B=1:
Approximately 0.3% of the oil additive that can be used in the present invention adheres to fibers that have been subjected to a prescribed heat treatment, and is attached to 10 d of acrylic fibers after dyeing with a treatment solution of 0.4%. Figure 2 also shows the smoothness between the fibers, which is a characteristic value for passability through the processing process, in terms of the drawing strength of the sliver of about 101'/m2. be. The adhesion rate of oil repellent has an extremely important effect on water and oil repellency and smoothness, and Figures 1 and 2 show improvements in smoothness within a range that does not reduce the desired water and oil repellency. In other words, in order to reduce the pulling force, 0
.. This indicates that a deposition rate of 2 to 2.0% is required.
本発明は紡績する直前に追油するものであるから、アク
リル繊維の形態としては原綿、トウ。In the present invention, oil is added just before spinning, so the form of the acrylic fiber is raw cotton or tow.
トップ等が前提となるが、この追油剤を紡績糸又(は製
品状態で処理することも何ら差支えない。Although it is assumed that the top etc. are used, there is no problem in treating this oil replenisher in the form of spun yarn or a product.
本発明方法で撥水撥油性能を付与して得られたアクリル
繊維の紡績糸からは防汚性−?撥水性能を有するカーペ
ットやセーター等の差別化部品を得ることができる。The spun yarn of acrylic fiber obtained by imparting water and oil repellency by the method of the present invention has antifouling properties. It is possible to obtain differentiated parts such as carpets and sweaters that have water-repellent properties.
以下実施例によって本発明を説明する。The present invention will be explained below with reference to Examples.
実施例1
ボンネル(三菱レイヨン(株)製アクリル繊維)プライ
ト10dの102朋を約15に!、、通常のパッケージ
染色を下記の条件で実施した。Example 1 Bonnel (acrylic fiber manufactured by Mitsubishi Rayon Co., Ltd.) Prite 10d 102 to about 15! ,,Ordinary package dyeing was carried out under the following conditions.
染色条件
C6I Ba5ic Blue −691,5%owf
酢酸(40%) 1.0 〃カテオゲン
ANスーパー 1.5〃(第一工業製薬(株)
カチオ/系活性炸0温度X時間 100℃
×60分浴比 1:10
上記染色原綿を水洗脱水して、各条件に分は第1表のよ
うな条件で繊維に対する付着率が纜維重量当り約0.3
−%になるように処理した。Staining conditions C6I Ba5ic Blue -691, 5% owf
Acetic acid (40%) 1.0 Cateogen AN Super 1.5 (Daiichi Kogyo Seiyaku Co., Ltd.)
Cation/system active explosion 0 temperature x time 100℃
x 60 minutes Bath ratio 1:10 The above dyed raw cotton was washed and dehydrated, and the adhesion rate to the fibers was approximately 0.3 per fiber weight under each condition as shown in Table 1.
-%.
* 処理剤A:アサヒガードAG−310(開成化学(
株)製、フルオロアルキル基
含有撥水撥油剤)
B:本文一般式(1)におけるアルキル基rRJの炭素
数が18でmが8で
あるポリアミン系カチオン活性剤
(三洋化成(株ツカチオ/系染色
仕上剤)
*** 処理浴条件 浴比・・・・・1:101 k
!−型パッケージ染色機→脱
アルキルリン酸エステル= 50/30/’201)加
工性
カード通過性=(良)◎−〇−△−x−xx(劣〕スラ
イバー引抜強カニカードスライバ−約10.P/7nの
引抜き強力をテン70ンを用
いて20本測定し、その平均値
として示した。* Processing agent A: Asahi Guard AG-310 (Kaisei Chemical Co., Ltd.)
(manufactured by Sanyo Kasei Co., Ltd., fluoroalkyl group-containing water and oil repellent) B: A polyamine-based cationic activator in which the alkyl group rRJ in general formula (1) in the text has 18 carbon atoms and m is 8 (manufactured by Sanyo Kasei Co., Ltd. Finishing agent) *** Processing bath conditions Bath ratio...1:101k
! -Type package dyeing machine → dealkyl phosphate ester = 50/30/'201) Workability Card passing properties = (Good) ◎ - 〇 - △ - x - xx (Poor) Sliver drawing strength Crab card sliver - Approx. 10. The drawing strength of P/7n was measured using a 70-ton tensile strength for 20 pieces, and the average value was shown.
(試長−1,1×繊維長9
2) 姿品性能
撥水性: DuPont法撥水性能測定榮件に準拠(良
) 5級〜1級 (劣)
撥油性: ’AATCC法撥油性能測定条件に準拠(良
) 8級〜1級 (劣)
第1表より本発明法に基づ< Nu 5並びに東140
条件は加工性、撥水撥油性能共に良好な結果が得られた
。しかしながらN1111〜隔4の条件は撥水撥油剤の
含有率の非常に高い場合もしくは単独処理における比較
例であり撥水撥油性能はすぐれているが、加工性が劣り
実用化は困難であった。(Test length - 1,1 x fiber length 9 2) Appearance performance Water repellency: Conforms to DuPont method water repellency performance measurement requirements (Good) 5th grade to 1st grade (Poor) Oil repellency: 'AATCC method oil repellency performance measurement Conforms to conditions (good) Grade 8 to Grade 1 (poor) Based on the method of the present invention from Table 1 < Nu 5 and East 140
Under the conditions, good results were obtained in both processability and water and oil repellency. However, the conditions of N1111 to 4 are comparative examples where the content of water and oil repellent is very high or when treated alone, and although the water and oil repellency is excellent, the processability is poor and practical application is difficult. .
■6〜(13の比較例は加工性は遅15の現行油剤条件
にほぼ近い位の良好な結果であるが撥水撥油性能、特に
撥油性が劣る物しか得られなかった。(2) Comparative Examples 6 to 13 had good workability, almost close to the current oil conditions of Slow 15, but only poor water and oil repellency, especially oil repellency, was obtained.
実施例2
7K 7 ネルフライ)3dの48万トータルデニール
のトウを下記条件でパッケージ染色を行なった。Example 2 A 480,000 total denier tow of 7K 7 Nellfly) 3d was package dyed under the following conditions.
C,I Ba5ic Red−232%Ow f酢酸(
40%) 1 〃
カチオゲンANスーパー 2 〃温度X時間
100’CX60分浴比
1:10
上記染色トウを水洗脱水して下記第2表の条件で実施例
1と同様に処理した。尚、この時の処理浴は70 ’C
X 20分、浴比1薯0で行ない、脱水後の熱処理ば1
30’CX10分実施した。C,I Ba5ic Red-232%Ow facetic acid (
40%) 1 Cationogen AN Super 2 Temperature x Time
100'CX60 minute bath ratio
1:10 The dyed tow was washed and dehydrated and treated in the same manner as in Example 1 under the conditions shown in Table 2 below. The temperature of the treatment bath at this time was 70'C.
Heat treatment after dehydration for 20 minutes at a bath ratio of 1 to 0.
It was carried out for 30'CX10 minutes.
そしてこの処理トウは繊維長64nmの足長カントされ
、紡績直前に追油して、紡毛方式で30メートル番手の
糸を紡出した。次にこの紡毛糸を用いてイス張り用モケ
ットを作った結果は第2表の通りで、 1IvL3及び
N7の本発明法によるものは加工性は良好で、且つ得ら
れた製品の撥水撥油性能は目標とする高い水準を有し、
又風合も良好なイス張り用モケットを得ることができた
。又N3に対しN7は帯電防止剤の添加により加工性が
向上していたが若干撥油性能が低下していた。尚、比較
例の嵐1は付着率が低く加工性が悪<、侮られた製品の
性能も低かったが、 NQ2及び%6は製品性能は良好
であったが加工性が劣っていた。更に又Na4.嵐5+
及び気8は加工性は述9の現行条件と同等のすぐれた
加工性であったが、製品の撥水撥油性能(はかなり劣る
ものしか得られなかった。Then, this treated tow was canted to a fiber length of 64 nm, added oil immediately before spinning, and spun into yarn with a count of 30 meters using a wool spinning method. Next, the results of making moquettes for chair upholstery using this woolen yarn are shown in Table 2. 1IvL3 and N7 made by the method of the present invention had good processability, and the resulting products were water and oil repellent. Performance has a high standard to aim for,
In addition, a moquette for chair upholstery with a good texture could be obtained. Furthermore, compared to N3, N7 had improved workability due to the addition of an antistatic agent, but its oil repellency was slightly lower. In addition, Arashi 1, a comparative example, had a low adhesion rate and poor workability, and the performance of the inferior product was also low, while NQ2 and %6 had good product performance but poor workability. Furthermore, Na4. Arashi 5+
and Qi 8 had excellent processability equivalent to that under the current conditions described in 9, but the water and oil repellency of the product was considerably inferior.
1)撥水撥油処理条件
(イ)処理剤A;アサヒガードAG740(明成化学製
、フルオロアル
キル基含有撥水撥油剤〕
B:ポリアミン系カチオン活性剤
(実施例1と同一品)
C:高分子カチオン系帯電防止剤
*タフロン320A:第−工業製薬(株)カチオン系柔
軟仕上剤
(ロ) 付着率:処理前後の浴濃度(減圧下60℃X
4 hr乾燥後の固形分9差か
ら付着率を算出
vx(cとニー(尤、□0゜
■=処理浴の総量<1)−=
01:処理浴の籾温濃度(P/l )
C2:処理後の浴濃度(P/l )
F;処理した繊維富貴(i)
2)追油処理条件
(イ) 追油剤・・・・・実施例1の追油剤Cと同一品
(ロ) 供給量・・・・・スプレ一方式で供給した量を
繊維1■量幽ワの固形分換算濃
度(%)で表示
3)加工性
制電性:加工工程中の制電効果
(良90−〇−へ一×(劣)
紡績性:紡毛紡績工程安定性
(良う◎−〇−へ一× (劣う
製織性:モケット生機製織工程安定性
(良う◎−〇−へ一× (劣り
4)製品性
撥水撥油性は実施例1に準拠
風合:柔軟性 (良)◎−〇−△−×(劣〕1) Water and oil repellent treatment conditions (a) Treatment agent A: Asahi Guard AG740 (manufactured by Meisei Chemical, water and oil repellent containing fluoroalkyl group) B: Polyamine-based cationic activator (same product as Example 1) C: High Molecular cationic antistatic agent *Taflon 320A: Dai-Kogyo Seiyaku Co., Ltd. Cationic softener (b) Adhesion rate: Bath concentration before and after treatment (60°C under reduced pressure
Calculate the adhesion rate from the solid content 9 difference after 4 hours drying vx (c and knee (y, □0゜■ = total amount of treatment bath < 1) - = 01: Rice temperature concentration of treatment bath (P/l) C2 : Bath concentration after treatment (P/l) F; Treated fiber Fuki (i) 2) Addition treatment conditions (a) Addition agent: Same product as addition oil agent C in Example 1 (b) Supply Amount: The amount supplied by one spray method is expressed as the solid content concentration (%) of 1 fiber.3) Workability Antistatic property: Antistatic effect during processing process (good 90-〇 - 1 × (Poor) Spinability: Wool spinning process stability (Good ◎ - 0 - 1 × (Poor weavability: Moquette greige weaving process stability (Good ◎ - 0 - 1 × (Poor 4) product Water and oil repellency is based on Example 1 Texture: Flexibility (Good) ◎-〇-△-× (Poor)
第1図はフルオロアルキル基含有撥水撥油剤+AJに対
して本文詳述のポリアミン系カチオン活性剤tBlを添
加比率A:B=1:0.4で染色後のアクリル繊維10
dに約0.3%付着させた原綿に本発明で用いる追油剤
の付着量と撥水性及び撥油性能との関係を示したもので
ある。尚、この時の撥水性能の測定はDuPont法で
撥油性能はAATCC法に準拠したものである。
第2図は同じく追油剤の付着量を変化させた時の繊維間
平滑性との関係をカードスライバ−(約1017m )
の引抜き強力で示したものである。
手続補正書 1゜
昭和58年 7月/グ)12゜
3゜
特Jイ「庁長君° 若杉和大 殿
4゜
1、事件の表利く
特願昭58−35549号
2、発明の名称
撥水撥油性を有するアクリル繊維の製造方法3、補正を
する者
事件との関係 特許出願人
東京都中央区京橋二丁「l 3 計1.95::(60
3)三菱レイヨン株式会社
ji’ZFH12L:’、iミ河崎晃大4、代 理 人
東京都中央区京+1G二丁[−13番19″;じ自発
の補正の対象
明細書
7、補正の内容
4頁7行]撥油」→「撥水撥油」
17貝1行「明放化学」→l旭硝子」
20頁12行「熾8は」→4熾8の」Figure 1 shows 10 acrylic fibers after dyeing at a ratio A:B=1:0.4 of the polyamine-based cationic activator tBl, which is described in detail in the text, to the fluoroalkyl group-containing water and oil repellent + AJ.
d shows the relationship between the amount of oil repellent applied in the present invention and water repellency and oil repellency on raw cotton with approximately 0.3% adhesion. The water repellency was measured using the DuPont method, and the oil repellency was measured based on the AATCC method. Figure 2 also shows the relationship between the interfiber smoothness and the amount of lubricant applied to a card sliver (approximately 1017 m).
This is shown in terms of the pull-out strength. Procedural amendment 1゜July 1983/G) 12゜3゜Special J-I “Chief of the Agency Mr. Kazuhiro Wakasugi 4゜1, Patent Application No. 58-35549 showing the case 2, name of the invention Process for producing acrylic fibers with water and oil repellency 3, relationship with the case of the person making the amendment Patent applicant: Kyobashi 2-cho, Chuo-ku, Tokyo "l 3 Total 1.95:: (60
3) Mitsubishi Rayon Co., Ltd. ji'ZFH12L:', i Mi Kawasaki Kodai 4, Agent Kyo + 1G 2-chome, Chuo-ku, Tokyo [-13-19''; Specification subject to voluntary amendment 7, Contents of amendment 4th line, 7th line] Oil repellent” → “Water and oil repellent” 17th line 1 line “Meiho Kagaku” → 1 Asahi Glass” 20th page, 12th line “8th wa” → 4th line 8th”
Claims (2)
撥水撥油剤(A+及び式(1)で示すポリアミン系カチ
オン活性剤(Blを固形分換算比率がA:B=l:0.
2〜0.6で且つ固形分総和濃度が!aKr41重量比
率で0.2%以上含有する溶液にて40〜80℃で少な
くとも20分以上浸貨処理し、100〜130℃の乾熱
で熱処理して得られたアクリル繊維を紡績する直前に融
点が10’C以下で沸点が280℃以下であるパラフィ
ンとポリアミン系カチオン活性剤とを主成分とする油剤
を固形分換算で0.2〜2.0重量%付与することを特
徴とする撥水撥油性を有するアクリル繊維の製造方法。 式中、Rはアルキル基CnH21+1でnば15〜25
2mは5〜2oの整数である。(1) Dyed acrylic fibers are coated with a fluoroalkyl group-containing water and oil repellent (A+) and a polyamine-based cationic activator represented by formula (1) (Bl in terms of solid content ratio of A:B=l:0.
2 to 0.6 and the total solid concentration! Immediately before spinning the acrylic fiber obtained by soaking it at 40 to 80°C for at least 20 minutes in a solution containing 0.2% or more of aKr41 by weight and heat-treating it with dry heat at 100 to 130°C, the melting point A water repellent characterized by applying an oil agent whose main components are paraffin having a temperature of 10'C or less and a boiling point of 280C or less and a polyamine cation activator in an amount of 0.2 to 2.0% by weight in terms of solid content. A method for producing oil-repellent acrylic fiber. In the formula, R is an alkyl group CnH21+1 and n is 15 to 25
2m is an integer from 5 to 2o.
ポリアミン系カチオン活性剤(Blを含有する溶液に高
分子カチオン系帯電防止剤(C1を固形分換算比率でA
: B : C= 1 : 0.2〜0.6 : 0
.2〜0.4となるよう添加する特許請求の範囲第1項
記載の方法。(2) Fluoroalkyl group-containing water and oil repellent (A),
Polyamine-based cationic activator (Bl-containing solution containing polymeric cationic antistatic agent (C1 in solid content equivalent ratio A)
:B:C=1:0.2~0.6:0
.. 2. The method according to claim 1, wherein the amount is added to be 2 to 0.4.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3554983A JPS59163481A (en) | 1983-03-04 | 1983-03-04 | Production of water and oil repellent acrylic fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3554983A JPS59163481A (en) | 1983-03-04 | 1983-03-04 | Production of water and oil repellent acrylic fiber |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS59163481A true JPS59163481A (en) | 1984-09-14 |
Family
ID=12444801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3554983A Pending JPS59163481A (en) | 1983-03-04 | 1983-03-04 | Production of water and oil repellent acrylic fiber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59163481A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5346949A (en) * | 1992-05-29 | 1994-09-13 | Hoechst Gosei K.K. | Fluorine containing aqueous composition having water repellent and oil repellent properties |
-
1983
- 1983-03-04 JP JP3554983A patent/JPS59163481A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5346949A (en) * | 1992-05-29 | 1994-09-13 | Hoechst Gosei K.K. | Fluorine containing aqueous composition having water repellent and oil repellent properties |
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