JP3651132B2 - Polyester fiber material and method for producing the same - Google Patents

Description

また、本発明のポリエステル系繊維材料の製造方法は、次の構成を有する。
【０００８】
ハロゲン化シクロアルカン化合物を含有する処理液で浴中処理した後、ポリアルキレングリコール、芳香族ジカルボン酸およびアルキレングリコールのブロック共重合体と、多孔質物質、金属酸化物、無機酸の金属塩、および有機酸の金属塩から選ばれる少なくとも一種の無機系化合物からなる消臭剤、前記一般式［１］に示されるポリビニルアミン化合物からなる消臭剤、および合成樹脂バインダーを含む処理液をパディング法で付与し、次いで熱処理することを特徴とするポリエステル系繊維材料の製造方法である。
【０００９】
あるいはまた、ポリアルキレングリコール、芳香族ジカルボン酸およびアルキレングリコールのブロック共重合体と、多孔質物質、金属酸化物、無機酸の金属塩、および有機酸の金属塩から選ばれる少なくとも一種の無機系化合物からなる消臭剤、前記一般式［１］に示されるポリビニルアミン化合物からなる消臭剤、合成樹脂バインダーおよびハロゲン化シクロアルカン化合物を含む処理液をパディング法で付与し、次いで熱処理することを特徴とするポリエステル系繊維材料の製造方法である。
【００１０】
【発明の実施の形態】
以下、本発明の内容について詳述する。
【００１１】
本発明のポリエステル系繊維材料は、ポリエチレンテレフタレート、ポリブチレンテレフタレートやこれらを主成分とした共重合体のポリエステル系繊維を含む繊維材料であり、ポリエステル系繊維以外の合成繊維や再生繊維あるいは天然繊維が混紡、混繊、交撚、交織、交編、混綿された混用素材であってもよい。繊維の形態としては、フィラメント、ステープルなどの繊維、あるいはフィラメント糸、紡績糸などの糸の形態、織物、編物、不織布などの布帛、あるいはこれらから得られる繊維製品などのいかなる形態であってもよい。
【００１２】
本発明に用いるポリアルキレングリコールは、分子中に−（Ｃ_n Ｈ_2nＯ）−（Ｎ＝２〜４）なる主鎖を有する分子量３００〜４０，０００のものが好ましく、１，０００〜１０，０００のものがより好ましく、例えばポリエチレングリコール、ポリプロピレングリコールまたはこれらのブロックポリマ等を使用する。分子量が小さすぎると耐久性が不十分となり、逆に大きすぎると分散性が低下して好ましくない。
【００１３】
芳香族ジカルボン酸は、例えばテレフタル酸またはテレフタル酸の低級アルキルエステルおよび／またはイソフタル酸またはイソフタル酸の低級アルキルエステルである。
【００１４】
アルキレングリコールは、一般式
ＨＯ−Ｃ_n Ｈ_2n−ＯＨ （ｎ＝２〜４）
で表されるものであり、例えばエチレングリコール、プロピレングリコール、ブチレングリコールなどが挙げられる。
【００１５】
ポリアルキレングリコール、芳香族ジカルボン酸およびアルキレングリコールのブロック共重合体においての各々のブロック共重合モル比は、１〜３１：１：２〜３のものが防汚性の面からみて好ましい。該ブロック共重合体は、ノニオン系またはアニオン系の界面活性剤を用いて水に分散させて用いるとよい。
【００１６】
上記のブロック共重合体は、ポリエステル系繊維材料重量に対し、固形分で０．０１〜３重量％付着させることが好ましく、０．０５〜０．５重量％付着させることがより好ましい。上記のブロック共重合体を付与することにより、水洗い洗濯中に用水中のＣａイオンやＭｇイオンと結び付いた金属石鹸などがポリエステル系繊維に付着するのを防止することが可能となる。ブロック共重合体の付与量が少なすぎると、防汚性が十分に発現されず、洗濯後の金属石鹸残留量が大きくなるため、難燃性の低下が大きくなってしまう。また、多すぎると生地の風合いが硬くなり、染色堅牢度も低下するため実用上好ましくない。
【００１７】
本発明に用いる無機系化合物からなる消臭剤としては、二酸化ケイ素、二酸化チタン、酸化亜鉛、酸化アルミニウムなどからなる多孔質物質や、ゼオライト、シリカゲル、活性炭などの多孔質物質、あるいは銅、亜鉛、銀、鉛、鉄、アルミニウム、カルシウム、マグネシウム、マンガン、ニッケル、コバルトなどの金属酸化物、水酸化物、塩化物、硫酸塩、硝酸塩などの無機酸の金属塩、酢酸塩、クエン酸塩などの有機酸の金属塩などが挙げられる。
【００１８】
水に難溶性の場合、無機系化合物の平均粒径は１００μｍ以下が好ましく、特に１０μｍ以下がよい。平均粒径が大きくなりすぎると、繊維材料表面のザラツキ感が大きくなり、風合いも粗硬になる。
【００１９】
多孔質物質としては、二酸化ケイ素と酸化亜鉛からなる非晶性物質が経済性と消臭性の面から好ましい。比表面積は、１０ｍ² ／ｇ以上が好ましく、５０ｍ² ／ｇ以上がより好ましい。また、硫化水素やメルカプタン類の臭気に対する消臭効果を大きくするために、銅、亜鉛の少なくともいずれかの化合物を含むことが好ましい。このような化合物としては、銅あるいは亜鉛の酸化物、水酸化物、塩化物、硫酸塩、硝酸塩などの無機酸塩、酢酸塩、クエン酸塩などの有機酸塩などが挙げられる。
【００２０】
無機系化合物の付着量は、繊維材料に対して０．０５〜１０％ｏｗｆであることが好ましく、０．１〜５％ｏｗｆであることがより好ましい。付着量が少なすぎると、十分な消臭効果が得られにくくなり、多すぎると、得られる繊維材料の風合いが粗硬でざらつき感も大きくなり、染色物では色相のダル化も大きくなってしまう。
【００２１】
本発明で用いるポリビニルアミン化合物は、下記一般式［１］で表される。
【００２２】
【化３】

ポリビニルアミン化合物は、アルデヒド類の消臭に効果があり、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミドなどを水溶液中で重合させ、酸または塩基により加水分解させることにより得ることができる。重合時にその他のビニルモノマー、例えばアクリル酸、アクリルアミド、アクリロニトリル、エチレン、スチレン、ビニルアセテートなどを共重合させてもよい。
【００２３】
上記のポリビニルアミン化合物の分子量は、１万〜２０万位の範囲が好ましい。分子量が小さいと水溶性が大きくなり、繊維材料に付着後の洗濯耐久性が不十分となる。また、分子量が大きすぎると粘度が高くなり、併用する無機系化合物との混合が困難になる。
【００２４】
ポリビニルアミン化合物の付着量は、繊維材料に対して０．０１〜１０％ｏｗｆが好ましく、０．０５〜５％ｏｗｆがより好ましい。付着量が少なすぎると、アルデヒド類に対して十分な消臭効果が得られにくくなり、多すぎると、得られる繊維材料の風合いが粗硬になり、難燃性も得られにくくなる。
【００２５】
本発明における合成樹脂バインダーは、無機系化合物とポリビニルアミン化合物を繊維材料に固着させるために用いられる。該合成樹脂バインダーとしては、ウレタン系樹脂、アクリル系樹脂、アミノプラスト樹脂、エポキシ系樹脂、グリオキザール系樹脂、エチレン尿素樹脂などが挙げられる。風合いおよび耐久性の面からは、ウレタン系樹脂やアクリル系樹脂が好ましく、特にウレタン系樹脂が良い。
【００２６】
ウレタン系樹脂としては、ポリウレタンエマルジョンあるいは水溶性ウレタン樹脂が用いられる。例えば、商品名として第一工業製薬（株）の“エラストロン”、“スーパーフレックス”、大日本インキ化学工業（株）の“ハイドラン”などが挙げられる。該樹脂バインダーの付着量は、ポリエステル系繊維材料に対して０．０１〜１０％ｏｗｆが好ましく、０．０２〜５％ｏｗｆがより好ましい。付着量が少なすぎると洗濯耐久性が不十分となり、多すぎると風合いが粗硬になり、難燃性も得られにくくなる。また、消臭性や難燃性を特に損なわない範囲内で、風合い加工剤、柔軟仕上剤、帯電防止剤、抗菌防臭加工剤、撥水剤などを処理液中に添加してもよい。
【００２７】
本発明におけるハロゲン化シクロアルカン化合物は、ポリエステル系繊維材料に難燃性を付与するために使用される。ハロゲン化シクロアルカン化合物は、環状飽和炭化水素化合物または少なくとも１個の環状飽和炭化水素基を有する飽和炭化水素化合物であって、水素原子の少なくとも１部分がハロゲンにより置換された化合物が適用できる。該化合物の具体例としては、例えば、１，２，３，４，５，６−ヘキサブロモシクロヘキサン、１，２，３，４−テトラブロモシクロオクタン（以下、ＴＢＣＯと略す）、１，２，５，６，９，１０−ヘキサブルモシクロドデカン（以下、ＨＢＣＤと略す）、１，２−ビス（３，４−ジブロモシクロヘキシル）１，２−ジブロモエタンまたはこれらの化合物の臭素が塩素で置換されたものなどを挙げることができる。特に、ハロゲンの大部分またはすべてを臭素としたものは、吸尽効率が高く、本発明には好適である。
【００２８】
ポリエステル系繊維に対するハロゲン化シクロアルカン化合物の含有量は、１．０〜２０％ｏｗｆ位がよい。含有量が少なすぎると、難燃性が不十分になる場合があり、多すぎると、吸尽効率が低下し、経済的ロスが大きくなるばかりか耐光堅牢度も低下することがある。
【００２９】
ポリエステル系繊維へのハロゲン化シクロアルカン化合物の付与方法は、浴中処理やパディング法などが適用可能であるが、吸尽効率の点から特に浴中処理が好ましい。浴中処理条件としては、通常１１０〜１５０℃位、好ましくは１２０〜１４０℃で１０〜６０分間でよい。この浴中処理を通常のポリエステル系繊維の染色と同時に実施するのは、好ましく行われる。すなわち、ポリエステル系繊維の浴中染色において、ハロゲン化シクロアルカン化合物を分散染料と併用することができる。ハロゲン化シクロアルカン化合物を浴中処理で付与した後、パディング法でも付与することは、優れた難燃性を得るために好ましい。なお、その他のハロゲン系難燃剤やリン系難燃剤をハロゲン化シクロアルカン化合物と併用することは、さらなる難燃性向上のため好ましく、何ら差支えない。
【００３０】
ポリアルキレングリコール、芳香族ジカルボン酸およびアルキレングリコールのブロック共重合体、無機系化合物、ポリビニルアミン化合物および合成樹脂バインダーを含む処理液の付与方法としては、パディング法、浸漬法、スプレー法、コーティング法、プリント法などが挙げられる。ポリアルキレングリコール、芳香族ジカルボン酸およびアルキレングリコールのブロック共重合体、無機系化合物、ポリビニルアミン化合物および合成樹脂バインダーをポリエステル系繊維繊維材料に耐久性良く、均一に付着させるためには、パディング法が特に好適である。
【００３１】
熱処理は、乾熱処理または湿熱処理が適用できる。湿熱処理は、浴中処理と蒸熱処理が挙げられる。蒸熱処理は、常圧飽和スチーム処理、過熱スチーム処理、高圧スチーム処理が挙げられる。乾熱処理または湿熱処理の温度は８０〜２１０℃位でよい。熱処理温度が低すぎると洗濯耐久性の面で十分でなく、高すぎると、繊維の黄化、脆化のおそれがあり好ましくない。実用上は、１１０〜１９０℃の乾熱処理が好適である。
【００３２】
以下、本発明を実施例によりさらに詳細に説明する。なお、実施例中の性能評価は、次の方法で行った。
【００３３】
〔水洗い洗濯方法〕
ＪＩＳ Ｌ １０４２ Ｆ法（ワッシャ法）で定められた洗濯装置に６０℃の温水６０リットルを入れた後、試験片８００ｇとＪＩＳ Ｋ ３３０３で規定された粉末洗濯石鹸（無添剤）６０ｇを投入し、１５分間運転した。次いで、４０℃の水で５分間のすすぎを３回繰り返し行なった後、試験片を取り出し、遠心脱水しタンブルドライヤーで乾燥させた。以上の操作を水洗い洗濯１回とする。
【００３４】
〔難燃性評価〕
ＪＩＳ Ｌ １０９１ Ｄ法（接炎試験）により測定した。
【００３５】
〔検知管法による消臭性評価〕
試料を３ｇ入れた５５０ｍｌの容器に初期濃度が２００ｐｐｍになるようにアンモニアガスを入れて密閉し、３０分間放置後、ガス検知管で残留アンモニア濃度を測定した。
【００３６】
同様な方法で硫化水素、アセトアルデヒド、酢酸の臭気に対しても初期濃度が各々２０ｐｐｍ、２００ｐｐｍ、２０ｐｐｍになるように設定し、残留ガス濃度を測定した。
【００３７】
〔たばこ臭に対する消臭性の嗅覚評価〕
５００ｍｌのガラス製三角フラスコを入り口を下にして、入り口の直下に発煙している紙巻きたばこを５秒間置いた後、すばやく三角フラスコを横にして試料３ｇを投入し、ガラス栓で密閉した。１時間放置後、ガラス栓を開け、残臭を嗅いで評価した。
【００３８】
〇：残臭がほとんどない △：やや残臭がある ×：残臭が大きい
実施例中の生地は、ポリエステル織物（東レ（株）製＃Ｆ１３０５ＧＮ、タテ糸、ヨコ糸共１５０Ｄ−４８ｆｉｌ）を用いた。この織物を通常の方法で糊抜き、精練し、乾熱セット後試験に供した。
【００３９】
（実施例１）
供試生地を分散染料Ｄｉａｎｉｘ Ｂｌａｃｋ ＢＧ−ＦＳ ２００％（ダイスタージャパン（株）製）３．０％ｏｗｆ、酢酸（８０％）０．５ｃｃ／ｌ、分散剤ＲＡＰ−５０（三洋化成工業（株）製）０．５ｇ／ｌ、ＨＢＣＤ乳化液（有効成分４０％）１５％ｏｗｆからなる浴で１３０℃×４５分間処理し、通常の方法で還元洗浄後、湯洗、乾燥した。得られた生地を下記組成の処理液に浸漬後、マングルで絞り（絞り率６５％）、１２０℃×３分で乾燥後、ピンテンターで１７０℃×１分乾熱処理を行い、評価に供した。
【００４０】

（実施例２）
処理液を下記組成とした以外は、実施例１と同じ処理を施して試料を作製し、評価に供した。
【００４１】

（実施例３）
処理液を下記組成とした以外は、実施例１と同じ処理を施して試料を作製し、評価に供した。
【００４２】

（実施例４）
処理液を下記組成とした以外は、実施例１と同じ処理を施して試料を作製し、評価に供した。
【００４３】

（実施例５）
供試生地を下記組成の処理液に浸漬後、マングルで絞り（絞り率６５％）、１２０℃×３分で乾燥後、ピンテンターで１７０℃×１分乾熱処理を行い、評価に供した。
【００４４】

（比較例１）
処理液を下記組成とした以外は、実施例１と同じ処理を施して試料を作製し、評価に供した。
【００４５】

（比較例２）
処理液を下記組成とした以外は、実施例１と同じ処理を施して試料を作製し、評価に供した。
【００４６】

（比較例３）
処理液を下記組成とした以外は、実施例１と同じ処理を施して試料を作製し、評価に供した。
【００４７】

（比較例４）
処理液を下記組成とした以外は、実施例１と同じ処理を施して試料を作製し、評価に供した。
【００４８】

（比較例５）
供試生地を下記組成の処理液に浸漬後、マングルで絞り（絞り率６５％）、１２０℃×３分で乾燥後、ピンテンターで１７０℃×１分乾熱処理を行い、評価に供した。
【００４９】

実施例１〜５、比較例１〜５で得られた生地について、消臭性および難燃性を測定した結果を表１、表２に示す。
【００５０】
【表１】

【表２】

【００５１】
【発明の効果】
本発明によれば、アンモニア、アミン類、硫化水素、メルカプタン類などの悪臭やタバコ臭に多く含まれるアルデヒド類、酢酸などに対し耐久性のある優れた消臭性を有し、洗濯後も難燃性の低下が小さく、しかも風合いの柔軟な消臭・難燃・防汚性を有するポリエステル系繊維材料を得ることができる。
【００５２】
従って、本発明の消臭・難燃・防汚性を有するポリエステル系繊維材料は、カーテン、カーペット、マット、毛布、シーツ、ふとんカバー、まくらカバー、ふとん綿、自動車の内装材などの建寝装材料やスーツ、ユニフォーム、シャツ、ブラウス、スラックス、スカート、セーター、靴下、パンティストッキング、芯地、裏地などの衣料材料、靴の中敷、内張り地、かばん地、風呂敷、クッション、ぬいぐるみなどの材料、布おむつ、おむつカバーなどの衛生材料、家具、冷蔵庫などの消臭材、フィルター類、不織布など広範な用途に適用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester fiber material having deodorant / flame retardant / antifouling properties and a method for producing the same. More specifically, it has excellent deodorizing properties that are durable against odors such as ammonia, amines, hydrogen sulfide, mercaptans, and aldehydes, acetic acid, pyridine, etc., which are abundant in tobacco odors, and has flame retardancy. Related to polyester fiber materials having a small reduction in flame retardancy even after washing to prevent adhesion of hindered metal soaps and oily substances and having a soft texture, deodorizing, flame retardant, and antifouling properties and a method for producing the same It is.
[0002]
[Prior art]
In recent years, there has been an increasing demand for textile products having an advanced deodorizing function. Conventionally, as a method of imparting deodorant properties to fibers, a method of kneading a deodorant into a fiber polymer at the raw yarn stage, or fixing a deodorant to the fiber surface with a binder at a post-processing stage has been performed. ing. For example, a polyester fiber (Japanese Patent Publication No. 7-81206) blended with titanium dioxide fine particles carrying phthalocyanine polyvalent carboxylic acid or a deodorant fiber (specialty) coated with a deodorizing catalyst that oxidatively decomposes odor components. Kaihei 7-189120) and the like have been proposed.
[0003]
However, the method of kneading the deodorant into the fiber has restrictions on the particle size, heat resistance, affinity with the fiber polymer, etc. in selecting the deodorant, and may impair the physical strength of the raw yarn. On the other hand, when applying a deodorant by a post-processing method, for applications that require flame retardancy, since the organic deodorant or synthetic resin binder inhibits the flame retardancy, imparting flame retardancy There was a difficult problem. In addition, after washing with water, metal soap associated with Ca ions and Mg ions in the washing water remains in the fiber product, which further reduces the flame retardancy.
[0004]
[Problems to be solved by the invention]
The object of the present invention is to have excellent deodorizing properties that are durable against odors such as ammonia, amines, hydrogen sulfide, mercaptans, aldehydes and acetic acid that are often contained in tobacco odors, and even after washing. It is an object of the present invention to provide a polyester fiber material having a small flame retardancy and having a soft texture and having a deodorant / flame retardant / antifouling property and a method for producing the same.
[0005]
[Means for Solving the Problems]
The polyester fiber material having deodorant / flame retardant / antifouling properties of the present invention has the following configuration in order to achieve the above-mentioned problems.
[0006]
That is, polyalkylene glycol, a block copolymer of an aromatic dicarboxylic acid and an alkylene glycol, a porous material, a metal oxide, a metal salt of an inorganic acid, and at least one inorganic compound selected from metal salts of organic acids comprising deodorant, deodorant comprising a polyvinyl amine compound represented by the following general formula [1], and the synthetic resin binder are attached, and polyester fiber characterized in that it contains a halogenated cycloalkane compound Material.
[0007]
[Chemical formula 2]

Moreover, the manufacturing method of the polyester fiber material of this invention has the following structure.
[0008]
After treatment in a bath with a processing solution containing a halogenated cycloalkane compound, polyalkylene glycols, and block copolymers of an aromatic dicarboxylic acid and an alkylene glycol, a porous material, a metal oxide, a metal salt of an inorganic acid and, A treatment liquid containing a deodorant comprising at least one inorganic compound selected from metal salts of organic acids, a deodorant comprising a polyvinylamine compound represented by the general formula [1], and a synthetic resin binder by a padding method. It is the manufacturing method of the polyester-type fiber material characterized by giving and then heat-processing.
[0009]
Alternatively, polyalkylene glycols, and block copolymers of an aromatic dicarboxylic acid and an alkylene glycol, a porous material, a metal oxide, a metal salt of an inorganic acid, and at least one inorganic compound selected from metal salts of organic acids deodorant consisting wherein the general formula [1] deodorant comprising a polyvinyl amine compound indicated, the treatment liquid was applied in a padding method comprising a synthetic resin binder and a halogenated cycloalkane compound and then heat-treated It is the manufacturing method of the polyester-type fiber material made into.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the contents of the present invention will be described in detail.
[0011]
The polyester fiber material of the present invention is a fiber material containing polyethylene terephthalate, polybutylene terephthalate or a polyester fiber of a copolymer based on these, and synthetic fibers, recycled fibers or natural fibers other than polyester fibers are used. It may be a blended material that is blended, blended, twisted, woven, knitted, or blended. The form of the fiber may be any form such as a fiber such as a filament or a staple, a thread such as a filament yarn or a spun yarn, a fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric, or a fiber product obtained therefrom. .
[0012]
Polyalkylene glycols used in the present invention, in the molecule _{- (C n H 2n O)} - preferably has a molecular weight 300～40,000 having (N = 2 to 4) comprising a main chain, 1,000～10, More preferably, for example, polyethylene glycol, polypropylene glycol, or a block polymer thereof is used. If the molecular weight is too small, the durability becomes insufficient, while if too large, the dispersibility decreases, which is not preferable.
[0013]
Aromatic dicarboxylic acids are, for example, terephthalic acid or lower alkyl esters of terephthalic acid and / or isophthalic acid or lower alkyl esters of isophthalic acid.
[0014]
Alkylene glycol has the general formula HO—C _n H _2n —OH (n = 2 to 4).
For example, ethylene glycol, propylene glycol, butylene glycol and the like can be mentioned.
[0015]
The block copolymer molar ratio in the block copolymer of polyalkylene glycol, aromatic dicarboxylic acid and alkylene glycol is preferably from 1 to 3: 1: 2 to 3 in view of the antifouling property. The block copolymer may be used by dispersing in water using a nonionic or anionic surfactant.
[0016]
The block copolymer is preferably attached in an amount of 0.01 to 3% by weight, more preferably 0.05 to 0.5% by weight, based on the weight of the polyester fiber material. By providing the above block copolymer, it becomes possible to prevent metal soap or the like associated with Ca ions or Mg ions in the irrigation water from adhering to the polyester fiber during washing with water. When the application amount of the block copolymer is too small, the antifouling property is not sufficiently exhibited, and the residual amount of metal soap after washing increases, resulting in a large reduction in flame retardancy. On the other hand, if the amount is too large, the texture of the dough becomes hard and the fastness to dyeing is lowered.
[0017]
As the deodorant composed of an inorganic compound used in the present invention, a porous material composed of silicon dioxide, titanium dioxide, zinc oxide, aluminum oxide, a porous material such as zeolite, silica gel, activated carbon, or copper, zinc, Metal oxides such as silver, lead, iron, aluminum, calcium, magnesium, manganese, nickel and cobalt , metal salts of inorganic acids such as hydroxide, chloride, sulfate, nitrate, acetate, citrate, etc. Examples include metal salts of organic acids.
[0018]
In the case of poor solubility in water, the average particle size of the inorganic compound is preferably 100 μm or less, and particularly preferably 10 μm or less. When the average particle size becomes too large, the feeling of roughness on the surface of the fiber material becomes large, and the texture becomes coarse.
[0019]
As the porous material, an amorphous material composed of silicon dioxide and zinc oxide is preferable from the viewpoints of economy and deodorization. The specific surface area is preferably 10 m ² / g or more, and more preferably 50 m ² / g or more. Moreover, in order to enlarge the deodorizing effect with respect to the odor of hydrogen sulfide or mercaptans, it is preferable to contain at least one compound of copper and zinc. Examples of such compounds include inorganic acid salts such as copper or zinc oxides, hydroxides, chlorides, sulfates and nitrates, and organic acid salts such as acetates and citrates.
[0020]
The adhesion amount of the inorganic compound is preferably 0.05 to 10% owf, and more preferably 0.1 to 5% owf with respect to the fiber material. If the amount of adhesion is too small, it will be difficult to obtain a sufficient deodorizing effect. If the amount is too large, the texture of the resulting fiber material will be rough and rough, and the color will become dull in the dyed product. .
[0021]
The polyvinylamine compound used in the present invention is represented by the following general formula [1].
[0022]
[Chemical 3]

The polyvinylamine compound is effective in deodorizing aldehydes, and can be obtained by polymerizing N-vinylformamide, N-vinylacetamide or the like in an aqueous solution and hydrolyzing with an acid or a base. Other vinyl monomers such as acrylic acid, acrylamide, acrylonitrile, ethylene, styrene, vinyl acetate may be copolymerized at the time of polymerization.
[0023]
The molecular weight of the polyvinylamine compound is preferably in the range of about 10,000 to 200,000. If the molecular weight is small, the water solubility becomes large and the washing durability after adhering to the fiber material becomes insufficient. On the other hand, if the molecular weight is too large, the viscosity becomes high and mixing with the inorganic compound used in combination becomes difficult.
[0024]
The adhesion amount of the polyvinylamine compound is preferably 0.01 to 10% owf, more preferably 0.05 to 5% owf with respect to the fiber material. If the adhesion amount is too small, it is difficult to obtain a sufficient deodorizing effect on aldehydes, and if it is too much, the texture of the resulting fiber material becomes coarse and flame retardancy is difficult to obtain.
[0025]
The synthetic resin binder in the present invention is used for fixing an inorganic compound and a polyvinylamine compound to a fiber material. Examples of the synthetic resin binder include urethane resin, acrylic resin, aminoplast resin, epoxy resin, glyoxal resin, and ethylene urea resin. From the viewpoints of texture and durability, urethane resins and acrylic resins are preferable, and urethane resins are particularly preferable.
[0026]
A polyurethane emulsion or a water-soluble urethane resin is used as the urethane resin. For example, “Elastron”, “Superflex” from Daiichi Kogyo Seiyaku Co., Ltd., “Hydran” from Dainippon Ink & Chemicals, Inc. are listed as trade names. The adhesion amount of the resin binder is preferably 0.01 to 10% owf, more preferably 0.02 to 5% owf with respect to the polyester fiber material. If the adhesion amount is too small, the washing durability becomes insufficient, and if it is too much, the texture becomes coarse and flame retardancy is hardly obtained. In addition, a texture processing agent, a softening finish, an antistatic agent, an antibacterial deodorizing agent, a water repellent, and the like may be added to the treatment liquid as long as the deodorizing property and flame retardancy are not particularly impaired.
[0027]
The halogenated cycloalkane compound in the present invention is used for imparting flame retardancy to a polyester fiber material. As the halogenated cycloalkane compound, a cyclic saturated hydrocarbon compound or a saturated hydrocarbon compound having at least one cyclic saturated hydrocarbon group, in which at least a part of hydrogen atoms is substituted with a halogen, can be applied. Specific examples of the compound include 1,2,3,4,5,6-hexabromocyclohexane, 1,2,3,4-tetrabromocyclooctane (hereinafter abbreviated as TBCO), 1,2, 5,6,9,10-hexabromomocyclododecane (hereinafter abbreviated as HBCD), 1,2-bis (3,4-dibromocyclohexyl) 1,2-dibromoethane or bromine in these compounds is replaced by chlorine Can be mentioned. In particular, those in which most or all of the halogen is bromine have high exhaustion efficiency and are suitable for the present invention.
[0028]
The content of the halogenated cycloalkane compound with respect to the polyester fiber is preferably about 1.0 to 20% owf. If the content is too small, the flame retardancy may be insufficient. If the content is too large, the exhaust efficiency may be reduced, the economic loss may increase, and the light fastness may also decrease.
[0029]
As a method for applying the halogenated cycloalkane compound to the polyester fiber, a treatment in a bath or a padding method can be applied, but treatment in a bath is particularly preferable from the viewpoint of exhaustion efficiency. The treatment conditions in the bath are usually about 110 to 150 ° C, preferably 120 to 140 ° C for 10 to 60 minutes. It is preferable to perform the treatment in the bath simultaneously with the dyeing of the normal polyester fiber. That is, a halogenated cycloalkane compound can be used in combination with a disperse dye in dyeing polyester fibers in a bath. In order to obtain excellent flame retardancy, it is preferable to apply the halogenated cycloalkane compound by treatment in a bath and then by padding. In addition, it is preferable to use other halogen-based flame retardants or phosphorus-based flame retardants in combination with halogenated cycloalkane compounds for further improving flame retardancy, and there is no problem.
[0030]
As a method for applying a treatment liquid containing a block copolymer of polyalkylene glycol, aromatic dicarboxylic acid and alkylene glycol, inorganic compound, polyvinylamine compound and synthetic resin binder, padding method, dipping method, spray method, coating method, The printing method etc. are mentioned. In order to adhere the block copolymer of polyalkylene glycol, aromatic dicarboxylic acid and alkylene glycol, inorganic compound, polyvinylamine compound and synthetic resin binder to the polyester fiber fiber material in a durable and uniform manner, a padding method is used. Particularly preferred.
[0031]
As the heat treatment, dry heat treatment or wet heat treatment can be applied. Examples of the wet heat treatment include in-bath treatment and steam heat treatment. Examples of steam heat treatment include normal pressure saturated steam treatment, superheated steam treatment, and high-pressure steam treatment. The temperature of the dry heat treatment or the wet heat treatment may be about 80 to 210 ° C. If the heat treatment temperature is too low, it is not sufficient in terms of washing durability, and if it is too high, there is a risk of yellowing and embrittlement of the fibers, which is not preferable. Practically, a dry heat treatment at 110 to 190 ° C. is preferable.
[0032]
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the performance evaluation in an Example was performed with the following method.
[0033]
[Washing washing method]
After putting 60 liters of hot water at 60 ° C into a washing machine specified by JIS L 1042 F method (washer method), put 800 g of test piece and 60 g of powder laundry soap (additive-free) specified by JIS K 3303. Drove for 15 minutes. Subsequently, after rinsing with water at 40 ° C. for 5 minutes three times, the test piece was taken out, centrifuged and dehydrated, and dried with a tumble dryer. The above operation is one wash and wash.
[0034]
[Flame Retardancy Evaluation]
Measured by JIS L 1091 D method (flame contact test).
[0035]
[Deodorization evaluation by detector tube method]
Ammonia gas was put in a 550 ml container containing 3 g of the sample so that the initial concentration was 200 ppm and sealed, and after standing for 30 minutes, the residual ammonia concentration was measured with a gas detector tube.
[0036]
In the same manner, the initial gas concentrations were set to 20 ppm, 200 ppm, and 20 ppm with respect to the odors of hydrogen sulfide, acetaldehyde, and acetic acid, respectively, and the residual gas concentrations were measured.
[0037]
[Odor sense evaluation of deodorant for tobacco odor]
A 500 ml glass Erlenmeyer flask was placed with the inlet facing down, and a cigarette that smoked immediately under the inlet was placed for 5 seconds. Then, the Erlenmeyer flask was placed sideways quickly, and 3 g of the sample was quickly put in, and sealed with a glass stopper. After leaving for 1 hour, the glass stopper was opened and the residual odor was smelled and evaluated.
[0038]
◯: Almost no residual odor Δ: Some residual odor ×: Large residual odor Polyester fabric (# F1305GN manufactured by Toray Industries, Inc., warp yarn, horizontal yarn 150D-48fil) is used as the fabric in the examples. It was. This woven fabric was desizing and scoured by a usual method, and subjected to a test after setting with dry heat.
[0039]
(Example 1)
Disperse dye Dianix Black BG-FS 200% (Dystar Japan Co., Ltd.) 3.0% owf, acetic acid (80%) 0.5 cc / l, dispersant RAP-50 (Sanyo Chemical Industries Co., Ltd.) )) 0.5 g / l, HBCD emulsion (active ingredient 40%) treated with 15% owf at 130 ° C. for 45 minutes, reduced and washed in the usual manner, then washed with hot water and dried. The obtained dough was immersed in a treatment solution having the following composition, then drawn with a mangle (drawing ratio 65%), dried at 120 ° C. for 3 minutes, and then subjected to a dry heat treatment at 170 ° C. for 1 minute with a pin tenter for evaluation.
[0040]

(Example 2)
A sample was prepared by performing the same treatment as in Example 1 except that the treatment liquid had the following composition, and was used for evaluation.
[0041]

(Example 3)
A sample was prepared by performing the same treatment as in Example 1 except that the treatment liquid had the following composition, and was used for evaluation.
[0042]

(Example 4)
A sample was prepared by performing the same treatment as in Example 1 except that the treatment liquid had the following composition, and was used for evaluation.
[0043]

(Example 5)
The test dough was immersed in a treatment solution having the following composition, then drawn with a mangle (drawing ratio 65%), dried at 120 ° C. for 3 minutes, and then subjected to a dry heat treatment at 170 ° C. for 1 minute with a pin tenter for evaluation.
[0044]

(Comparative Example 1)
A sample was prepared by performing the same treatment as in Example 1 except that the treatment liquid had the following composition, and was used for evaluation.
[0045]

(Comparative Example 2)
A sample was prepared by performing the same treatment as in Example 1 except that the treatment liquid had the following composition, and was used for evaluation.
[0046]

(Comparative Example 3)
A sample was prepared by performing the same treatment as in Example 1 except that the treatment liquid had the following composition, and was used for evaluation.
[0047]

(Comparative Example 4)
A sample was prepared by performing the same treatment as in Example 1 except that the treatment liquid had the following composition, and was used for evaluation.
[0048]

(Comparative Example 5)
The test dough was immersed in a treatment solution having the following composition, then drawn with a mangle (drawing ratio 65%), dried at 120 ° C. for 3 minutes, and then subjected to a dry heat treatment at 170 ° C. for 1 minute with a pin tenter for evaluation.
[0049]

Tables 1 and 2 show the results of measuring the deodorizing property and flame retardancy of the fabrics obtained in Examples 1 to 5 and Comparative Examples 1 to 5.
[0050]
[Table 1]

[Table 2]

[0051]
【The invention's effect】
According to the present invention, it has excellent deodorizing properties that are durable against odors such as ammonia, amines, hydrogen sulfide, mercaptans, etc., aldehydes and acetic acid that are often contained in tobacco odors, and is difficult even after washing. It is possible to obtain a polyester-based fiber material having a small decrease in flammability and having a soft texture and having deodorant / flame retardant / antifouling properties.
[0052]
Therefore, the polyester fiber material having deodorant / flame retardant / antifouling property of the present invention is used for bedding such as curtains, carpets, mats, blankets, sheets, futon covers, pillow covers, futons, and automobile interior materials. Materials and suits, uniforms, shirts, blouses, slacks, skirts, sweaters, socks, pantyhose, interlining, lining and other clothing materials, insoles, linings, bags, furoshiki, cushions, stuffed animals, etc. It can be applied to a wide range of applications such as cloth diapers, sanitary materials such as diaper covers, furniture, deodorants such as refrigerators, filters, and non-woven fabrics.

Claims (8)

Polyalkylene glycols, and block copolymers of an aromatic dicarboxylic acid and an alkylene glycol, a porous material, a metal oxide, a metal salt of an inorganic acid, and of at least one inorganic compound selected from metal salts of organic acids vanishing Nioizai, polyester fiber materials, characterized deodorant comprising a polyvinyl amine compound, and a synthetic resin binder are attached, and in that it contains a halogenated cycloalkane compound represented by the following general formula [1].

2. The polyester fiber material according to claim 1, wherein the deodorant comprising the inorganic compound contains at least one selected from a porous material, copper, and zinc. The polyester fiber material according to claim 2, wherein the porous substance contains silicon dioxide and zinc oxide. The polyester fiber material according to claim 1, wherein the synthetic resin binder is a urethane resin. The polyester fiber material according to any one of claims 1 to 4, wherein the polyester fiber material is fiber, yarn, woven fabric, knitted fabric, non-woven fabric, or a fiber product obtained therefrom . After treatment in a bath with a processing solution containing a halogenated cycloalkane compound, polyalkylene glycols, and block copolymers of an aromatic dicarboxylic acid and an alkylene glycol, a porous material, a metal oxide, a metal salt of an inorganic acid and, A treatment liquid containing a deodorant comprising at least one inorganic compound selected from metal salts of organic acids, a deodorant comprising a polyvinylamine compound represented by the general formula [1], and a synthetic resin binder by a padding method. A method for producing a polyester fiber material, characterized by applying and then heat-treating. After treatment in a bath with a processing solution containing a halogenated cycloalkane compound, polyalkylene glycols, and block copolymers of an aromatic dicarboxylic acid and an alkylene glycol, a porous material, a metal oxide, a metal salt of an inorganic acid and, comprising at least one inorganic consisting of compounds deodorizing agent selected from metal salts of organic acids, deodorant comprising a polyvinyl amine compound represented by the general formula [1], synthetic resin binder, and a halogenated cycloalkane compound A method for producing a polyester fiber material, characterized in that a treatment liquid is applied by a padding method and then heat-treated. Polyalkylene glycols, and block copolymers of an aromatic dicarboxylic acid and an alkylene glycol, a porous material, a metal oxide, a metal salt of an inorganic acid, and of at least one inorganic compound selected from metal salts of organic acids vanishing Nioizai the general formula [1] deodorant comprising a polyvinyl amine compound indicated, the synthetic resin binder, and the treatment liquid was applied in a padding method comprising halogenated cycloalkane compound, then characterized by heat treatment A method for producing a polyester fiber material.