JP3462912B2 - Method for removing residual formalin from fabric - Google Patents
Method for removing residual formalin from fabricInfo
- Publication number
- JP3462912B2 JP3462912B2 JP25514794A JP25514794A JP3462912B2 JP 3462912 B2 JP3462912 B2 JP 3462912B2 JP 25514794 A JP25514794 A JP 25514794A JP 25514794 A JP25514794 A JP 25514794A JP 3462912 B2 JP3462912 B2 JP 3462912B2
- Authority
- JP
- Japan
- Prior art keywords
- formaldehyde
- cloth
- cellulosic fiber
- gas
- fabric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Treatment Of Fiber Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は，ホルムアルデヒドガス
を用いて行うセルロース系繊維布帛の気相加工時に，布
帛に残留するホルマリンを除去する方法に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing formalin remaining on a cloth when the cellulose fiber cloth is vapor-phase processed using formaldehyde gas.
【０００２】[0002]
【従来の技術】セルロース系繊維布帛よりなる縫製品に
ホルムアルデヒドガスを用いて気相加工を施し，ホルム
アルデヒドを繊維のセルロース分子間に架橋することに
より，セルロース系繊維縫製品にイージーケアー性 (
ウォッシュ・アンド・ウェアー性）等の性能を付与する
ことは従来から公知であり，広く一般に行われている。
しかしながら，この方法によって得られる加工布帛の欠
点は，生地表面に未反応で残存しているホルムアルデヒ
ドにあり，加工直後には１０００〜２０００ppmも存在
している。2. Description of the Related Art A sewn product made of a cellulosic fiber cloth is subjected to a gas phase process using formaldehyde gas, and by cross-linking formaldehyde between cellulose molecules of the fiber, an easy care property (
It has been publicly known to give performances such as wash and wear property), and it is widely performed.
However, the disadvantage of the processed cloth obtained by this method is in the unreacted formaldehyde remaining on the surface of the cloth, and 1000 to 2000 ppm is present immediately after processing.
【０００３】この残留ホルマリンを除去するために一般
的に行われている方法として，４分間程度のスチーム処
理を施したり，アンモニアガス処理を施したりする方法
があるが，これらの方法ではホルマリンを３００〜５０
０ppm までしか低減できず，外衣以外の中衣，肌着には
適用できなかった。As a method generally used for removing this residual formalin, there is a method in which steam treatment for about 4 minutes or ammonia gas treatment is carried out. ~ 50
It could only be reduced to 0ppm and could not be applied to inner and outer garments other than outer garments.
【０００４】残留ホルマリンを低減させる他の方法とし
て，気相加工後の製品を水で洗浄する方法があり，これ
によってホルマリンを０〜２０ppm まで低減することが
できるが，この方法では，洗浄装置や乾燥装置を必要と
し，洗浄工程，乾燥工程等の加工工程が増えてしまい，
資金的，時間的な加工コストの負担が大きくなってしま
う。As another method for reducing the residual formalin, there is a method of washing the product after the gas phase processing with water, which can reduce the formalin to 0 to 20 ppm. A drying device is required, and the number of processing steps such as cleaning and drying steps increases,
The financial and time-consuming processing costs will increase.
【０００５】[0005]
【発明が解決しようとする課題】本発明は，このような
現状に鑑みて行われたもので，セルロース系繊維布帛の
ホルムアルデヒドガスによる気相加工に際して，生地に
残存する未反応のホルムアルデヒドを洗浄装置等を用い
ることなく除去する方法を得ることを目的とするもので
ある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is an apparatus for cleaning unreacted formaldehyde remaining in a cloth when vapor-processing a cellulosic fiber cloth with formaldehyde gas. The object is to obtain a method for removing the above without using the above.
【０００６】[0006]
【課題を解決するための手段】本発明は，上述の目的を
達成するもので，次の構成よりなるものである。すなわ
ち，本発明は，「セルロース系繊維布帛にホルムアルデ
ヒドガスを吸着させ，熱処理してセルロース分子間に架
橋せしめるホルムアルデヒドによる気相加工において，
該熱処理後にアミン系化合物の雰囲気中で布帛を処理す
ることを特徴とするセルロース系繊維布帛の残留ホルマ
リン除去方法」並びに「セルロース系繊維布帛にホルム
アルデヒドガスを吸着させ，熱処理してセルロース分子
間に架橋せしめるホルムアルデヒドによる気相加工にお
いて，該熱処理後にアミン系化合物の雰囲気中で布帛を
処理し，しかる後にスチーム処理することを特徴とする
セルロース系繊維布帛の残留ホルマリン除去方法」を要
旨とするものである。以下，本発明を詳細に説明する。The present invention achieves the above-mentioned object and has the following configuration. That is, the present invention relates to "in vapor-phase processing with formaldehyde, in which formaldehyde gas is adsorbed on a cellulosic fiber cloth and heat-treated to crosslink between cellulose molecules,
A method for removing residual formalin from a cellulosic fiber cloth, characterized in that the cloth is treated in an atmosphere of an amine compound after the heat treatment "and" formaldehyde gas is adsorbed to the cellulosic fiber cloth and heat treated to crosslink between cellulose molecules In the vapor-phase processing with squeezing formaldehyde, a method for removing residual formalin from a cellulosic fiber cloth is characterized in that the cloth is treated in an atmosphere of an amine compound after the heat treatment, and then steamed. . Hereinafter, the present invention will be described in detail.
【０００７】本発明でいうセルロース系繊維布帛とは，
木綿，麻等の天然繊維，レーヨン，ポリノジック等の再
生セルロース繊維を含有する織物，編物，不織布等をい
い，その他の繊維としてポリエステル，ナイロン等の合
成繊維が混紡，混繊，交織等の形で混用されていてもよ
い。もちろん，セルロース系繊維１００％よりなる布帛
であってもよい。The term "cellulosic fiber cloth" as used in the present invention means
Woven fabric, knitted fabric, non-woven fabric, etc. containing natural fibers such as cotton and hemp, regenerated cellulose fibers such as rayon and polynosic, and synthetic fibers such as polyester and nylon as other fibers. It may be mixed. Of course, a cloth made of 100% cellulosic fibers may be used.
【０００８】本発明では上述のセルロース系繊維布帛に
ホルムアルデヒドガスを吸着させ，熱処理してセルロー
ス分子間に架橋せしめるホルムアルデヒドによる気相加
工が行われる。この気相加工の際のセルロース系繊維布
帛の形態は，シート状の形態であっても，縫製品の形態
であっても，一向に差し支えない。In the present invention, vapor-phase processing is performed with formaldehyde, which adsorbs formaldehyde gas on the above-mentioned cellulosic fiber cloth and heat-treats it to crosslink between cellulose molecules. The form of the cellulosic fiber cloth at the time of the vapor phase processing may be a sheet form or a sewn product form.
【０００９】本発明では，ホルムアルデヒドガスによる
気相加工を施す前に，予め布帛の水分率を均一に調節す
る。このとき，生地の水分率は１〜５０％で，かつ水分
が生地に均一に分布しているように調節する。生地の水
分率が１％以下であると，ホルムアルデヒドガスが生地
に十分吸着しなくなり，逆に５０％以上になると，酸触
媒によって生地が脆化してしまうおそれが出てくるの
で，注意を要する。また，生地に水分が均一に分布して
いないと，ホルムアルデヒドガスが均一に吸着しなくな
るので，この点にも注意を要する。水分率を均一に調節
するためには，いかなる手段を用いてもよいが，通常
は，恒温恒湿室に布帛や縫製品を２４時間以上放置する
方法を用いるとよい。According to the present invention, the moisture content of the cloth is adjusted to be uniform before the vapor-phase processing with formaldehyde gas. At this time, the water content of the dough is adjusted to 1 to 50% and the water content is uniformly distributed in the dough. When the moisture content of the dough is 1% or less, formaldehyde gas is not sufficiently adsorbed on the dough, and when it is 50% or more, the acid catalyst may cause embrittlement of the dough. In addition, if moisture is not evenly distributed in the dough, formaldehyde gas will not be adsorbed uniformly. Any means may be used to adjust the moisture content uniformly, but it is usually preferable to use a method of leaving the cloth or sewn product in a constant temperature and constant humidity chamber for 24 hours or more.
【００１０】水分率を調節した後，本発明では，布帛に
ホルムアルデヒドによる気相加工を行う。気相加工に際
しては，常圧密閉型の反応室と，ホルムアルデヒドガス
の供給手段，加熱装置を有する気相加工装置を用いるこ
とができる。気相加工装置として，ＡＴＰ社（American
Textile Processing Co.)製の気相加工装置（特開昭５
−１１７９５８号）を用いてもよい。この気相加工装置
内でのホルムアルデヒドガス濃度は，１〜２０％の範囲
が望ましく，１％以下であると，架橋反応が不十分とな
り，２０％以上となっても，効果はそれ以上あがらなく
なる。After adjusting the moisture content, in the present invention, the fabric is subjected to vapor processing with formaldehyde. In the gas phase processing, a gas phase processing apparatus having an atmospheric pressure closed reaction chamber, a formaldehyde gas supply means, and a heating device can be used. ATP (American
Textile Processing Co.) vapor-phase processing equipment
-117958) may be used. The formaldehyde gas concentration in the vapor phase processing apparatus is preferably in the range of 1 to 20%, and if it is 1% or less, the crosslinking reaction becomes insufficient, and even if it is 20% or more, the effect is no longer exhibited. .
【００１１】架橋反応をさせる際に用いる触媒は，予め
布帛に触媒溶液をパディングした後に気相処理を行って
もよいし，触媒溶液もしくは液化している触媒を気化ま
たはミストして布帛に吸着させてもよい。The catalyst used for the cross-linking reaction may be subjected to a gas phase treatment after padding the fabric with the catalyst solution in advance, or the catalyst solution or the liquefied catalyst may be vaporized or mist to be adsorbed on the fabric. May be.
【００１２】触媒の種類に関しては，予めパディングす
る場合は，従来の樹脂加工と同じ触媒，例えば，硝酸亜
鉛のような酸の金属塩，ルイス酸，ブレンステッド酸が
用いられる。また，気化させる場合は，塩化水素のよう
な揮発性で沸点の低い酸が望ましい。Regarding the type of catalyst, when padding is performed in advance, the same catalyst as used in conventional resin processing, for example, a metal salt of an acid such as zinc nitrate, a Lewis acid or a Bronsted acid is used. When vaporizing, a volatile acid with a low boiling point, such as hydrogen chloride, is desirable.
【００１３】触媒濃度に関しては，ガスで処理する場合
には，0.１〜3.０％の範囲が望ましい。ガス濃度が0.１
％以下であると，架橋反応が不十分となり，3.０％以上
になると，それ以上の効果があがらなくなり，しかも過
度の生地強度の低下も発生するので，注意を要する。触
媒を水溶液でパディングして付着させる場合の触媒濃度
は，５〜１００ｇ／リットルの範囲が望ましい。濃度が
５ｇ／リットル以下になると，架橋反応が不十分とな
り，１００ｇ／リットル以上になっても，それ以上の効
果があがらなくなり，しかも過度の生地強度の低下も発
生するので，注意を要する。The catalyst concentration is preferably in the range of 0.1 to 3.0% when treated with gas. Gas concentration is 0.1
If the content is less than 0.1%, the crosslinking reaction will be insufficient, and if it is more than 3.0%, the effect will not be further improved, and excessive lowering of the fabric strength will occur. When the catalyst is padded with an aqueous solution and attached, the catalyst concentration is preferably in the range of 5 to 100 g / liter. When the concentration is 5 g / liter or less, the crosslinking reaction becomes insufficient, and even when it is 100 g / liter or more, the effect is not improved further, and the fabric strength is excessively lowered, so caution is required.
【００１４】ホルムアルデヒドガスを吸着させた後，セ
ルロース系繊維布帛を熱処理して架橋反応を行うが，こ
の熱処理は，１００〜１８０℃の範囲の温度で，0.５〜
１０分間の処理を行うことにより架橋反応を完結するこ
とができる。After adsorbing the formaldehyde gas, the cellulosic fiber cloth is subjected to a heat treatment to carry out a crosslinking reaction. This heat treatment is performed at a temperature in the range of 100 to 180 ° C. for 0.5 to 0.5
The crosslinking reaction can be completed by performing the treatment for 10 minutes.
【００１５】本発明では，上述の熱処理後，布帛をアミ
ン系化合物の雰囲気中で処理する。ここで用いるアミン
系化合物としては，アミノ基を含有する低分子化合物，
高分子化合物等からなる繊維仕上げ加工用の柔軟仕上げ
剤，樹脂加工剤，ホルムアルデヒド捕捉剤などを挙げる
ことができ，具体的には，アミノ変性シリコン誘導体，
ポリアミド誘導体，脂肪酸アミド誘導体，アルキルアミ
ド誘導体，ポリアミン誘導体等の柔軟仕上げ剤，有機ア
ミン系，アミド系等の樹脂加工剤等の樹脂加工剤，尿
素，エチレン尿素又はベンゾトリアゾール，ピロール，
イミダゾール，1,2,４−トリアゾール，インドロール等
のホルマリン捕捉剤等を挙げることができる。布帛をア
ミン系化合物の雰囲気中で処理するには，アミン系化合
物を含む小滴を含有するエアロゾルミストを気相加工装
置内に吹き込み，生地に吸収させるようにすることによ
り行うことができる。In the present invention, after the above-mentioned heat treatment, the cloth is treated in the atmosphere of the amine compound. As the amine compound used here, a low molecular weight compound containing an amino group,
Examples include softening agents made of polymer compounds for finishing fibers, resin finishing agents, formaldehyde scavengers, and more specifically, amino-modified silicon derivatives,
Polyamide derivatives, fatty acid amide derivatives, alkylamide derivatives, polyamine derivatives and other softening agents, organic amine-based and amide-based resin processing agents and other resin processing agents, urea, ethylene urea or benzotriazole, pyrrole,
Examples thereof include formalin scavengers such as imidazole, 1,2,4-triazole and indolol. The treatment of the cloth in the atmosphere of the amine compound can be performed by blowing an aerosol mist containing droplets containing the amine compound into the gas phase processing apparatus so that the cloth is absorbed.
【００１６】アミン系化合物での処理後，さらに布帛を
スチームで処理すると，残留ホルマリン除去効果をより
一層向上させることができる。ここで用いるスチームの
圧力は，１〜１０kg／cm2 の範囲に調節し，処理時間
は，１〜６０分の範囲で処理する。このスチーム処理時
間中には，気相加工装置の排気口を開けておく必要があ
る。この理由は，装置内が高圧にならないようにすると
ともに，装置内に充満しているホルマリンの濃度を徐々
に下げていくためである。本発明は，以上の構成よりな
るものである。If the cloth is further treated with steam after the treatment with the amine compound, the effect of removing the residual formalin can be further improved. The pressure of the steam used here is adjusted within the range of 1 to 10 kg / cm 2 , and the processing time is within the range of 1 to 60 minutes. During this steam processing time, it is necessary to open the exhaust port of the vapor processing equipment. The reason for this is to prevent the pressure inside the device from becoming high and to gradually reduce the concentration of formalin filled in the device. The present invention has the above configuration.
【００１７】[0017]
【作用】本発明のごとく，セルロース系繊維布帛のホル
ムアルデヒドガスによる気相加工において，ベーキング
工程後の最終工程でアミン系化合物の雰囲気中で処理を
行うと，布帛に残存していた未反応のホルムアルデヒド
とアミン系化合物とが反応し，遊離ホルムアルデヒドが
減少するので，残留ホルマリン量を低減させることがで
き，また，この上にさらにスチーム処理を行うと，スチ
ームによってホルムアルデヒドとアミンの縮合物や残留
ホルマリンがスチーム中の微細な水滴に溶解して除去さ
れるため，布帛中の残留ホルマリン量をより一層低減さ
せることができる。As in the present invention, when the cellulosic fiber cloth is vapor-phase-processed with formaldehyde gas, the unreacted formaldehyde remaining on the cloth is left untreated when the treatment is performed in the atmosphere of the amine compound in the final step after the baking step. The amount of residual formalin can be reduced because the free formaldehyde is reduced by the reaction of the amine compound with the amine compound. Further, when steam treatment is further performed on the residual formalin, the condensation product of formaldehyde and amine and residual formalin are generated by steam. Since it is dissolved in fine water droplets in the steam and removed, the amount of residual formalin in the fabric can be further reduced.
【００１８】[0018]
【実施例】次に，本発明を実施例によってさらに具体的
に説明するが，実施例における布帛の性能の測定，評価
は，下記の方法で行った。
（１）残留ホルマリン量
ＪＩＳＬ−１０４１により測定。EXAMPLES Next, the present invention will be described in more detail with reference to Examples. Measurement and evaluation of the performance of the fabrics in Examples were carried out by the following methods. (1) Residual formalin amount Measured according to JIS L-1041.
【００１９】実施例１
木綿繊維１００％ニット（表鹿子）生地のポロシャツ
を，２０℃，６５％ＲＨの環境室に放置することにより
水分率を8.０％に調節し，続いて，幅２ｍ，長さ３ｍ，
高さ２ｍのステンレススチール製の反応室を有する気相
加工装置を用いて次のように気相加工を行った。まず，
加工装置内にポロシャツを入れ，密閉し，1.２Ｋg ／cm
2 および１０５℃のスチームでインジェクターおよびス
チーム導管を介してフォルムアルデヒド水溶液を1.５分
間室内に供給し，２４００ｇのフォルムアルデヒド水溶
液を注入した。次いで亜硫酸ガス6.８Ｋg を注入し２分
間浸漬後，ポロシャツに保持されなかった遊離のフォル
ムアルデヒドおよび亜硫酸ガスを排気し，室内温度を１
２７℃に上昇させた。この後，尿素１０％水溶液を５分
間噴霧しながら８０℃で５分間処理し，続いて乾燥し
た。Example 1 A polo shirt made of 100% cotton fiber knit (front fawn) fabric was left in an environment room at 20 ° C. and 65% RH to adjust the moisture content to 8.0%, and subsequently to a width of 2 m. , Length 3m,
Gas phase processing was performed as follows using a gas phase processing apparatus having a reaction chamber made of stainless steel and having a height of 2 m. First,
Put the polo shirt in the processing device and seal it to 1.2 kg / cm.
The formaldehyde aqueous solution was supplied to the room for 1.5 minutes through an injector and a steam conduit with steam at 2 and 105 ° C., and 2400 g of the formaldehyde aqueous solution was injected. Then, 6.8 kg of sulfurous acid gas was injected, and after soaking for 2 minutes, free formaldehyde and sulfurous acid gas not retained on the polo shirt were exhausted, and the room temperature was adjusted to 1
Raised to 27 ° C. After that, a 10% aqueous solution of urea was sprayed for 5 minutes, treated at 80 ° C. for 5 minutes, and then dried.
【００２０】本発明との比較のため，本実施例において
尿素の噴霧処理を省く他は，本実施例とまったく同一方
法により比較用の加工布（比較例１）を得た。また，本
発明方法との比較のため，本実施例において尿素溶液の
噴霧処理に代えて従来方法によるアンモニアガス処理
（濃度0.５％）を行うほかは，本実施例とまったく同一
の方法により比較用の加工布（比較例２）を得た。For comparison with the present invention, a comparative work cloth (Comparative Example 1) was obtained in the same manner as in the present Example except that the spray treatment of urea was omitted in this Example. In addition, for comparison with the method of the present invention, the method is exactly the same as that of this example except that the conventional method is replaced with the ammonia gas treatment (concentration: 0.5%) in place of the spray treatment of the urea solution. A processed cloth for comparison (Comparative Example 2) was obtained.
【００２１】本発明および比較用の加工布の性能を測
定，評価し，その結果を合わせて表１に示した。The performances of the present invention and the comparative work cloth were measured and evaluated, and the results are shown in Table 1.
【表１】 [Table 1]
【００２２】表１より明らかなごとく，本発明方法によ
る加工布は，残留ホルマリン量が大幅に低減されてい
た。As is clear from Table 1, the processed fabric produced by the method of the present invention had a significantly reduced residual formalin content.
【００２３】実施例２
上記実施例１において，その最終工程の尿素噴霧処理
後，３kg／cm2 のスチームを２０分間噴霧し，以下乾燥
した。残留ホルマリン量を測定したところ１１６ppm で
あった。この残留量は，実施例１の場合の１９８ppm と
比較して，これを大幅に下回る低減であり，優れた残留
ホルマリン除去効果が認められた。Example 2 In Example 1 above, after the final step of the urea spraying treatment, 3 kg / cm 2 of steam was sprayed for 20 minutes, and then dried. When the amount of residual formalin was measured, it was 116 ppm. This residual amount was a reduction significantly lower than 198 ppm in the case of Example 1, and an excellent residual formalin removing effect was recognized.
【００２４】[0024]
【発明の効果】本発明方法によれば，セルロース系繊維
布帛に未反応の形で残留するホルムアルデヒドを大幅に
低減することができる。According to the method of the present invention, formaldehyde remaining in unreacted form on the cellulosic fiber cloth can be significantly reduced.
Claims (2)
ドガスを吸着させ，熱処理してセルロース分子間に架橋
せしめるホルムアルデヒドによる気相加工において，該
熱処理後にアミン系化合物の雰囲気中で布帛を処理する
ことを特徴とするセルロース系繊維布帛の残留ホルマリ
ン除去方法。1. In vapor-phase processing with formaldehyde, which adsorbs formaldehyde gas on a cellulosic fiber cloth and heat-treats it to crosslink between cellulose molecules, the cloth is treated in an amine compound atmosphere after the heat treatment. A method for removing residual formalin from a cellulosic fiber cloth.
ドガスを吸着させ，熱処理してセルロース分子間に架橋
せしめるホルムアルデヒドによる気相加工において，該
熱処理後にアミン系化合物の雰囲気中で布帛を処理し，
しかる後にスチーム処理することを特徴とするセルロー
ス系繊維布帛の残留ホルマリン除去方法。2. In vapor phase processing with formaldehyde, which adsorbs formaldehyde gas on a cellulosic fiber cloth and heat-treats it to crosslink between cellulose molecules, after the heat treatment, the cloth is treated in an atmosphere of an amine compound,
A method for removing residual formalin from a cellulosic fiber cloth, which is characterized by performing steam treatment thereafter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25514794A JP3462912B2 (en) | 1994-10-20 | 1994-10-20 | Method for removing residual formalin from fabric |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25514794A JP3462912B2 (en) | 1994-10-20 | 1994-10-20 | Method for removing residual formalin from fabric |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08120562A JPH08120562A (en) | 1996-05-14 |
| JP3462912B2 true JP3462912B2 (en) | 2003-11-05 |
Family
ID=17274738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25514794A Expired - Fee Related JP3462912B2 (en) | 1994-10-20 | 1994-10-20 | Method for removing residual formalin from fabric |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3462912B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090004391A1 (en) * | 2007-06-29 | 2009-01-01 | Olang Fatemeh N | Method of reducing formaldehyde emissions from an insulation product |
| WO2016196095A1 (en) * | 2015-05-29 | 2016-12-08 | The Procter & Gamble Company | Fluid fabric enhancer compositions |
| CN114959966B (en) * | 2022-07-15 | 2023-04-18 | 苏州赛恩环境科技有限公司 | Fiber line production equipment and method for injecting formaldehyde scavenger |
-
1994
- 1994-10-20 JP JP25514794A patent/JP3462912B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08120562A (en) | 1996-05-14 |
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