JPH07122077B2 - Hydrogen peroxide bleach stabilizer - Google Patents
Hydrogen peroxide bleach stabilizerInfo
- Publication number
- JPH07122077B2 JPH07122077B2 JP62126923A JP12692387A JPH07122077B2 JP H07122077 B2 JPH07122077 B2 JP H07122077B2 JP 62126923 A JP62126923 A JP 62126923A JP 12692387 A JP12692387 A JP 12692387A JP H07122077 B2 JPH07122077 B2 JP H07122077B2
- Authority
- JP
- Japan
- Prior art keywords
- bleaching
- hydrogen peroxide
- present
- salt
- stabilizer
- 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
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Description
【発明の詳細な説明】 産業上の利用分野 本発明は過酸化水素で繊維類を漂白する場合に用いる漂
白浴中の過酸化水素の安定剤に関するものである。TECHNICAL FIELD The present invention relates to a stabilizer for hydrogen peroxide in a bleaching bath used when bleaching fibers with hydrogen peroxide.
先行技術の説明 一般に過酸化水素による漂白はアルカリ性で行われる
が、単にアルカリ性にしただけでは漂白浴中に存在する
鉄、銅、マンガン等の重金属イオンによって、式 2H2O2→2H2O＋O2 で示される過酸化水素の分解が多く起り、式 H2O2→H+＋OOH- で示される、漂白に関与するとされるパーヒドロキシル
イオン（OOH-）の生成が減少して、漂白効果が上らない
ことが知られている。この場合通常は過酸化水素漂白浴
に安定剤を添加して過酸化水素の分子状酸素への分解を
抑制する方法が取られている。Description of the Prior Art Bleaching with hydrogen peroxide is generally performed in an alkaline manner. However, if it is simply made alkaline, heavy metal ions such as iron, copper, and manganese present in the bleaching bath cause the formula 2H 2 O 2 → 2H 2 O + O 2 in occur much decomposition of hydrogen peroxide represented the formula H 2 O 2 → H + + OOH - represented by, par hydroxyl ions to be involved in bleach (OOH -) generation of decreases, above bleaching effect It is known not to. In this case, usually, a stabilizer is added to the hydrogen peroxide bleaching bath to suppress the decomposition of hydrogen peroxide into molecular oxygen.
これに用いられる安定剤としては古くから、ケイ酸ソー
ダが用いられており、之によつて安定効果に秀れ、秀れ
た白度の向上をもたらすことが見出されているが、その
反面この方法によると被処理物にケイ酸スケールが付着
して、繊維の風合を害するという欠点があり、更には装
置にケイ酸スケールが沈着する等の欠点もある。Sodium silicate has been used for a long time as a stabilizer used for this purpose, and it has been found that it has an excellent stability effect and brings an excellent whiteness improvement. According to this method, there is a drawback that the silicic acid scale adheres to the object to be treated and the texture of the fiber is impaired, and further there is a drawback that the silicic acid scale is deposited on the apparatus.
更に現在の所ケイ酸ソーダ以外にもEDTA、DTPA等の有機
キレート剤、縮合リン酸塩等の無機キレート剤（MOL、
４月号/1968、42ページ）、大豆タンパク、カゼイン等
の水溶性タンパク質（特公昭50−34675号公報）がこの
目的に用い得ることが知られている。In addition to sodium silicate at present, organic chelating agents such as EDTA and DTPA, inorganic chelating agents such as condensed phosphates (MOL,
It is known that water-soluble proteins such as soybean protein and casein (Japanese Patent Publication No. 50-34675) can be used for this purpose.
しかし乍ら、これらのケイ酸ソーダ以外の安定剤は、浴
比の大きなバツチ方式においては、或る程度の安定効果
を発揮し、工業的にも成果をあげているが、浴比の小さ
い連続方式においてはケイ酸ソーダに比べて、安定効果
と製品の白度、脆化防止等の効果の点で劣り、又作業の
安定性にも劣り、未だ工業的に充分な成果を得るには至
つていない（的場由穂、動的因果関係と未来染色の考
察、No.132,染色経済新聞）。However, these stabilizers other than sodium silicate have a certain stabilizing effect in the batch method with a large bath ratio and have been industrially successful, but they have a small continuous bath ratio. Compared with sodium silicate, the method is inferior in terms of stability and whiteness of the product, the effect of preventing embrittlement, etc., and also inferior in stability of work, and it is still difficult to obtain industrially sufficient results. Not (Yuho Matoba, Dynamic Causal Relationship and Future Dyeing, No.132, Dyeing Economy Newspaper).
一方、特開昭52−103386号公報に開示されているポリ−
α−ヒドロキシルアクリル酸ナトリウムから成る漂白安
定剤が、非ケイ酸系化合物としては今までに例をみない
程の安定化、白度の上昇、その他の秀れた性能を示し、
ケイ酸塩に置き換え得る程の安定化作用、過酸化水素分
解触媒の分解作用抑制能の向上が見られ、更に保護剤と
しての作用を有することが認められている。しかし乍
ら、この化合物は過酸化水素の安定化力が余りに強いの
で、時として漂白効果、綿種子除去力を妨げる場合があ
る。On the other hand, the poly-type disclosed in Japanese Patent Laid-Open No. 52-103386
A bleaching stabilizer composed of sodium α-hydroxyl acrylate shows a stabilization that is unprecedented as a non-silicic acid compound, an increase in whiteness, and other excellent performance,
It has been found that the stabilizing action to the extent that it can be replaced with a silicate and the ability to suppress the decomposition action of the hydrogen peroxide decomposition catalyst are improved, and that it also has a function as a protective agent. However, since this compound has too strong a stabilizing effect on hydrogen peroxide, it sometimes interferes with the bleaching effect and the cotton seed removing effect.
又、この化合物は非常に高価であつて、充分な効果を発
揮させるに必要な量をこの化合物単体で購うとなると、
価格高のために工業的には使用出来ない。In addition, this compound is very expensive, and if one purchases the amount of the compound required to exert a sufficient effect by itself,
It cannot be used industrially due to the high price.
この為、特開昭55−76161号公報では、ポリ−α−ヒド
ロキシアクリル酸ナトリウムに縮合リン酸塩を組み合せ
て用いる方法が開示されているが、この方法では布の風
合を悪化する傾向があり好ましくない。ポリ−α−ヒド
ロキシアクリル酸ナトリウムとケイ酸ソーダの組み合せ
によつても良い結果は得られない。Therefore, JP-A-55-76161 discloses a method in which sodium poly-α-hydroxyacrylate is used in combination with a condensed phosphate, but this method tends to deteriorate the texture of the cloth. There is not preferable. Good results are not obtained with the combination of sodium poly-α-hydroxyacrylate and sodium silicate.
発明の略解 ここにおいて、本発明者はポリ−α−ヒドロキシアクリ
ル酸ナトリウム（以下、PHASと称すこともある）の秀れ
た特性に注目し、之を用いて工業的に有利に漂白操作を
行える様改良すべく研究を重ね、ポリ−α−ヒドロキシ
アタリル酸、その塩又はそのラクトンを、後記する一般
式又はの有機ホスホン酸、又はその塩と組み合わせ
て用いることによりPHASを単独で使用した場合、或るい
はケイ酸ソーダを使用した場合に得られる以上の漂白効
果を示し、さらには過酸化水素分解触媒の分解作用抑
制、種子除去、保護剤としての効果にも秀れ、更には風
合も良好であることが見出されて本発明を完成した。BRIEF SUMMARY OF THE INVENTION Here, the present inventor pays attention to the excellent properties of sodium poly-α-hydroxyacrylate (hereinafter, sometimes referred to as PHAS), and can perform bleaching operation industrially with In the case of using PHAS alone by repeating researches to improve it, poly-α-hydroxyatalylic acid, its salt or its lactone is used in combination with the organic phosphonic acid of the following general formula or of the following, or its salt. , Or shows a bleaching effect more than that obtained when sodium silicate is used, and is also excellent in suppressing the decomposition action of hydrogen peroxide decomposition catalyst, removing seeds, and as a protective agent. It was found that the above was also good, and the present invention was completed.
従つて、本発明の目的は、ケイ酸塩障害が無く、連続式
漂白法においても、ケイ酸ソーダ或るいはPHASを、単独
で使用した場合以上の漂白効果を上げ、かつ綿種子除去
性に秀れ、風合のよい被漂白物が得られて、経済性の上
からも工業的に実施出来る漂白安定剤を提供するにあ
る。Therefore, the object of the present invention, without silicate damage, even in the continuous bleaching method, sodium silicate or PHAS, enhance the bleaching effect more than when used alone, and in cotton seed removability An object of the present invention is to provide a bleaching stabilizer which can be bleached and which is excellent in texture and which can be industrially implemented from the economical viewpoint.
本発明者等は、本発明の過酸化水素漂白安定剤による漂
白効果については、PHASと有機ホスホン酸の有するキレ
ート特性に差異があつて、PHASの過酸化水素に対する強
い安定化作用が、有機ホスホン酸の作用により生地内部
まで浸透して之を活性化し、之等の作用が相乗効果とし
て現われることによるものと考えられる。Regarding the bleaching effect of the hydrogen peroxide bleaching stabilizer of the present invention, the present inventors have a difference in the chelating properties of PHAS and organic phosphonic acid. It is considered that the action of acid permeates the inside of the dough and activates it, and these actions appear as a synergistic effect.
発明の具体的な説明 更に詳しくは、本発明はポリ−α−ヒドロキシアクリル
酸とその塩、或るいはそのポリラクトンより成る群から
選ばれた少なくとも１種のヒドロキシアクリル酸重合体
と、 一般式 （式中、A,B,Cは−CH2PO3H2又は水素であり、ｍは３〜1
2の整数、ｎは１〜４の整数である。） （式中、Ｄは−CH2PO3H2又は水素であり、Ｅは炭素数１
〜12のアルキル基である。） で表わされる有機ホスホン酸、又はそれらの塩から成る
群より選ばれた少なくとも１種の化合物との組み合せよ
り成ることを特徴とする過酸化水素系漂白浴の安定剤を
提供するものである。DETAILED DESCRIPTION OF THE INVENTION More specifically, the present invention relates to at least one hydroxyacrylic acid polymer selected from the group consisting of poly-α-hydroxyacrylic acid and a salt thereof or a polylactone thereof, and a compound represented by the general formula: (In the formula, A, B and C are —CH 2 PO 3 H 2 or hydrogen, and m is 3 to 1
An integer of 2 and n is an integer of 1 to 4. ) (In the formula, D is —CH 2 PO 3 H 2 or hydrogen, and E is a carbon number 1
~ 12 alkyl groups. The present invention provides a stabilizer for a hydrogen peroxide bleaching bath, which comprises a combination with an organic phosphonic acid represented by the formula (1) or at least one compound selected from the group consisting of salts thereof.
ポリ−α−ヒドロキシアクリル酸は、水溶性で金属イオ
ンと錯塩を作りキレート作用を示す比較的新しい化合物
の１つであつて、イオン封鎖作用も示す。本発明に用い
るには、平均分子量1,000〜1,000,000、好ましくは2,00
0〜800,000のものが好ましい。Poly-α-hydroxyacrylic acid is one of the relatively new compounds that is water-soluble and forms a complex salt with a metal ion and exhibits a chelating action, and also exhibits an ion sequestering action. For use in the present invention, an average molecular weight of 1,000 to 1,000,000, preferably 2,000.
Those of 0 to 800,000 are preferable.
本発明に用いる塩としては、１価の金属塩例えば、ナト
リウム塩、カリウム塩、またはアンモニウム塩等を好ま
しく用いることが出来、その使用量は浴中0.05g/以
上、好ましくは0.2g/以上を用い、その上限には特に
限定はないが、その使用量は経済性と漂白効果を考慮し
て10g/以下で使用するのが一般的である。As the salt used in the present invention, a monovalent metal salt such as sodium salt, potassium salt, or ammonium salt can be preferably used, and the amount thereof is 0.05 g / or more in the bath, preferably 0.2 g / or more. The upper limit is not particularly limited, but the amount used is generally 10 g / or less in consideration of economy and bleaching effect.
本発明で用いるα−ヒドロキシアクリル酸のポリラクト
ン（以下PLACと略称する）とは、この重合体の酸基とヒ
ドロキシル基との反応によつて得られる分子内及び／又
は分子間エステルである。The polylactone of α-hydroxyacrylic acid (hereinafter abbreviated as PLAC) used in the present invention is an intramolecular and / or intermolecular ester obtained by the reaction between an acid group and a hydroxyl group of this polymer.
上記ヒドロキシアクリル酸重合体と共に用いる上記一般
式又はで表わされる有機ホスホン酸又はその塩は錯
塩を作つてキレート能を有し、又緩衝作用を示すが、そ
の塩としてはナトリウム、カリウム又はアンモニウム塩
が好ましく用いられる。その使用量としては0.2〜5g/
、好ましくは、0.3〜2g/が用いられる。The organic phosphonic acid represented by the above-mentioned general formula or represented by the use with the hydroxyacrylic acid polymer or a salt thereof has a chelating ability by forming a complex salt and also has a buffering action, and as the salt, a sodium, potassium or ammonium salt is used. It is preferably used. The amount used is 0.2-5g /
, Preferably 0.3 to 2 g / is used.
一般式又はの化合物を例示すれば、プロピレンジア
ミンテトラメチレンホスホン酸、ヘキサメチレンジアミ
ンテトラメチレンホスホン酸、ジプロピレントリアミン
ペンタメチレンホスホン酸、ドデシルアミンジメチレン
ホスホン酸等を挙げることができる。Examples of the compound of the general formula or are propylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, dipropylenetriaminepentamethylenephosphonic acid, dodecylaminedimethylenephosphonic acid and the like.
本発明組成物は、上記安定剤を漂白液中に所定量添加し
て、常温より沸騰点迄の所定温度下に常法により用いれ
ばよく、界面活性剤等の添加剤は通常の如く任意に用い
得る。用いる繊維類としては主として木綿に用いること
が出来るが、他の繊維に対しても用いることが出来る。The composition of the present invention may be prepared by adding the stabilizer in a predetermined amount to a bleaching solution and using it in a conventional manner at a predetermined temperature from room temperature to the boiling point, and additives such as surfactants may be arbitrarily added as usual. Can be used. The fibers to be used can be mainly used for cotton, but can also be used for other fibers.
本発明安定剤を用いる漂白機としては、ウインスー、キ
ヤー、オーバーマイヤー、ジツカー等のバツチ式漂白機
も勿論使用出来るが、特に望ましくはＪ−ボツクス、Ｌ
−ボツクス、パープルレンジ、ベントラー等の連続漂白
機による連続式漂白に用いて秀れた漂白効果を挙げるこ
とが出来る。As the bleaching machine using the stabilizer of the present invention, batch type bleaching machines such as Winsoo, Kear, Overmeier, and Zicker can be used, of which J-box, L is particularly preferable.
-It can be used for continuous bleaching with a continuous bleaching machine such as a box, a purple range, a bentler, etc., and has an excellent bleaching effect.
発明の効果 本発明によれば、PHAS類を前述の有機ホスホン酸または
その塩と共に用いて得られる相乗効果によつて、ケイ酸
ソーダを用いた場合よりも秀れた漂白効果を得ることが
出来るものであるが、ケイ酸ソーダを使用した際に悩ま
されるケイ酸塩障害の問題から開放されると共に、PHAS
類を単独で用いた場合よりも製品の白度が向上し、綿種
子除去性にも秀れ、又漂白後の繊維の強度低下が少な
く、金属除去能力、金属イオン封鎖力にも秀れ、風合も
よい被漂白物が得られる。この様に、本発明によれば、
既知の過酸化水素漂白剤によつては得られない秀れた効
果が得ることが出来るのである。EFFECTS OF THE INVENTION According to the present invention, the synergistic effect obtained by using PHASs together with the aforementioned organic phosphonic acid or a salt thereof makes it possible to obtain an excellent bleaching effect as compared with the case of using sodium silicate. However, PHAS is freed from the problem of silicate disorders that plagues the use of sodium silicate.
The whiteness of the product is improved as compared with the case of using the compounds alone, the cotton seed removability is also excellent, the strength reduction of the fiber after bleaching is small, the metal removing ability and the sequestering power of metal ions are excellent, A bleached product with a good texture is obtained. Thus, according to the present invention,
The excellent effect which cannot be obtained by the known hydrogen peroxide bleach can be obtained.
以下、実施例により本発明を説明する。Hereinafter, the present invention will be described with reference to examples.
実施例１ 綿メリヤス（40番手）を下記の条件の下でスチーミング
漂白を行つた。漂白結果を表１に示す。比較例として在
来の漂白剤を用いて得られた結果も表１に示した。Example 1 A cotton knit (40th count) was steamed and bleached under the following conditions. The bleaching results are shown in Table 1. The results obtained with the conventional bleach as a comparative example are also shown in Table 1.
漂白浴の組成および漂白条件は次の通りである。The composition of the bleaching bath and the bleaching conditions are as follows.
H2O2 （35％） 40ml/ 安定剤 PHAS又はPLAC＊ 表１に示す通り 有機ホスホン酸 表１に示す通り サンモール Ｓ−50 1g/ （日華化学工業（株）製アニオン系、及び非イオン系界
面活性剤の混合物） NaOH （フレーク） 3g/ 絞り率・・・ 100％ 温度および処理時間・・100℃,40分 ＊PLACはソルベー社製CLARENE−Ｌ（平均分子量100,00
0）を用いた。PHASは上記PLACをNaOHと反応させて得ら
れたポリ−α−ヒドロキシアクリル酸ナトリウムを用い
た。H 2 O 2 (35%) 40ml / Stabilizer PHAS or PLAC * As shown in Table 1 Organic phosphonic acid As shown in Table 1 Sunmol S-50 1g / (Nika Kagaku Kogyo Co., Ltd. Mixture of ionic surfactants) NaOH (flakes) 3 g / squeezing rate ・ ・ ・ 100% Temperature and processing time · 100 ℃, 40 minutes * PLAC is CLARENE-L (average molecular weight 100,00 manufactured by Solvay)
0) was used. PHAS used was sodium poly-α-hydroxyacrylate obtained by reacting PLAC with NaOH.
白度：マクベスMS−2020側色機 反射率測定・・・波長 440mμ 風合：東洋ボールドウイン（株）製テンシロンを用いて
10cm×10cmの布を直径3cm厚さ0.5mmのステンレス製のリ
ング内を通過させるときの抵抗値で示した。Whiteness: Macbeth MS-2020 side color machine Reflectance measurement ... wavelength 440mμ Hand feeling: Using Toyo Baldwin Co., Ltd. Tensilon
The resistance value was obtained when a 10 cm × 10 cm cloth was passed through a stainless ring having a diameter of 3 cm and a thickness of 0.5 mm.
表１の結果より明らかな如く、本発明漂白剤を用いて、
在来品に勝る秀れた結果が得られた。As is clear from the results of Table 1, using the bleaching agent of the present invention,
Excellent results over conventional products have been obtained.
実施例２ 綿ブロード（40番手）を下記の条件の下でスチーミング
漂白を行つた。漂白結果を表２に示した。Example 2 Cotton broad (40th count) was steamed and bleached under the following conditions. The bleaching results are shown in Table 2.
漂白浴の組成および漂白条件は次の通りである。The composition of the bleaching bath and the bleaching conditions are as follows.
H2O2 （35％） 20ml/ 安定剤 PHAS＊＊ 表２に示す通り 有機ホスホン酸 表２に示す通り サンモール Ｓ−50 1g/ （日華化学工業（株）製アニオン系、及び非イオン系界
面活性剤の混合物） NaOH（フレーク） 2g/ 絞り率・・・ 90％ 温度および処理時間・・・95℃,30分 ＊＊実施例１に用いたものと同じ。H 2 O 2 (35%) 20ml / Stabilizer PHAS ** Organic phosphonic acid as shown in Table 2 Organic phosphonic acid as shown in Table 2 Sunmol S-50 1g / (Nika Chemical Co., Ltd. anionic and nonionic Mixture of surfactants) NaOH (flakes) 2 g / squeezing rate ... 90% Temperature and treatment time ... 95 ° C., 30 minutes ** Same as used in Example 1.
綿種子除去性：視覚判定による ○は種子全く無し △はわずか残つている ×はかなり残つている 表２より明らかな如く、本発明漂白剤によれば、在来品
に勝る秀れた結果が得られた。Cotton Seed Removability: According to visual judgment, ○ means no seeds, Δ means a slight amount is left, and × is a considerable amount. As is clear from Table 2, the bleaching agent of the present invention has excellent results superior to conventional products. Was obtained.
実施例３ 綿ポブリン（40番手）糊抜精練布にFeSO4・7H2O1％水溶
液又はCuSO4・5H2Oの１％水溶液を一定量スポツトし、
乾燥後、実施例２と同じ条件で漂白を行ない、この漂白
布の引張り強度を測定した。得られた結果を表３に示し
た。Example 3 A fixed amount of FeSO 4 .7H 2 O 1% aqueous solution or CuSO 4 .5H 2 O 1% aqueous solution was spotted onto a cotton pobulin (40th count) desizing scouring cloth,
After drying, bleaching was performed under the same conditions as in Example 2, and the tensile strength of this bleached cloth was measured. The results obtained are shown in Table 3.
強度：引張り強度 オートグラフJIS−Ｌ−1068（定速緊張型）ツカミ間隔5
cm、引張り速度200mm/分の条件下に５回測定し平均値を
算出して、結果を表３に示した。Strength: Tensile strength Autograph JIS-L-1068 (constant speed tension type) Grip interval 5
The measurement was performed 5 times under the conditions of cm and pulling speed of 200 mm / min, the average value was calculated, and the results are shown in Table 3.
表３の結果より明らかな如く、本発明漂白安定剤により
在来品に勝る秀れた結果が得られた。As is clear from the results of Table 3, the bleaching stabilizer of the present invention gave excellent results superior to conventional products.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−21973（ＪＰ，Ａ) 特開 昭55−76161（ＪＰ，Ａ) 特開 昭61−155208（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 63-21973 (JP, A) JP 55-76161 (JP, A) JP 61-155208 (JP, A)
Claims (1)
の塩或いはそのポリラクトンのうちより選ばれた少なく
とも１種のヒドロキシアクリル酸重合体と、下記の一般
式〜で示される有機ホスホン酸またはその塩の少な
くとも１種より成ることを特徴とする過酸化水素漂白安
定剤。 一般式 （式中、A,B,Cは−CH2PO3H2又は水素であり、ｍは３〜1
2の整数、ｎは１〜４の整数である。） （式中、Ｄは−CH2PO3H2又は水素であり、Ｅは炭素数１
〜12のアルキル基である。）1. A poly (α-hydroxyacrylic acid) or a salt thereof, or at least one hydroxyacrylic acid polymer selected from a polylactone thereof, and an organic phosphonic acid represented by the following general formula (1) to a salt thereof: A hydrogen peroxide bleaching stabilizer comprising at least one kind. General formula (In the formula, A, B and C are —CH 2 PO 3 H 2 or hydrogen, and m is 3 to 1
An integer of 2 and n is an integer of 1 to 4. ) (In the formula, D is —CH 2 PO 3 H 2 or hydrogen, and E is a carbon number 1
~ 12 alkyl groups. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62126923A JPH07122077B2 (en) | 1987-05-26 | 1987-05-26 | Hydrogen peroxide bleach stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62126923A JPH07122077B2 (en) | 1987-05-26 | 1987-05-26 | Hydrogen peroxide bleach stabilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63291998A JPS63291998A (en) | 1988-11-29 |
| JPH07122077B2 true JPH07122077B2 (en) | 1995-12-25 |
Family
ID=14947247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62126923A Expired - Fee Related JPH07122077B2 (en) | 1987-05-26 | 1987-05-26 | Hydrogen peroxide bleach stabilizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07122077B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3720806C2 (en) * | 1986-07-03 | 1997-08-21 | Clariant Finance Bvi Ltd | Use of a stabilizer in peroxide bleaching processes |
-
1987
- 1987-05-26 JP JP62126923A patent/JPH07122077B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63291998A (en) | 1988-11-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |