JPH03285999A - Liquid bleaching agent composition - Google Patents

Liquid bleaching agent composition

Info

Publication number
JPH03285999A
JPH03285999A JP2086986A JP8698690A JPH03285999A JP H03285999 A JPH03285999 A JP H03285999A JP 2086986 A JP2086986 A JP 2086986A JP 8698690 A JP8698690 A JP 8698690A JP H03285999 A JPH03285999 A JP H03285999A
Authority
JP
Japan
Prior art keywords
acid
weight
molecular weight
hydrogen peroxide
average molecular
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
Application number
JP2086986A
Other languages
Japanese (ja)
Inventor
Kazuhiro Takanashi
高梨 和宏
Muneo Aoyanagi
青柳 宗郎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to JP2086986A priority Critical patent/JPH03285999A/en
Publication of JPH03285999A publication Critical patent/JPH03285999A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions

Abstract

PURPOSE:To provide the title colored, weakly acidic composition good in storage stability, containing hydrogen peroxide, carboxylic acid-based polymer and metal-contg. dye at specified proportion. CONSTITUTION:The objective composition with a pH1.5-6, containing (A) 0.5-10wt.% of hydrogen peroxide, (B) 0.05-5wt.% of a carboxylic acid-based polymer including polyacrylic acid (salt) or poly-alpha-hydroxyacrylic acid (salt) pref. 1000-100000 in average molecular weight and/or maleic aid-based polymer 500-100000 in average molecular weight, and (C) 0.0001-1wt.% of a pref. phthalocyanine-based metal-contg. dye.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は貯蔵安定性の良好な着色された液体漂白剤組成
物に関する。
DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a pigmented liquid bleach composition with good storage stability.

〔従来の技術〕[Conventional technology]

近年、衣料その他を洗浄漂白する目的から、過酸化水素
を使用した液体酸素系漂白剤が市販され、安全性や簡便
性、色柄物に対する低影響性等の特徴ある漂白作用等に
より広く利用さ゛れるに至っている。
In recent years, liquid oxygen bleaches using hydrogen peroxide have been commercially available for the purpose of cleaning and bleaching clothing and other items, and are widely used due to their unique bleaching properties such as safety, convenience, and low impact on colored and patterned fabrics. It has reached this point.

これらの液体酸素系漂白剤には色味付け、その他の目的
から少量の染料、顔料等の色材類が着色料として配合さ
れることがある。洗浄漂白剤に配合されるこれらの着色
料には洗浄漂白に供された際に着色料の局部的な染着に
よって衣料等を汚したり、貯蔵中に変褪色や変質、変性
を起こしたりしないこと及び過酸化水素の分解を促進し
ないこと等が要求される。
A small amount of coloring materials such as dyes and pigments may be added to these liquid oxygen bleaches for coloring purposes and other purposes. These coloring agents added to cleaning bleaching agents should not cause local staining of clothing when subjected to cleaning bleaching, nor cause discoloration, deterioration, or denaturation during storage. It is also required that the decomposition of hydrogen peroxide is not promoted.

特開昭55−108500号公報には、着色料とじて染
料を配合した過酸化水素液体漂白剤に、アミノ酸等の窒
素含有化合物を添加することにより変褪色がなく、過酸
化水素の損失も少ない着色液体漂白剤が得られることが
記載されている。
JP-A-55-108500 discloses that by adding a nitrogen-containing compound such as an amino acid to a hydrogen peroxide liquid bleach containing a coloring agent and a dye, there is no discoloration or fading and there is little loss of hydrogen peroxide. It is stated that colored liquid bleaches are obtained.

また、特開昭53−39276号公報の実施例にはウル
トラマリン顔料と部分架橋ポリアクリル酸増粘剤と界面
活性剤を配合したp)! 6.7の粘稠な着色過酸化水
素漂白剤は室温で安定であることが記載されている。
Moreover, in the example of JP-A-53-39276, p)! is formulated with an ultramarine pigment, a partially crosslinked polyacrylic acid thickener, and a surfactant. 6.7 viscous colored hydrogen peroxide bleach is described as being stable at room temperature.

〔発明が解決しようとする課題〕[Problem to be solved by the invention]

しかしながら、前者は着色料として金属含有染料を使用
した場合には充分な貯蔵安定性が得られず、また後者は
顔料は比較的安定に分散されるものの、高温貯蔵安定性
が十分でないというような問題がある。
However, in the former case, sufficient storage stability cannot be obtained when metal-containing dyes are used as colorants, and in the latter case, although pigments are dispersed relatively stably, high-temperature storage stability is not sufficient. There's a problem.

〔課題を解決するための手段〕[Means to solve the problem]

本発明者らは、金属含有染料を使用し、かつ高温貯蔵時
にも変褪色や変質、過酸化水素の分解を起こさない着色
液体漂白剤について鋭意研究した結果、特定のポリマー
化合物を共存させればよいことを見出し本発明を完成す
るに至った。
The present inventors have conducted extensive research on colored liquid bleaches that use metal-containing dyes and do not cause discoloration, deterioration, or decomposition of hydrogen peroxide even when stored at high temperatures. This discovery led to the completion of the present invention.

すなわち本発明は、 (a)  過酸化水素       0.5〜10重量
%(ロ)カルボン酸系ポリマー  0.05〜5重量%
(c)  含金属系染料     0.0001〜1重
量%を含有してなり、且つpHが1.5〜6の範囲にあ
る液体漂白剤組成物を提供するものである。
That is, the present invention includes (a) hydrogen peroxide 0.5 to 10% by weight (b) carboxylic acid polymer 0.05 to 5% by weight
(c) A liquid bleach composition containing 0.0001 to 1% by weight of a metal-containing dye and having a pH in the range of 1.5 to 6 is provided.

本発明において、漂白基剤である過酸化水素(a)は組
成物中に0.5〜10重量%、好ましくは3〜7重量%
配合される。
In the present invention, hydrogen peroxide (a) as a bleaching base is contained in the composition in an amount of 0.5 to 10% by weight, preferably 3 to 7% by weight.
It is blended.

本発明に(ロ)成分として用いられるカルボン酸系ポリ
マーは水溶性であり、例えば次の構造を有する平均分子
量が500〜工0万のものが好ましい。
The carboxylic acid polymer used as component (b) in the present invention is water-soluble, and preferably has the following structure and an average molecular weight of 5,000 to 0,000, for example.

〔式中、 R:H,、CH,又はOH Y  : CQOMff又は−〇C0CHxp、q:O
〜I H8Mz、?h : H、アルカリ金属又はアンモニウ
ム を意味する。〕 就中、ポリアクリル酸(塩)又はマレイン酸系ポリマー
が特に好ましい。ポリアクリル酸又はその塩は、平均分
子量が1ooo〜1o万、好ましくは2000〜200
00の範囲のものである。平均分子量が1000未満あ
るいは1o万を越えると貯蔵安定化効果は低下する。尚
、過酸化水素系酸性液体漂白剤に増粘剤としてよく使用
されているカーボボールは分子量の非常に大きい、しか
も部分架橋されているポリアクリル酸であり、本発明で
使用する架橋されていないポリアクリル酸とは別のもの
である。
[In the formula, R:H,, CH, or OH Y: CQOMff or -〇C0CHxp, q:O
~I H8Mz,? h: H means an alkali metal or ammonium. ] Among these, polyacrylic acid (salt) or maleic acid-based polymers are particularly preferred. Polyacrylic acid or its salt has an average molecular weight of 100 to 10,000, preferably 2000 to 200.
00 range. When the average molecular weight is less than 1,000 or more than 10,000, the storage stabilizing effect decreases. Carboball, which is often used as a thickener in hydrogen peroxide-based acidic liquid bleach, is polyacrylic acid that has a very large molecular weight and is partially cross-linked, whereas the non-cross-linked polyacrylic acid used in the present invention It is different from polyacrylic acid.

また、マレイン酸系ポリマーとしては、マレイン酸ホモ
ポリマー又はマレイン酸と他のビニル単量体とのコポリ
マー(これらの部分及び完全中和塩を含む)が挙げられ
る。コポリマーとしては、例えばアクリル酸、メタクリ
ル酸、アクリル酸エステル、メタクリル酸エステル、酢
酸ビニル等から選ばれるビニル単量体とマレイン酸との
コポリマーが挙げられる。就中、アクリル酸又はメタク
リル酸とマレイン酸とのコポリマーが好ましい。マレイ
ン酸と他の単量体のモノマー比はマレイン酸/単量体=
90/10〜4゜/60の範囲にあるのが望ましい。マ
レイン酸系ポリマーは平均分子量が500〜1o万、好
ましくは500−10(100、更に好ましくは6oo
〜3ooo)範囲ムこあるものが用いられる。ポリマー
の平均分子量が500未満或いは1o万を越えると貯蔵
安定化効果は急速に低下する。(b)成分のポリマーは
組成物中に総量で0.05〜5重量%、好ましくは0.
5〜3重量%配合される。ポリマーの配合量が0.05
重量%未満では充分な効果が得られず、また5重量%を
越えるとポリマーの分離問題を生ずる恐れがある。
Examples of maleic acid-based polymers include maleic acid homopolymers and copolymers of maleic acid and other vinyl monomers (including their portions and completely neutralized salts). Examples of the copolymer include copolymers of maleic acid and vinyl monomers selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, vinyl acetate, and the like. Among these, copolymers of acrylic acid or methacrylic acid and maleic acid are preferred. The monomer ratio of maleic acid and other monomers is maleic acid/monomer =
It is desirable that it be in the range of 90/10 to 4°/60. The maleic acid polymer has an average molecular weight of 500 to 10,000, preferably 500-10 (100, more preferably 60,000
to 3ooo) can be used. When the average molecular weight of the polymer is less than 500 or more than 10,000, the storage stabilizing effect rapidly decreases. The total amount of the component (b) polymer in the composition is 0.05 to 5% by weight, preferably 0.05% by weight.
It is blended in an amount of 5 to 3% by weight. The amount of polymer blended is 0.05
If it is less than 5% by weight, sufficient effects cannot be obtained, and if it exceeds 5% by weight, there is a risk of polymer separation problems.

本発明に(c)成分として用いられる含金属系染料とし
ては、例えばカラーインデックス・アシッド・レッド1
98、カラーインデックス・アシッド・ブルー158、
カラーインデックス・アシッド・グリーン35、或いは
フタロシアニン系顔料、例えばカラーインデックス・ダ
イレクト・ブルー86、カラーインデックス・ダイレク
ト・ブルー199等が好適である。中でも特にフタロシ
アニン系染料が好適に用いられる。本発明の液体漂白剤
組成物に所望の色調を付与するために、これらの染料の
1種もしくは数種を併用する。含金属系染料の組成物中
の含有量は0.0001〜1重量%、好ましくは0.0
01〜0.1重量%である。
Examples of metal-containing dyes used as component (c) in the present invention include Color Index Acid Red 1
98, Color Index Acid Blue 158,
Color Index Acid Green 35 or phthalocyanine pigments such as Color Index Direct Blue 86 and Color Index Direct Blue 199 are suitable. Among them, phthalocyanine dyes are particularly preferably used. One or more of these dyes may be used in combination to impart a desired color tone to the liquid bleach composition of the present invention. The content of the metal-containing dye in the composition is 0.0001 to 1% by weight, preferably 0.0%.
01 to 0.1% by weight.

本発明の組成物は通常上記(a)〜(c)成分に水を加
えてバランスをとる。
The composition of the present invention is usually balanced by adding water to the above components (a) to (c).

本発明の組成物には洗浄漂白刃の向上或いは顔料の分散
性を更に向上させるために界面活性剤を配合することが
できる。
A surfactant may be added to the composition of the present invention in order to further improve the cleaning/bleaching properties or the dispersibility of the pigment.

界面活性剤は組成物中に総量で0.1〜20重量%、好
ましくは3〜15重量%配合される。界面活性剤として
はアニオン性又はノニオン性界面活性剤が望ましく、特
に好ましいアニオン性界面活性剤は直鎖アルキル(cs
=C+s)ベンゼンスルホン酸塩、アルキル(08〜c
18)エーテル(エチレンオキサイド付加モル数1〜1
0)硫酸塩、α−オレフィン(cog〜Cl1l)スル
ホン酸塩、アルキル(ca〜C+s)硫酸塩等であり、
また特に好ましいノニオン性界面活性剤(c)はポリオ
キシエチレン(付加モル数1〜30)アルキルエーテル
でアル。特に、アニオン性界面活性剤とノニオン性界面
活性剤を、アニオン性界面活性剤/ノニオン性界面活性
剤重量比が115〜5/1、好ましくは1/3〜3/1
となるように用いるのが望ましい。
The surfactant is incorporated in the composition in a total amount of 0.1 to 20% by weight, preferably 3 to 15% by weight. As the surfactant, anionic or nonionic surfactants are desirable, and particularly preferred anionic surfactants are linear alkyl (cs
=C+s) benzenesulfonate, alkyl (08-c
18) Ether (number of moles of ethylene oxide added 1 to 1
0) sulfates, α-olefin (cog~Cl11) sulfonates, alkyl (ca~C+s) sulfates, etc.
A particularly preferred nonionic surfactant (c) is polyoxyethylene (additional mole number 1 to 30) alkyl ether. In particular, the anionic surfactant and the nonionic surfactant are mixed at an anionic surfactant/nonionic surfactant weight ratio of 115 to 5/1, preferably 1/3 to 3/1.
It is desirable to use it so that

また、本発明の組成物にはエタノール、イソプロパツー
ル、エチレングリコール等のアルコール類、増粘剤、ポ
リリン酸もしくはその塩等のビルダー、EDTA、 N
TA等のキレート剤、香料、酵素、金属不含有染料、顔
料等を必要に応じて配合してもよい。
The composition of the present invention also contains alcohols such as ethanol, isopropanol and ethylene glycol, thickeners, builders such as polyphosphoric acid or its salts, EDTA, N
Chelating agents such as TA, perfumes, enzymes, metal-free dyes, pigments, etc. may be blended as necessary.

本発明の組成物の原液のpHは塩酸、硫酸等の無機酸、
P−)ルエンスルホン酸、クエン酸等の有機酸或いは水
酸化ナトリウム、水酸化カリウムやアミン等の塩基を用
いて1.5〜6、好ましくは2.0〜4.5に調整され
る0組成物のpHが6を越えると貯蔵安定性が著しく低
下する。
The pH of the stock solution of the composition of the present invention is
P-) 0 composition adjusted to 1.5 to 6, preferably 2.0 to 4.5 using an organic acid such as luenesulfonic acid or citric acid or a base such as sodium hydroxide, potassium hydroxide or an amine. If the pH of the product exceeds 6, the storage stability will be significantly reduced.

〔実 施 例〕〔Example〕

以下実施例にて本発明を説明するが、本発明はこれらの
実施例に限定されるものではない。
The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

実施例1 第1表に示す配合組成の漂白剤組成物を調製し、以下の
試験を行なった。
Example 1 A bleach composition having the formulation shown in Table 1 was prepared, and the following tests were conducted.

保存安定性 ■璽力広 第1表の漂白剤組成物を第1図(A)に示すポリエチレ
ン製シリンダボトル(ハイターボトル:滴注量725d
、底部肉厚0 、6 mm )に600d充填密封し、
50°Cで14日間保存した後、外部に取り出してシリ
ンダボトルの膨らみと配合液の変褪色を肉眼で観察した
Storage Stability ■ The bleaching agent composition shown in Table 1 was added to the polyethylene cylinder bottle shown in Fig.
, bottom wall thickness 0,6 mm) filled with 600d and sealed,
After being stored at 50°C for 14 days, it was taken out and the swelling of the cylinder bottle and discoloration of the blended liquid were observed with the naked eye.

なお、第1図(A)は正常状態のボトルであり、底部2
は内方に凹んだ状態にある。また第1図(B)は膨らん
だシリンダボトル1を示すもので、その底部2が外方に
膨出している例を示すものである。ここで、ボトルの膨
らみと配合液の変褪色の評価基準は以下の通りである。
Note that FIG. 1(A) shows the bottle in a normal state, with the bottom 2
is concave inward. Further, FIG. 1(B) shows a swollen cylinder bottle 1, and shows an example in which the bottom portion 2 of the bottle 1 is bulged outward. Here, the evaluation criteria for bottle swelling and discoloration of the blended liquid are as follows.

評価基準 (ボトル外観) ○:変化なし〔第1図(A)〕 △:ボトル底部がやや膨らみ、ボトルのすわりが悪くな
る ×:ボトル底部が膨らみ、ボトルが倒れる(なお、0.
6 kg/cfl1以上の内圧でこの状態となる)〔第
1図(B)〕 (配合液の変褪色) O:変化なし △:やや褪色している ×:褪色している これらの結果を第1表に示す。
Evaluation Criteria (Bottle Appearance) ○: No change [Figure 1 (A)] △: The bottom of the bottle swells slightly and the bottle becomes difficult to sit ×: The bottom of the bottle swells and the bottle falls over (note that 0.
This state occurs at an internal pressure of 6 kg/cfl1 or more) [Figure 1 (B)] (Discoloration and discoloration of the compounded liquid) O: No change △: Slightly discolored ×: Discolored These results are shown below. It is shown in Table 1.

第 1 表 3)カラーインデックス・ダイレクト・ブルー199 4)全体を100とするためのバランス量の略No. 1 table 3) Color Index Direct Blue 199 4) Abbreviation for balance amount to make the whole 100

【図面の簡単な説明】[Brief explanation of drawings]

第1図(A)は正常状態のシリンダボトル、第1図(B
)は膨らんだシリンダボトルの断面図である。 1ボトル 2底部 1)平均分子量8000 2)カラーインデックス・ダイレクト・ブルー86
Figure 1 (A) shows the cylinder bottle in normal condition, Figure 1 (B)
) is a cross-sectional view of an inflated cylinder bottle. 1 Bottle 2 Bottom 1) Average molecular weight 8000 2) Color Index Direct Blue 86

Claims (1)

【特許請求の範囲】 1 (a)過酸化水素0.5〜10重量% (b)カルボン酸系ポリマー0.05〜5重量%(c)
含金属系染料0.0001〜1重量%を含有してなり、
且つpHが1.5〜6の範囲にある液体漂白剤組成物。 2 カルボン酸系ポリマーが、平均分子量1000〜1
0万のポリアクリル酸或いはポリ−α−ヒドロキシアク
リル酸もしくはそれらの塩、及び/又は平均分子量50
0〜10万のマレイン酸系ポリマーである請求項1記載
の液体漂白剤組成物。 3 マレイン酸系ポリマーがアクリル酸又はメタクリル
酸とマレイン酸のコポリマーである請求項1又は2記載
の液体漂白剤組成物。 4 含金属系染料がフタロシアニン系染料である請求項
1〜3の何れか1項記載の液体漂白剤組成物。
[Claims] 1 (a) Hydrogen peroxide 0.5-10% by weight (b) Carboxylic acid polymer 0.05-5% by weight (c)
Containing 0.0001 to 1% by weight of metal-containing dye,
and a liquid bleach composition having a pH in the range of 1.5 to 6. 2 The carboxylic acid polymer has an average molecular weight of 1000 to 1
00,000 polyacrylic acid or poly-α-hydroxyacrylic acid or salts thereof, and/or average molecular weight 50
The liquid bleach composition according to claim 1, which is a maleic acid-based polymer having a molecular weight of 0 to 100,000. 3. The liquid bleach composition according to claim 1 or 2, wherein the maleic acid-based polymer is a copolymer of acrylic acid or methacrylic acid and maleic acid. 4. The liquid bleach composition according to any one of claims 1 to 3, wherein the metal-containing dye is a phthalocyanine dye.
JP2086986A 1990-03-30 1990-03-30 Liquid bleaching agent composition Pending JPH03285999A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2086986A JPH03285999A (en) 1990-03-30 1990-03-30 Liquid bleaching agent composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2086986A JPH03285999A (en) 1990-03-30 1990-03-30 Liquid bleaching agent composition

Publications (1)

Publication Number Publication Date
JPH03285999A true JPH03285999A (en) 1991-12-17

Family

ID=13902187

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2086986A Pending JPH03285999A (en) 1990-03-30 1990-03-30 Liquid bleaching agent composition

Country Status (1)

Country Link
JP (1) JPH03285999A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0745663A1 (en) * 1995-05-31 1996-12-04 The Procter & Gamble Company Colored acidic aqueous liquid compositions comprising a peroxy-bleach
JP2007016244A (en) * 1994-01-14 2007-01-25 Rohm & Haas Co Cleaning composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007016244A (en) * 1994-01-14 2007-01-25 Rohm & Haas Co Cleaning composition
EP0745663A1 (en) * 1995-05-31 1996-12-04 The Procter & Gamble Company Colored acidic aqueous liquid compositions comprising a peroxy-bleach

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