CN87100624A - Stabilizer for hydrogen peroxide bleaching agent - Google Patents

Stabilizer for hydrogen peroxide bleaching agent Download PDF

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Publication number
CN87100624A
CN87100624A CN87100624.3A CN87100624A CN87100624A CN 87100624 A CN87100624 A CN 87100624A CN 87100624 A CN87100624 A CN 87100624A CN 87100624 A CN87100624 A CN 87100624A
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China
Prior art keywords
bleaching
hydrogen peroxide
formula
hydrogen
phas
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Granted
Application number
CN87100624.3A
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Chinese (zh)
Other versions
CN1022940C (en
Inventor
町田靖
�田勉
木材纪夫
渡道正俊
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.)
Japanese Chemical Industry Co ltd
Nippon Peroxide Co Ltd
Original Assignee
Japanese Chemical Industry Co ltd
Nippon Peroxide Co Ltd
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Publication of CN87100624A publication Critical patent/CN87100624A/en
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Publication of CN1022940C publication Critical patent/CN1022940C/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents

Abstract

A stabilizer for hydrogen peroxide bleaching agent is characterized by selecting at least poly! -a hydroxyacrylic acid or a salt thereof, or a polylactone thereof, and a compound having the following general formula (1) and at least one organophosphonic acid having the following general formula (2) or a salt thereof.
A, B in the formula (1) and D, E, F, m and n in the formula (2) are defined in the specification.

Description

The stabilizing agent of hydrogen peroxide bleaching
The present invention is relevant during with hydrogen peroxide bleaching fiber-like article, in order to the stabilizing agent of stable peroxide hydrogen bleaching agent.
Generally speaking, during with hydrogen peroxide bleaching, mostly under alkali condition, carry out.Yet, only be under the single condition of alkalescence, to carry out, heavy metal ion such as the iron that exists in the bleaching agent, copper, manganese can make hydrogen peroxide comply with following reaction equation and accelerated decomposition,
Opposite, according to the hydroperoxy-ion (OOH of the following reaction equation generation relevant with discoloration -) then can reduce,
Thereby can't improve its bleaching effect.In this case, normally adding stabilizing agent in hydrogen peroxide, is oxygen molecule to suppress hydrogen peroxide decomposes.
For a long time, the stabilizing agent of this respect all adopts sodium metasilicate, and its stablizing effect is fairly good, and can obtain goodish whiteness, and still, it also has shortcoming, that is, can on processed article, stay silicate precipitates, thereby the quality of infringement fiber.In addition, also can depositing silicon hydrochlorate dirt on bleaching equipment.
In addition, except that above-mentioned sodium metasilicate, also use organic sequestering agents such as EDTA, DTPA at present, reach inorganic chelator (MOL such as condensed phosphate, April number/1968, the 42nd page), soybean protein, the protein (Japan's " special permission communique " 1975 No. 34675/1975) that casein etc. are water-soluble etc.
Yet, though the stabilizing agent beyond these sodium metasilicate can bleaching bath than big fraction operation on performance to a certain degree stablizing effect and also in the industrial achievement that obtained, but, bleaching bath than little continued operation in, its stablizing effect, whiteness and prevent that embrittlement effect etc. is then than the silicic acid sodium error, also relatively poor in industrial stability, can not reach effect of sufficient (field by investigation, the No.132 of fringe, moving causality and following dyeing, dyeing Economic News) industrial.
On the other hand; poly-alpha-hydroxy sodium acrylate (the being designated hereinafter simply as PHAS) bleaching stibilizer that disclosed for No. 103386/1977 of Japan's " special permission communique " then is that not seen before beyond a kind of sodium metasilicate has the good stable effect; improve the stabilizing agent of whiteness and other performances; to replace sodium metasilicate; it not only can improve the inhibition hydrogen peroxide and be subjected to the effect of catalytic decomposition, and has protectant function.Yet, because this PHAS is too strong to the stabilizing power of hydrogen peroxide, the situation that infringement bleaching effect and cottonseed are removed power takes place sometimes.
In addition, the price of this PHAS is quite expensive, if will bring into play effect of sufficient, then need buy the PHAS monomer of capacity, because of its appropriate litigation fees height, so that can't reach plant-scale use.
Because this reason, Japan's " special permission communique " just discloses for 1980 No. 76161/1980 about utilizing the method for poly-alpha-hydroxy sodium acrylate and condensation phosphonate and usefulness, and still, the method but has the tendency of infringement cloth quality, can not be satisfactory.In addition, the combination about PHAS and sodium metasilicate can't obtain good result too.
The inventor pays close attention to the excellent specific property of PHAS; especially it is continued the research improvement; make it can help industrial bleaching operation; found that PHAS; when the organic phospho acid shown in its esters or its lactone and formula of hereinafter addressing (1) and/or the formula (2) or its salt are used in combination; better bleaching effect in the time of can obtaining than independent use PHAS or sodium metasilicate; in addition; the catalytic decomposition that can suppress hydrogen peroxide; and have excellent removal cottonseed and as protectant effect, and can make by the bleaching thing and keep good quality.
Therefore, the object of the present invention is to provide a kind of bleaching stibilizer that is worth and is suitable for commercial Application through squeezing that has.This stabilizing agent does not have the silicate infringement by the shortcoming of bleaching thing, is applicable to the operation of batch formula and continous mode, can obtain than independent use sodium metasilicate or the better bleaching effect of PHAS, has the ability of removing cottonseed of excellence, and keeps by the good quality of bleaching thing.
The inventor knows, the bleaching effect of the stabilizing agent of the present invention's hydrogen peroxide bleaching is because PHAS and organic phospho acid have been brought into play synergistic effect, that is, the huge legendary turtle of PHAS and organic phospho acid is closed variant mutually, but PHAS has the stabilization of strong row to hydrogen peroxide, the effect of organic phospho acid then is to make it infilter to the cloth and then make its activation, therefore brings into play its synergism effectiveness.
More particularly, the present invention provides a kind of stabilizing agent with hydrogen peroxide bleaching of following characteristic, that is, it is characterized in that selecting for use at least a kind of hydroxyl acrylic polymer among PHAS or its esters or its polylactone and have the compound of following general formula (1) and/or at least a organic phospho acid with following general formula (2) or its esters to constitute the stabilizing agent of hydrogen peroxide bleaching.
Figure 87100624_IMG4
In the formula (1), A represents that hydrogen or carbon number are 1～3 alkyl; B represents that hydrogen, hydroxyl or carbon number are 1～3 alkyl, and A and B identical or differently all can;
Figure 87100624_IMG5
In the formula (2), D, E and F all represent methylene phosphonic acid base or hydrogen; M is 1～15 integer; M is 0～4, better is 0～2 integer, and still, D and E represent in the situation of hydrogen is not included in simultaneously.
PHAS is a kind of compound that can form the comparison novelty of complex salt with water-soluble metal ion, has the ion sealing process.This base polymer of the present invention's use, its mean molecule quantity is 1,000～1,000,000, is preferably 2,000～800,000.
The PHAS salt that the present invention uses is example with 1 valency salt, is preferably sodium salt, sylvite or ammonium salt.Its use amount is more than 0.05 grams per liter, better is more than 0.2 grams per liter, and its upper limit is not particularly limited, if consider its economic benefit and 4 bleaching effects, then generally to be advisable below 10 grams per liters.
The Alpha-hydroxy acrylic acid lactone (hereinafter to be referred as PLAC) that the present invention uses is meant the interior and/or intermolecular ester of the molecule that carboxyl and hydroxyl reaction formed of this polymer.
The chemical formula (1) of common uses of above-mentioned and hydroxyl acrylic polymer and/or the organic phospho acid shown in (2) or its esters have the sequestering power of formation complex salt and have cushioning effect.Its esters is preferably sodium salt, sylvite or ammonium salt; Its use amount is 0.2～5 grams per liter, better is 0.3～2 grams per liter.
The example of above-mentioned formula (1) compound can be methylene-1,1-di 2 ethylhexyl phosphonic acid, ethylidene-1,1-di 2 ethylhexyl phosphonic acid, fourth fork-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxyl-propylidene-1,1-di 2 ethylhexyl phosphonic acid etc.During n=0, the example of formula (2) compound can be amino three (methylene phosphonic acids) etc.Again, during n=1, the example of formula (2) compound can be ethylene diamin(e) four (methylene phosphonic acid); During n=2, the example of formula (2) compound can be diethylentriamine five (methylene phosphonic acid) etc.N=3～4 o'clock, the example of formula (2) compound can be triethylenetetramine six (methylene phosphonic acid).
The present composition, as long as be added in the bleaching liquid according to the use amount of aforementioned stable agent, then in room temperature between boiling temperature, use according to conventional method to get final product.The additive of surfactant etc. can arbitrarily use according to conventional method.The fiber-like of processing is based on kapok, and still, other fiber-like can be used too.
Batch formula bleaching machine such as Winch type, Kier type, Obermaier type, jigger type etc. can use stabilizing agent of the present invention certainly, and use continous mode bleaching machine such as J-box, L-Box Perble Range, Benteler etc. can obtain excellent especially bleaching effect.
According to the present invention, at least select PHAS or its esters, or a kind of hydroxyl acrylic polymer among its poly-propyl ester and aforementioned organic phospho acid or its esters are when shared, can obtain composite effect, therefore, can reach bleaching effect more excellent when using sodium metasilicate, and can exempt caused when using sodium metasilicate by the damage on albic material ground, in addition, during again than independent use PHAS, can obtain better whiteness, better remove cottonseed, the bleaching back is few to the infringement of fibre strength, the metal removal ability is strong, metal ion sealing effect excellence, and also preferable by the quality of bleaching thing.Therefore, according to the present invention, can obtain the effect more more excellent than the known in which hydrogen peroxide bleaching agent of present use.
Below, further describe the present invention in detail with embodiment.
Embodiment 1
Cotton knitwear (No. 40) is carried out the steam bleaching under following condition.Bleaching results is as shown in table 1.Comparative example is to adopt the bleaching agent that uses at present, and its result also records and narrates in table 1 in the lump.
The composition of bleaching liquid and conditions of bleaching are as shown in following:
H 2O 2(35%) 40 milliliter/liter
Stabilizing agent
PHAS or PLAC *Ormal weight shown in the table 1
Ormal weight shown in the organic phospho acid table 1
Sanmol S-50 *1 grams per liter
The NaOH(sheet) 3 grams per liters
Wring out rate 100%
100 ℃ of temperature and processing times, 40 minutes
* PLAS: the CLARENE-L(mean molecule quantity that adopts Sorbe company to make is 100,000).
PHAS is the poly-alpha-hydroxy sodium acrylate that adopts PLAC and NaOH reaction to be produced.
* Sanmol S-50: anion system and nonionic that solar corona chemical industry (strain) is made are surfactant mixtures.
Whiteness: Makbes MS-2020 colour examining machine
The measuring reflectance wavelength is 440 millimicrons
Quality: use Japan Boldwin(strain) the Tensiion Instrument measuring of making.By 3 centimetres of diameters, the resistance the when stainless steel ring that thickness is 0.5 millimeter is inner is represented it with 10 centimetres of cloths of 10 cm x.
By table 1 result as can be known, use bleaching agent of the present invention, can obtain than using the comparatively excellent result of existing goods person.
Embodiment 2
Wide cut cotton (No. 40) is carried out the steam bleaching under following condition.Bleaching results is as shown in table 2.
The composition of bleaching liquid and conditions of bleaching are as shown in following:
H 2O 2(35%) 20 milliliter/liter
Stabilizing agent
PHAS *Shown in the table 2
Shown in the organic phospho acid table 2
Sanmol S-50 1 grams per liter
(anionic property that solar corona chemical industry (strain) is made and the mixture of nonionic surfactant)
The NaOH(sheet) 2 grams per liters
Wring out rate 90%
95 ℃ of temperature and processing times, 30 minutes
* is identical with embodiment 1.
The cottonseed property removed: judge with vision.
0: seed completely without.
△: residual little by little seed.
*: residual considerable seed.
As shown in table 2, stabilizing agent of the present invention has more excellent effect than existing product.
Embodiment 3
As shown in table 3, except organic phospho acid and the acrylic acid salt of poly-alpha-hydroxy are to adopt sylvite or the ammonium salt, other condition is all identical with embodiment 1.Under this condition, to cotton knitwear (No. 40) bleach.Its result is as shown in table 3.
Figure 87100624_IMG8
Embodiment 4
The destarch of cotton poplin (No. 40) is made with extra care cloth with 1%FeSO 4.7H 2The O aqueous solution or 1%CuSO 4.5H 2The O aqueous solution has made it a certain amount of spot.After the drying, under the condition identical, bleach, then this bleached cotton fabric is carried out tension intensity and measure with embodiment 2.Its result is as shown in table 4.
Tension intensity: with Autograph JIS-L-1068(constant speed catatonic type) measures.The clamping square is from being 5 centimetres, and pulling force speed is 200 cm per minute, measures with this understanding 5 times, asks its mean value to represent it.Its result is as shown in table 4.
By table 4 result as can be known, bleaching stibilizer of the present invention has more excellent effect than the product that uses at present.
Figure 87100624_IMG9
Note) PHAP: poly-alpha-hydroxy potassium acrylate
PHAA: poly-alpha-hydroxy ammonium acrylate

Claims (1)

  1. A kind of stabilizing agent of hydrogen peroxide bleaching, it is characterized in that selecting for use at least a kind of hydroxyl acrylic polymer among poly-alpha-hydroxy acrylic acid or its esters or its polylactone and have the compound and at least a organic phospho acid or its esters of following general formula (1) with general formula (2).
    Figure 87100624_IMG2
    In the formula (1), A represents that hydrogen or carbon number are 1～3 alkyl, and B represents that hydrogen, hydroxyl or carbon number are 1～3 alkyl, A and B be identical or different all can,
    In the formula (2), D, E and F all represent methylene phosphonic acid base or hydrogen, and m is 1～15 integer, and n is 0～4, better are 0～2 integers, and still, D and E represent in the situation of hydrogen is not included in simultaneously.
CN87100624A 1986-02-10 1987-02-06 Stabilizer for hydrogen peroxide bleaching Expired - Fee Related CN1022940C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP27547 1986-02-10
JP61027547A JPS62185797A (en) 1986-02-10 1986-02-10 Hydrogen peroxide bleaching stabilizer
JP27547/86 1986-02-10

Publications (2)

Publication Number Publication Date
CN87100624A true CN87100624A (en) 1987-08-19
CN1022940C CN1022940C (en) 1993-12-01

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KR (1) KR900001352B1 (en)
CN (1) CN1022940C (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100430532C (en) * 2005-11-25 2008-11-05 中国科学院化学研究所 Stabilizer for use in hydrogen peroxide degumming and bleaching of flax and its preparation method and application
CN101798745A (en) * 2010-03-08 2010-08-11 张家港市德宝化工有限公司 Phosphorus-free biodegradable hydrogen peroxide bleaching stabilizer
CN103061104A (en) * 2012-12-14 2013-04-24 日华化学研发（上海）有限公司 One dosage type low temperature scouring and bleaching agent and application thereof
CN106520406A (en) * 2010-12-17 2017-03-22 科莱恩金融(Bvi)有限公司 Compositions containing hydrogen peroxide or substances releasing hydrogen peroxide
CN111455709A (en) * 2020-05-19 2020-07-28 山东太阳纸业股份有限公司 Production process of APMP

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3720277A1 (en) * 1987-06-19 1988-12-29 Degussa METHOD FOR REDUCING THE TENSION TO BAKING UP PARTICULATE ACTIVE OXYGEN COMPOUNDS
JPH0826349B2 (en) * 1989-06-20 1996-03-13 日華化学株式会社 Detergency improver
JP2602563B2 (en) * 1989-12-15 1997-04-23 花王株式会社 Liquid oxygen bleach composition
US9137525B2 (en) 2002-07-15 2015-09-15 Pure Depth Limited Multilayer video screen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU71985A1 (en) * 1975-03-06 1977-01-28

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100430532C (en) * 2005-11-25 2008-11-05 中国科学院化学研究所 Stabilizer for use in hydrogen peroxide degumming and bleaching of flax and its preparation method and application
CN101798745A (en) * 2010-03-08 2010-08-11 张家港市德宝化工有限公司 Phosphorus-free biodegradable hydrogen peroxide bleaching stabilizer
CN106520406A (en) * 2010-12-17 2017-03-22 科莱恩金融(Bvi)有限公司 Compositions containing hydrogen peroxide or substances releasing hydrogen peroxide
CN103061104A (en) * 2012-12-14 2013-04-24 日华化学研发（上海）有限公司 One dosage type low temperature scouring and bleaching agent and application thereof
CN103061104B (en) * 2012-12-14 2015-05-20 日华化学研发（上海）有限公司 One dosage type low temperature scouring and bleaching agent and application thereof
CN111455709A (en) * 2020-05-19 2020-07-28 山东太阳纸业股份有限公司 Production process of APMP
CN111455709B (en) * 2020-05-19 2021-12-03 山东太阳纸业股份有限公司 Production process of APMP

Also Published As

Publication number Publication date
JPS62185797A (en) 1987-08-14
CN1022940C (en) 1993-12-01
KR870008077A (en) 1987-09-24
JPH0434595B2 (en) 1992-06-08
KR900001352B1 (en) 1990-03-08

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