JPH05302289A - Bleaching agent composition and method for bleaching - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent storage stability and bleaching properties, comprising a peroxide and a specific water-soluble polymer. CONSTITUTION:A bleaching agent composition comprises (A) a peroxide and (B) a water-soluble polymer having a structure of the formula [R<1> and R<2> are independently H or a carbon-containing substituent group and at least one of R<1> and R<2> is CH2COOX<1>, CH2CH2COOX<2>, etc., (X1 and X2 are independently H, monovalent metal, etc.)] at the side chain. The water-soluble polymer is obtained by subjecting an epoxy group-containing polymer such as poly(meth) allyl glycidyl ether or polyglycidyl ether (meth)acrylate and an acid anhydride- based polymer such as maleic anhydride polymer to ring-opening addition reaction with a primary or a secondary amino compound such as iminodiacetic acid (salt), iminodipropionic acid (salt), iminodisuccinic acid (salt), carboxymethyliminosuccinic acid (salt), hydroxyiminodisuccinic acid (salt), N- methylglycine (salt), dithiocarbamic acid (salt) or thiourea.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a bleaching composition and a bleaching method used for bleaching clothes, wood pulp, cellulosic fibers and the like.

[0002]

2. Description of the Related Art Conventionally, since cellulosic fibers still have natural pigments in the fibers even after the refining step, bleaching is carried out to remove the natural pigments and secondary adhered coloring matters. As the bleaching agent, peroxide-based agents such as hydrogen peroxide, sodium percarbonate, sodium peroxide, and peracetic acid, and chlorine-containing agents such as chlorine, bleaching powder, chlorine dioxide, and sodium chlorite are used. Has been.

Since chlorine-containing bleaching agents are expensive and have the drawback of severely corroding bleaching equipment, peroxide-based bleaching agents have become the mainstream in recent years. In addition, among peroxides, hydrogen peroxide is rarely used because it does not damage fibers.

On the other hand, wood pulp such as mechanical pulp (M
P), chemical mechanical pulp (CGP) and other so-called high-yield pulp bleaching methods include the above-mentioned oxidative bleaching method using hydrogen peroxide, sodium percarbonate, sodium peroxide, peracetic acid and sodium hydrosulfite. There is a reduction bleaching method using zinc hydrosulfite.
The reduction bleaching method has a characteristic as a relatively inexpensive bleaching method, but the bleaching property is not sufficient and it is limited to low-whiteness pulp, and the reduction bleaching method has been decreasing in recent years.

Deinked pulp (DIP) has shown a great increase in recent years, and an oxidative bleaching method mainly using hydrogen peroxide has been adopted as a bleaching method. In addition, bleaching of chemical pulp such as soda pulp (AP) and kraft pulp (KP) is performed by chlorine-based bleaching agents such as chlorine, bleaching powder, chlorine dioxide, sodium chlorite, thiosulfates, and sulfites.
A so-called multi-stage bleaching method is used in which a sulfur-containing reducing bleaching agent such as bisulfite is combined.

However, the chlorine-based oxidative bleaching agent corrodes the bleaching apparatus violently as in the case of the above-mentioned fiber due to the increase of residual chlorine and the temperature rise. Furthermore, there is a problem of dioxin generation. Further, although chlorine dioxide is one of the most frequently used chlorine bleaching agents and exhibits excellent bleaching properties, it has the drawbacks of being expensive and increasing the drainage load. In order to eliminate the drawbacks of these chlorine-based bleaching agents, the use of peroxide-based bleaching agents has been expanding in the bleaching of chemical pulp in recent years. In addition, as a bleaching agent for clothes in general households,
From the viewpoint of safety, a bleach composition containing a peroxide bleach as a main component instead of a chlorine bleach has started to spread.

By the way, such a peroxide-based bleaching composition containing peroxide as a main component gradually undergoes peroxide oxidation during long-term storage due to the catalytic action of a trace amount of polyvalent metal ions in the composition. Product containers may require special ones as they are decomposed to generate gas.

Further, since peroxide such as hydrogen peroxide alone has a low bleaching effect, it may be bleached at high pH using an alkaline agent such as sodium hydroxide.

[0009] The hydrogen peroxide in the alkaline range, H ₂ O ₂ + OH ^-
→ It is known that peroxyhydroxy ion is generated like OOH ⁻ + H ₂ O, and this peroxyhydroxy ion shows a bleaching effect. However, at this time, by the catalytic action of various polyvalent metal ions such as iron ions, copper ions and manganese ions present in the water to be bleached or bleached product, the above reaction to generate peroxy ions does not occur,

[0010]

[Chemical 5]

As described above, hydrogen peroxide is unnecessarily decomposed.

Auxiliaries are usually used to suppress these decompositions. As this auxiliary agent, an inexpensive silicic acid-based agent such as sodium silicate is often used.

However, since the silicic acid chemicals do not have a sufficient function of suppressing the unnecessary decomposition of hydrogen peroxide, for example, leather cut marks (scratches like razor cuts) or pinholes are formed on the fiber after bleaching. There was a problem such as occurrence. Further, silicic acid or polymerized silicic acid when a silicic acid-based agent is used binds to polymetal ions or the like to form a so-called insoluble salt (scale), which is deposited on the bleached substance and the device during the bleaching process. When the material to be bleached is a fiber, if the scale is deposited on the fiber, the whiteness of the fiber is not improved, and the texture is coarsely hardened, which causes a problem in the sewability. Further, if the scale is continuously deposited on the bleaching device for a long time, it may cause a serious accident called scale trouble.

Two methods have been proposed to overcome the above problems of the silicic acid type drug. One is a method of using a silicic acid-based drug substitute, and the other is a method of using a silicic acid-based drug in combination with other auxiliary agents to complement the silicate.

Substitutes for silicic acid-based agents include sulfites and sodium poly-α-hydroxyacrylate (see Japanese Patent Laid-Open No. 5-312058).
2-103386) has been proposed. Sulfite is used as an inexpensive wood pulp bleaching aid, but it forms an insoluble salt by combining with a polyvalent metal in wood and an alkaline earth metal compound or an aluminum compound added as an aid. It is easy to cause scale problems such as clogging on the refiner plate.
In addition, sodium poly-α-hydroxyacrylate is extremely expensive and cannot be used as a substitute for a silicic acid-based drug.

On the other hand, as an auxiliary agent used in combination with a silicic acid-based agent, an aminocarboxylic acid-based agent such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxylethylenediaminetriacetic acid and nitrilotriacetic acid (JP-A-49-52784) or tripolyline Condensed phosphoric acid-based auxiliaries such as acids, hexametaphosphoric acid, and pyrophosphoric acid are used (for example, Japanese Examined Patent Publication No. 40-7774).

However, the aminocarboxylic acid type auxiliary agent requires a large amount of addition because its emulsifying and dispersing power to the scale is extremely weak. Further, the condensed phosphoric acid-based auxiliary agent is
As wastewater, it flows into the sea through rivers and becomes a causative substance such as red tide. In the bleaching step, under high temperature and high alkaline conditions, the effect is reduced by being hydrolyzed to phosphoric acid, and the phosphoric acid produced by the hydrolysis becomes a causative substance that promotes scale if combined with various polyvalent metal ions.

[0018]

DISCLOSURE OF THE INVENTION In order to eliminate the drawbacks of the aminocarboxylic acid-based and condensed phosphoric acid-based auxiliaries, a fiber bleaching aid is disclosed in JP-A-59-211673.
JP-A-59-216973, JP-A-60-146
No. 076 and the like propose the use of (co) polymers using one or more unsaturated carboxylic acid type monomers such as (meth) acrylic acid and maleic acid. However, since these (co) polymers have weak chelating ability for manganese ion, iron ion, copper ion and the like, hydrogen peroxide is wastefully decomposed, and as a result, the bleached product is not sufficiently bleached. Moreover, the (co) polymer itself easily forms scales with the above polyvalent metal ions, and the present situation is that a drastic solution has not been reached.

Further, JP-A-61-289187 proposes the use of a copolymer of an olefin and an unsaturated dicarboxylic acid type monomer, and this copolymer is also disclosed in JP-A-59-2.
11673, JP-A-59-216973, JP-A-6
It was about the same as the copolymer described in 0-146076.

Further, in JP-A-62-32195, a (co) polymer containing one or more unsaturated carboxylic acid type monomers such as (meth) acrylic acid and maleic acid is used in combination with aldonic acid. It has been proposed to do so, but with some improvements, it is still problematic.

It is also possible to use a copolymer obtained by reacting maleic acid with a polyoxyalkylene monoallyl ether type monomer as an auxiliary agent.
No. 6 is proposed. However, since such an auxiliary agent has a weak emulsifying and dispersing power of the scale, it is not possible to sufficiently suppress the deposition of the scale on an object to be bleached or a bleaching device, and there is still a problem.

Further, JP-A-1-250467 proposes a copolymer of a specific unsaturated carboxylic acid type monomer and an unsaturated alcohol type monomer. Japanese Patent Laid-Open No. 1-25046
No. 8 proposes a copolymer of a specific unsaturated carboxylic acid monomer and an unsaturated (meth) allyl ether monomer. Although these polymers have received relatively good evaluations, they are polyvalent metals that uselessly decompose peroxides such as manganese ions, iron ions, and copper ions that are eluted from the bleached substance or are present in the water. When the ion concentration is high, there is a problem that bleaching cannot be performed sufficiently.

Further, as a bleaching aid for wood pulp, use of carboxylic acid type polymers such as sodium polyacrylate and sodium polymaleate in JP-A-1-52892, JP-A-1-148890 and JP-A-1-148891. Proposed, but still problematic.
Further, as an auxiliary agent for a liquid bleaching agent, JP-A-3-91597.
No. 3, JP-A-3-91598, JP-A-3-188198
JP-A-3-285998, JP-A-3-28599
No. 9 and JP-A-3-286000 propose the use of carboxylic acid-based polymers such as sodium polyacrylate and sodium polymaleate.

Further, as an auxiliary agent for a solid bleaching agent, JP-A-62-62
The use of carboxylic acid type polymers such as sodium polyacrylate and sodium polymaleate has been proposed in JP-A-253697, JP-A-3-215599, JP-A-3-215600 and JP-A4-1299.

The bleaching agent composition containing these carboxylic acid type polymers has low bleachability and insufficient storage stability. Further, there is a problem that the peroxide is decomposed with the lapse of time to deteriorate the bleaching performance and a special storage container is required for the generated gas.

In view of the above problems, it is an object of the present invention to provide a bleaching composition and a bleaching method which are inexpensive and have improved storage stability and bleachability. Another object of the present invention is to provide a bleaching method using a bleaching aid that does not cause scale hindrance and has improved bleaching properties when used in combination with a silicate which is a commonly used aid.

[0027]

The bleaching composition according to the present invention has a peroxide and the following formula in order to solve the above problems. A)), X ^{1 to} X ¹¹ each independently or together represent hydrogen, a monovalent metal, a divalent metal, an inorganic or organic ammonium group, and a and b are 1 to 1;
(Representing an integer of 7) is contained in the side chain of the water-soluble polymer having a structural unit (I).

The bleaching method according to the present invention is a method in which the above water-soluble polymer is used as a bleaching aid and bleaching is performed using a peroxide.

The method for obtaining the water-soluble polymer having the structural unit (I) in the side chain is not particularly limited, and a wide range of methods can be adopted. For example, polymers containing an epoxy group such as poly (meth) allyl glycidyl ether, polyglycidyl (meth) acrylate, and acid anhydride polymers such as polymaleic anhydride are treated with iminodiacetic acid (salt), iminodipropionic acid ( (Salt), iminodisuccinic acid (salt), carboxymethyliminosuccinic acid (salt), hydroxyiminodisuccinic acid (salt), N-methylglycine (salt), dithiocarbamic acid (salt), thiourea etc. It is obtained by ring-opening addition using a secondary amine as a raw material.

Further, a monomer containing an epoxy group such as (meth) allyl glycidyl ether or glycidyl (meth) acrylate and an acid anhydride type monomer such as maleic anhydride are used as the above primary or secondary amine. It is of course also possible to obtain it by (co) polymerizing the monomer obtained by ring-opening addition with.

[0031] A polymer having a side chain, formalin and phosphorous acid can be used as raw materials. Alternatively, it is of course possible to derive from a monomer having —NH— in the side chain and a monomer obtained by using the above raw materials.

In addition, a water-soluble polymer having a structural unit (I) in its side chain can be produced from a polymer and a monomer by a dehydrochlorination reaction, an esterification reaction and the like.

At least one of R ¹ and R ^{2 in} the structural unit (I) is in the above substituent group (A). It is preferable to select from (Substituent group (B)) because the resulting water-soluble polymer has a high chelating power for various polyvalent metal ions, resulting in improved bleaching property.

Further, the substituent group (B) can be easily introduced into the water-soluble polymer, and is therefore preferable for obtaining an inexpensive water-soluble polymer. Further, it is more preferable to select both R ¹ and R ² from the substituent group (B) since the chelating power of the obtained water-soluble polymer is further improved.

As the water-soluble polymer having the structural unit (I) in the side chain, there are various kinds as described above, and among them, the following formula

[0036]

[Chemical 6]

[0037] And X ^{1 to} X ⁶ represent the above-mentioned meaning).

Among them, a water-soluble polymer in which Z ¹ is hydrogen and Z ² is —CH ₂ — is more preferable because it can be produced at a low cost and can be used under extremely severe conditions (high temperature, high alkali, etc.).

The ratio of the structural unit (II) in the water-soluble polymer is not particularly limited, but Z ² is --CH ₂ % Is preferred. A water-soluble polymer out of this ratio range tends to have a reduced bleaching property.

When the water-soluble polymer containing the structural unit (II) is a copolymer, its comonomer component is not particularly limited and a wide range of monomers can be used.
For example, the general formula (In the formula, A ¹ and A ² each independently represent hydrogen, a methyl group or —COOX ¹³ , and A ¹ and A ² are simultaneously represented by —
It does not become COOX ¹³ , A ³ represents hydrogen, a methyl group or —CH ₂ COOX ¹⁴ and A ³ represents —CH ₂ COO.
In the case of X ¹⁴ , A ¹ and A ² each independently represent hydrogen or a methyl group, and X ¹² , X ¹³ and X ¹⁴ are independently or together hydrogen, a monovalent metal, a divalent metal, an ammonium group or Unsaturated carboxylic acid type monomer (III) represented by (representing an organic amine group) [as such unsaturated carboxylic acid type monomer (III), acrylic acid, methacrylic acid, crotonic acid or their Monovalent metal, divalent metal, ammonia, partially neutralized or fully neutralized product with organic amine, (anhydrous) maleic acid, itaconic acid, fumaric acid, citraconic acid or their monovalent metal, divalent metal, ammonia,
Examples include partially neutralized products and fully neutralized products with organic amines. Examples of the monovalent metal include sodium and potassium, and examples of the divalent metal include calcium and magnesium. The organic amines include alkylamines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine and triethylamine, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and dimethylethanolamine, pyridine. Etc. can be given. Of these, sodium is most preferable because it is inexpensive and industrially available]; (meth) acrylamide, amide-based monomers such as t-butyl (meth) acrylamide; (meth) acrylic acid ester, styrene, 2-methylstyrene, Hydrophobic monomers such as vinyl acetate; vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-
Acrylamide-2-methylpropanesulfonic acid, 3-
Allyloxy-2-hydroxypropanesulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, 2-hydroxysulfopropyl (meth) acrylate, sulfoethylmaleimide or their monovalent metal, divalent metal, ammonia, organic amine Unsaturated sulfonic acid monomers such as partially neutralized products and fully neutralized products; 3-methyl-3-buten-1-ol (isoprenol), 3-methyl-2-buten-1-ol (prenol) , 2-methyl-3-buten-2-ol (isoprene alcohol), 2-hydroxyethyl (meth)
Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol monoisoprenol ether, polypropylene glycol monoisoprenol ether, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether,
Unsaturated hydroxyl group-containing monomers such as glycerol monoallyl ether, α-hydroxyacrylic acid, N-methylol (meth) acrylamide, glycerol mono (meth) acrylate and vinyl alcohol; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl ( Cationic monomers such as (meth) acrylamide; nitrile monomers such as (meth) acrylonitrile; ethylene, propylene, 1-butene, isobutylene, α-amylene,
2-methyl-1-butene, 3-methyl-1-butene (α
-Isoamylene), 1-hexene, 1-heptene, and other α-olefin-based monomers. Above all, it is preferable to use the unsaturated carboxylic acid monomer (III).

The molecular weight of the water-soluble polymer is not particularly limited, but the weight average molecular weight is 500 to 10,000.
00 is particularly preferred. When the weight average molecular weight is less than 500, the chelating power is lowered, and as a result, the bleaching property tends to be lowered. When the weight average molecular weight exceeds 1,000,000, the polyvalent metal ion tends to cause the water-soluble polymer to gel, and as a result, the bleaching property tends to decrease.

The water-soluble polymer in the present invention is a polymer having a solubility in water of 1% or more, and either an acid type or a salt type can be used. Examples of the salt type include monovalent metal salts, divalent metal salts, and inorganic or organic ammonium salts.

Examples of the monovalent metal salt include sodium salt,
Examples thereof include potassium salt and lithium salt. Examples of the divalent metal salt include calcium salt and magnesium salt. Examples of the inorganic or organic ammonium salt include alkylamine salts such as ammonium salt, monomethylamine salt, dimethylamine salt, trimethylamine salt, monoethylamine salt, diethylamine salt and triethylamine salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt. Examples thereof include alkanolamine salts such as monoisopropanolamine salt and dimethylethanolamine salt, and pyridine salt. Of these, sodium salt is most preferable because it is inexpensive and industrially available.

Further, in order to make the polymer water-soluble, the content of the divalent metal salt is preferably 10 mol% or less based on the total carboxylic acid groups.

The reason why the water-soluble polymer of the present invention exhibits excellent bleaching properties when used as an auxiliary agent is not clear, but in the case of bleaching wood pulp, it is presumed as follows.

That is, when a water-soluble polymer is used as an assistant, 1) delignification is promoted, 2) Mn, Cu, Fe, Ni, Co, etc. which are eluted from the wood pulp or are present in the water Chelate the polyvalent metal ion of the above to suppress the unnecessary decomposition of the peroxide, 3) to suppress the auto-oxidation of the chromophore in the wood, especially the quinones, 4) colored metallic water such as Fe, Cu and Ni It may be possible to prevent the insoluble substance of oxide from being (re) attached to the wood pulp as a scale.

Further, when a water-soluble polymer and a silicate are used together as an auxiliary agent, the reason for preventing the silica-based scale from adhering to various devices is not clear, but the water-soluble polymer has a specific structure. It is considered that this is because it has a high crystal growth suppressing ability and / or a dispersing ability with respect to the silica-based scale.

From the above reasons, it is presumed that the use of the water-soluble polymer improves the bleaching property and eliminates the scale trouble as compared with the conventionally known auxiliaries.

Examples of the above-mentioned peroxides include hydrogen peroxide, percarbonates such as sodium percarbonate and potassium percarbonate, sodium peroxide, peracetic acid and the like. Among them, hydrogen peroxide and percarbonate are particularly preferable. .. The bleaching composition is a liquid when it contains hydrogen peroxide and a liquid or solid composition when it contains a percarbonate.

Examples of the bleaching product in the bleaching method include clothes, wood pulp, non-wood pulp, and cellulosic fibers. Wood pulp that can be suitably bleached includes mechanical pulp (MP) and chemical mechanical pulp (C
High yield pulp such as GP), deinking pulp (DIP), chemical pulp such as soda pulp (AP) and kraft pulp (KP) can be mentioned.

The amount of the water-soluble polymer used for bleaching the wood pulp is not particularly limited, but 0.04 to 0.8% by weight is usually preferred for the absolutely dry pulp. When the amount used is less than 0.04% by weight, the bleaching property tends to decrease. Further, even if it is used in an amount exceeding 0.8% by weight, the effect commensurate with the increase in amount cannot be obtained.

Cellulose fibers that can be suitably bleached include, for example, natural cellulose fibers such as cotton and hemp, regenerated cellulose fibers such as rayon and cupra, and nylon, polyester, acrylic and the like. There are mixed fibers with synthetic fibers, and also mixed fibers with semi-synthetic fibers such as acetate. The bleaching forms are also fibers, threads, cheese, woven fabrics, knitted fabrics, non-woven fabrics, and even clothing,
Any form such as final textile products such as bedding products can be used.

As a method for bleaching these fibers using a water-soluble polymer, a usual method can be applied, and a pad / steam method, a pressure boiling method, a boiling method, a dipping method or the like can be appropriately selected. Furthermore, the water-soluble polymer can be applied not only to the bleaching described so far, but also to bleaching performed in one bath at the same time as other steps such as refining / bleaching, desizing / refining / bleaching. ..

The amount of the water-soluble polymer used for bleaching the cellulosic fibers by such a method is not particularly limited, but 0.5 to 15 g per 1 liter of the bleaching solution is usually used. If the amount used is less than 0.5 g / liter, the bleaching property tends to decrease. Further, even if the amount exceeds 15 g / liter, the effect commensurate with the increase in amount cannot be obtained.

When bleaching is carried out using a water-soluble polymer as an auxiliary agent, an aminocarboxylic acid salt which has been conventionally used,
Condensed phosphates such as silicates, sulfites, tripolyphosphates, alkaline earth metal compounds such as magnesium and calcium, aluminum compounds, polycarboxylates such as polyacrylates, poly α-hydroxyacrylates, etc. You may use together the auxiliary agent of.

Further, the water-soluble polymer is not only an auxiliary agent for peroxide bleaching as in the present invention, but also has a slightly inferior effect, but chlorine, bleaching powder, chlorine dioxide, chlorine-containing chlorite and other chlorine-based oxidation agents are used. It is also effective as a bleaching agent and an auxiliary agent for sulfur-containing reducing bleaching agents such as sodium hydrosulfite, zinc hydrosulfite, thiosulfates, sulfites, and bisulfites.

On the other hand, the blending amount of the water-soluble polymer in the bleaching agent composition is not particularly limited, but usually 0.05 to 20% by weight is preferred. When the amount used is less than 0.05% by weight, the bleaching property tends to decrease. Even if it is used in an amount exceeding 20% by weight, the effect commensurate with the increase in amount cannot be obtained.

The blending amount of the peroxide in the bleaching composition is not particularly limited, but 0.5 to 60% by weight is preferably used.

The bleaching composition for household use such as clothes preferably contains a surfactant, and the surfactant is not particularly limited and a wide range can be used. For example, anionic surfactants such as linear alkylbenzene sulfonate, polyoxyethylene alkyl ether sulfate, α-olefin sulfonate, alkyl sulfate, and the like;
Examples thereof include nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether; amphoteric surfactants such as betaine type. The amount of the surfactant in the composition is not particularly limited, but 0.1 to 20% by weight is preferably used.

In the case of a liquid bleaching composition using hydrogen peroxide as a peroxide, the bleaching composition of the present invention usually contains water and a pH adjusting agent in addition to the water-soluble polymer. The pH adjusting agent is not particularly limited, but inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as citric acid, malic acid and gluconic acid, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate, An alkali metal carbonate such as potassium carbonate is used.

The pH adjusting agent is preferably added so that the composition has a pH in the range of 1 to 7, and particularly preferably in the range of 2 to 6.5. When the pH is lower than the above range, skin irritation becomes strong, and when the pH exceeds the above range, the storage stability of the composition may become insufficient.

It is, of course, possible to incorporate the auxiliaries conventionally used in the above-mentioned household bleaching compositions for clothing and the like. Examples of such auxiliaries include condensed phosphoric acid-based auxiliaries such as sodium tripolyphosphate and potassium pyrophosphate, aminocarboxylic acids such as ethylenediaminetetraacetic acid (salt), diethylenetriaminepentaacetic acid (salt), and nitrilo3acetic acid (salt). Acid (salt), alkylidene diphosphonic acid (salt),
Examples thereof include organic phosphonic acids (salts) such as nitrilotrimethylenephosphonic acid (salts), carboxylic acid-based polymers such as poly α-hydroxyacrylic acid (salts), sodium polyacrylate and sodium polymaleate.

It is also possible to add a coloring agent such as a pigment or dye for tinting, if necessary.

As the pigment, for example, color index vat blue 4, color index vat blue 6,
Organic pigments such as Color Index Pigment Blue 22, Color Index Butt Red 23, Color Index Pigment Blue 15, Color Index Pigment Blue 17, Color Index Pigment Green 36; navy blue, ultramarine blue or cobalt pigments, cadmium pigments, iron oxides, dioxide Inorganic pigments such as titanium may be mentioned.

As the dye, color index acid blue 229, color index acid blue 9, color index acid blue 112, Alizarin
e Fast Blue ERL (Yamada Chemical Co., Ltd.), Alizarine Fast Blue
Acid dyes such as 3GL (manufactured by Yamada Chemical Co., Ltd.), Fastogen Blue 5380 (manufactured by Dainippon Ink and Chemicals, Inc.), Color Index Acid Red 198, Color Index Acid Blue 158, Color Index Acid Green 35, Color Index Direct Blue 86, Color Index Direct Examples include metal-containing dyes such as Blue 199.

[0066]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Further, in the examples, "parts" means "parts by weight" and "%" means "weight%" unless otherwise specified.

Example 1 Method for Producing Water-Soluble Polymer 1 A glass reactor having a capacity of 2 liters equipped with a stirrer and a condenser was charged with 433.8 parts of ion-exchanged water, 429.6 parts of 48% sodium hydroxide and iminodimine. 342.9 parts of acetic acid was charged. 293.7 parts of allyl glycidyl ether was dropped from the dropping nozzle in 60 minutes while maintaining the temperature at 65 ° C. under stirring.
After completion of dropping, the reaction was completed by keeping the same temperature for 30 minutes.

Chemical formula with a concentration of 50% A monomer (D) having an iminodi structure represented by

In a glass reactor having a capacity of 2 liters equipped with a stirrer and a condenser, the above monomer (D) 50 was added.
% Aqueous solution 573 parts and ion exchange water 449.5 parts were charged and the temperature was raised to 95 ° C. 80% acrylic acid aqueous solution 3 with stirring
Polymerization was completed by adding 54.4 parts and 123.1 parts of a 20% aqueous sodium persulfate solution through separate dropping nozzles over 60 minutes and maintaining the same temperature for 10 minutes.

Mainly monomer (D) / acrylic acid = 2
A water-soluble polymer 1 composed of a / 8 (molar ratio) copolymer was obtained. The total polymerization rate of water-soluble polymer 1 was 99 mol%.
Further, the weight average molecular weight was measured by an aqueous GPC, and the results are shown in Table 1.

Water-soluble polymer 2-25 Water-soluble polymer 2-2 in the same manner as water-soluble polymer 1
Got 5.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

[0077]

[Table 6]

[Experimental Example 1] In a polyethylene bottle having a capacity of 600 ml, 35% hydrogen peroxide solution 71.4 g, polyoxyethylene alkyl ether (having 12 carbon atoms in the alkyl group,
Ethylene oxide addition mole number 10) 15 g, straight chain sodium alkylbenzene sulfonate (alkyl group carbon number 12) 35 g, water-soluble polymer 1 obtained as described above 10 g (solid component conversion) and tap water 300 g It was put and dissolved uniformly.

Next, the pH was adjusted to 4.5 with dilute sulfuric acid, and then tap water was added to bring the total amount to 500 g, to obtain a bleaching agent composition (a). Storage stability was evaluated by sealing the bottle and visually observing the state of the bottle after leaving it at 55 ° C. for 14 days. The results are shown in Table 7.

Next, the bleaching composition (a) was dissolved in 1 liter of tap water containing 10 ppm of Fe ³⁺ ions so that the effective oxygen concentration was 0.05%, and the temperature was raised to 30 ° C. Five pieces of black tea-contaminated cloth prepared as described below were immersed in the cloth for 30 minutes, rinsed with tap water and dried, and the bleaching rate was calculated by the following formula. The results of the obtained bleaching rate are also shown in Table 7.

[0081]

[Equation 1]

Preparation Method of Black Tea-Contaminated Cloth 80 g of black tea is boiled in 3 liters of ion-exchanged water for 15 minutes, then rubbed with desalted cotton, and cotton gold cloth # 2003 cloth is dipped in this liquid and boiled for 15 minutes. Remove from heat, let stand for 2 hours, let dry naturally, wash with water until the washing liquid does not become colored, dehydrate, press, and make a test piece of 8 cm x 8 cm.

[Experimental Examples 2 to 36] The bleaching composition was repeated by repeating the same procedure except that the water-soluble polymer 1 in Experimental Example 1 was replaced with the water-soluble polymers 2 to 36 shown in Tables 1 to 6, respectively. I got a thing. Using the obtained bleaching agent composition, storage stability and bleachability were evaluated in the same manner as in Experimental Example 1. The results are shown in Tables 7 and 8.

[Experimental Example 37] The same as Experimental Example 1 except that the pH of the composition in Experimental Example 1 was set to 5.5 and the water-soluble polymer 1 was changed to the water-soluble polymer shown in Table 8. The operation was repeated to obtain a bleaching agent composition. The storage stability and bleaching property of the obtained bleaching agent composition were evaluated. The results are shown in Table 8.

[0085]

[Table 7]

[0086]

[Table 8]

[Comparative Examples 1 to 6] A bleaching composition for comparison was obtained in the same manner as in Experimental Example 1 except that the auxiliary agents shown in Table 9 were used instead of the water-soluble polymer 1 in Experimental Example 1. .. The storage stability and bleaching property of the obtained comparative bleaching composition were evaluated.
The results are also shown in Table 9.

[0088]

[Table 9]

[Experimental Example 38] A bleaching agent composition (b) was obtained according to the blending amounts shown below. C _14-18 sodium α-olefinsulfonate 10% chain alkyl (C ₁₂ ) sodium benzenesulfonate 10% Softanol EP12050 (manufactured by Nippon Shokubai Co., Ltd.) 5% C ₁₈ fatty acid sodium 5% sodium carbonate 20% sodium percarbonate 20 % Tetraacetylethylenediamine 6% Zeolite 8% Water-soluble polymer 1 3% Sodium sulphate 6% Moisture 7% 150 ml of the bleaching composition (b) was put into a glass mayonnaise bottle with a volume of 225 ml and recycled at 45 ° C ← → 25 ° C. Stored under conditions for 1 month. Thereafter, 5 g of the bleaching agent composition (b) was sampled, 50 ml of a 50% aqueous acetic acid solution was added, the amount of available oxygen was determined by iodometry, and the available oxygen remaining rate was calculated by the following formula.

[0090]

[Equation 2]

The results obtained are shown in Table 10.

[Experimental Examples 39 to 73] Instead of the water-soluble polymer 1 in Experimental Example 38, water-soluble polymers 2 to 36 were used.
The same operation as in Experimental Example 38 was repeated except that the above was used to obtain a bleaching agent composition. The available oxygen residual ratio (%) was measured using each of the obtained bleaching compositions. The results are shown in Tables 10 and 11.

[0093]

[Table 10]

[0094]

[Table 11]

[Comparative Examples 7 to 10] A bleaching composition for comparison was obtained in the same manner as in Experimental Example 38 except that the auxiliary agents shown in Table 12 were used instead of the water-soluble polymer 1 in Experimental Example 38. .. The available oxygen residual ratio (%) was measured using each of the obtained comparative bleaching compositions. The results are also shown in Table 12.

[0096]

[Table 12]

[Experimental Example 74] A bleaching agent composition (c) was obtained according to the blending amounts shown below. Polyoxyethylene alkyl ether 15% (alkyl carbon number 12, ethylene oxide addition mol number 8) sodium linear alkylbenzene sulfonate (C ₁₄ ) 3% soap (beef tallow) 1% synthetic zeolite (4A type) 35% No. 1 silicic acid Sodium 10% Sodium carbonate 5% Polyoxyethylene glycol (Molecular weight 14000) 2% Enzyme (protease) 1% Sodium percarbonate 8% Sodium sulfate residual amount Acyl compound (Note i) 3% Water-soluble polymer 12% Fluorescent dye Trace amount Fragrance Trace amount of water 4%

[0098]

[Chemical 7]

The bleaching detergency of the bleaching agent composition (c) was evaluated according to the formulation shown below. Bleached product to be bleached Red wine contaminated cloth (Note ii) Bleaching agent composition (c) Concentration 0.08% Bath ratio 1/60 Water temperature 20 ° C Water quality Fe ³⁺ 10ppm in tap water washer Targotometer Washing time 10 minutes (Note ii) Contamination cloth for red wine Put red wine (R10JA "Siglo") in a vat, and 8x50
A cloth having a size of cm was soaked for 10 seconds on each side, passed through a roller, and air-dried. The reflectance of the washed stained cloth at 520 nm was measured, and the bleaching washing rate was calculated according to the following formula.

[0100]

[Equation 3]

The obtained results are shown in Table 13.

[Experimental Examples 75 to 109] In Experimental Example 74, the water-soluble polymer 1 was replaced with the water-soluble polymers 2 to 3 respectively.
The same operation as in Experimental Example 74 was repeated except that 6 was used to obtain a bleaching agent composition. The bleaching cleaning rate was calculated using each of the obtained bleaching agent compositions. The obtained results are shown in Tables 13 and 14.

[0103]

[Table 13]

[0104]

[Table 14]

Comparative Examples 11 to 14 A bleaching composition for comparison was obtained in the same manner as in Experimental Example 74 except that the auxiliary agents shown in Table 15 were used instead of the water-soluble polymer 1 in Experimental Example 74. ..
The bleaching cleaning rate (%) of the obtained comparative bleaching agent composition was calculated, and the results are also shown in Table 15.

[0106]

[Table 15]

Example 2 The water-soluble polymers 1-36 produced in Example 1 were used to bleach cellulosic fibers.

[Experimental Example 110] A water-soluble polymer 1 was used as an auxiliary agent in an amount of 2 g / liter, and a refined cotton knitted fabric knit was bleached under the following conditions. The results are shown in Table 16.

Water used Himeji-shi Water bath ratio of Cu ²⁺ , Fe ³⁺ and Mn ²⁺ added 10ppm each 1:25 Temperature 85 ° C Time 30 minutes Agent used Hydrogen peroxide 10g / l Sodium hydroxide 2g / l No. 3 sodium silicate 5 g / l Evaluation method The texture of the treated cloth was judged by a sensory test method. The whiteness is measured by using a 3M color computer SM-3 (manufactured by Suga Test Instruments Co., Ltd.), and a Lab-based whiteness formula is used.

[0110]

[Equation 4]

The whiteness (W) was obtained and evaluated by. The sewability was evaluated by the number of ground yarn breakage points when four sheets of cloth were stacked and sewn by 30 cm with a lock stitch machine using needle # 11S.

[Experimental Examples 111 to 145] Bleaching was performed in the same manner as in Experimental Example 110 except that the water-soluble polymers 2 to 36 were used as auxiliary agents. The obtained results are shown in Tables 16 and 17.

[Experimental Example 146] Bleaching was carried out in the same manner as in Experimental Example 110 except that 7 g / liter of the water-soluble polymer 1 was used without using No. 3 sodium silicate. The results obtained are shown in Table 17.

[0114]

[Table 16]

[0115]

[Table 17]

[Comparative Examples 15 to 23] Bleaching was performed in the same manner as in Experimental Example 110 except that the compounds shown in Table 18 were used as auxiliary agents. The obtained results are also shown in Table 18.

[Comparative Example 24] Instead of the water-soluble polymer 1,
Bleaching was performed in the same manner as in Experimental Example 146 except that sodium poly-α-hydroxyacrylate was used. The obtained results are shown in Table 18.

[0118]

[Table 18]

Example 3 The water-soluble polymers 1-36 produced in Example 1 were used to bleach pulp.

[Experimental Example 147] In a beaker having a capacity of 500 ml, 30 parts of unbleached refiner ground pulp, which is a kind of high-yield pulp, was charged as an absolute dry weight, and then Fe ³⁺ , C was added.
Water containing 20 ppm each of u ²⁺ and Mn ²⁺ was added in an amount necessary for finally obtaining a pulp concentration of 14%. Under low speed stirring, 0.06 parts (0.2% of pulp) of water-soluble polymer 1 as an auxiliary agent as a solid component and 3.43 parts of 35% hydrogen peroxide as peroxide (vs. pulp) 4%) and 0.9 part of sodium silicate No. 3 (vs. pulp 3%) were added, and the pH of the system was adjusted to 11.0 using sodium hydroxide.

This was transferred to a polyethylene bag, the inlet was turned back so as to prevent water from evaporating, and then heat-treated in a water bath adjusted to 65 ° C. for 5 hours. The pulp slurry thus bleached was dehydrated and then washed with 1000 parts of ion-exchanged water. A portion of the pulp thus obtained is diluted to 3% and the pH is adjusted with a sulfite solution.
Adjusted to 4.5. Using this diluted and pH-adjusted pulp slurry, two handmade sheets were prepared by the TAPPI standard method, air-dried, and then measured for whiteness by a Hunter whiteness meter. The obtained results are shown in Table 19.

[Experimental Examples 148 to 182] Water-soluble polymer 2
The whiteness of the handmade sheet was measured in the same manner as in Experimental Example 147 except that ~ 36 was used. The obtained results are shown in Tables 19 and 20.

[0123]

[Table 19]

[0124]

[Table 20]

[Comparative Examples 25 to 31] The whiteness of the handmade sheet was measured in the same manner as in Experimental Example 147 except that the auxiliaries shown in Table 21 were used. The obtained results are also shown in Table 21.

[0126]

[Table 21]

[Experimental Example 183] 1500 parts of water containing 65 ppm of Fe ³⁺ , Cu ²⁺ and Mn ²⁺ at a temperature of 65 ° C and 2 cm x 2 in a standard disaggregator described in JIS P-8209.
75 parts of waste newspaper, shredded into 2 cm pieces, was charged and lightly disaggregated for 1 to 2 minutes. The waste paper pulp slurry obtained by scraping off the sample adhering to the propeller and the inner wall contains 0.1% (to pulp) of the water-soluble polymer 1 as an auxiliary agent as solid content, 1.5% of hydrogen peroxide. (Vs pulp), sodium hydroxide 1.5%
(Vs. pulp), No. 3 sodium silicate 3% (vs. pulp)
And 0.2% of deinking agent (sodium oleate) (vs pulp) were added, and the mixture was disintegrated at 60 ° C. for 20 minutes. After disintegration, transfer the waste paper pulp slurry to a polyethylene bag, fold back the inlet to prevent water from evaporating, and then preheat at 60 ° C.
It was aged in a water bath adjusted to 2 hours. The disintegrated waste paper pulp slurry after aging was diluted to 1%, subjected to flotation at 30 ° C. for 10 minutes, filtered through a standard mesh sieve, and dehydrated to a concentration of 10%. Next, dilute the pulp slurry to a concentration of 1% and use aluminum sulfate to adjust the pH.
Adjusted to 5.3.

Using the pH-adjusted deinked pulp slurry, a handmade sheet having a basis weight of 100 g / m ² was prepared by a tappy sheet machine, and after air drying, the whiteness was measured by a Hunter whiteness meter. The results obtained are shown in Table 22.

[Experimental Examples 184 to 218] Water-soluble polymer 2
A hand-made sheet was prepared and the whiteness thereof was measured in the same manner as in Experimental Example 183 except that Nos. 36 to 36 were used. The obtained results are shown in Tables 22 and 23.

[Experimental Example 219] A handmade sheet was prepared and its whiteness was measured in the same manner as in Experimental Example 183 except that the predetermined amount of the auxiliary agent shown in Table 23 was used. The obtained results are also shown in Table 23.

[Experimental Example 220] Hand-made sheet in the same manner as in Experimental Example 183 except that 1.5% of hydrogen peroxide (relative to pulp) and 1.5% of sodium peroxide (relative to pulp) were used. Was prepared and its whiteness was measured. The results obtained are shown in Table 23.
It was shown to.

[Experimental Example 221] Except that 0.5% hydrogen peroxide (to pulp) and 0.5% hydrogen peroxide (to pulp) and peracetic acid 1.0% (to pulp) were used instead of 1.5% hydrogen peroxide (to pulp). A handmade sheet was prepared in the same manner as in Experimental Example 183, and its whiteness was measured.
The obtained results are shown in Table 23.

[Experimental Example 222] A handmade sheet was prepared in the same manner as in Experimental Example 183 except that the water-soluble polymer 1 and the water-soluble polymer 8 were used in the same amount and the whiteness thereof was measured. The obtained results are shown in Table 23.

[0134]

[Table 22]

[0135]

[Table 23]

Comparative Examples 32 to 38 Hand-made sheets were prepared in the same manner as in Experimental Example 183 except that the auxiliaries shown in Table 24 were used, and the whiteness thereof was measured. The results obtained are shown in Table 24.
Are also shown.

[0137]

[Table 24]

Example 4 The following test was carried out in order to evaluate the ability of the auxiliaries to suppress the deposition of silicate scale on the bleached product or bleaching apparatus.

Experimental Example 223 In a glass mayonnaise bottle having a capacity of 225 ml, 150 parts of ion-exchanged water, 3 parts of a 0.4% aqueous solution of water-soluble polymer 1 (60 ppm), 10 parts of a 0.84% aqueous sodium hydrogen carbonate solution, Sodium metasilicate (9 hydrate) 1.09% aqueous solution of 10 parts and magnesium sulfate (7
After adding 10 parts of a 0.986% aqueous solution, the pH was adjusted to 9.0 with dilute hydrochloric acid. Then, ion-exchanged water was added so that the total amount would be 200 parts, the container was sealed, and heat-treated at 70 ° C. for 40 hours. After the heat treatment was completed, the mixture was filtered with a 0.2 μm membrane filter, and the Si content in the filtrate was analyzed by ICP to evaluate the silicic acid-based scale inhibiting ability. The results are shown in Table 25.
It was shown to.

The amount of the water-soluble polymer 1 added was 30 ppm,
The evaluation was performed by changing it to 100 ppm, 200 ppm, and 400 ppm. The results are also shown in Table 25.

[Experimental Examples 224 to 258] Water-soluble polymer 2
In the same manner as in Experimental Example 223 except that ~ 36 was used, the silicic acid-based scale inhibition ability was evaluated. The results are shown in Tables 25 and 26.
It was shown to.

[0142]

[Table 25]

[0143]

[Table 26]

[Comparative Examples 39 to 49] Silica-based scale inhibiting ability was evaluated in the same manner as in Experimental Example 223 except that the auxiliaries shown in Table 27 were used. The results are also shown in Table 27.

[0145]

[Table 27]

[0146]

INDUSTRIAL APPLICABILITY As described above, the bleaching composition according to the present invention suppresses wasteful decomposition of peroxides, thereby improving storage stability, and at the same time, it is inexpensive and has improved bleaching properties as compared with conventional ones. Produce an effect.

Further, according to the bleaching method of the present invention, the bleaching property is remarkably improved with a small amount of the auxiliary agent. Further, when a silicate is used as a peroxide stabilizer, an insoluble salt (scale), a silicic acid-based polyvalent metal salt, is not produced during the bleaching step, or is produced. Also has the effect of being able to suppress the bleaching property and scale problems caused by depositing on the bleached material and various bleaching devices.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C11D 3/395 7/54 D06L 3/00 7199-3B D21C 9/10 Z 7199-3B 9/153 7199-3B

Claims (11)

[Claims] 1. A peroxide and the following formula: Each independently or together represent hydrogen, a monovalent metal, a divalent metal, an inorganic or organic ammonium group, and a and b represent an integer of 1 to 7) in the side chain. A bleaching composition comprising a water-soluble polymer. 2. The water-soluble polymer has the following formula: The bleaching composition according to claim 1, characterized in that both R ¹ and R ² have a structural unit represented by the above meaning. 3. At least one of R ¹ and R ² in the above formula of the water-soluble polymer is The bleaching composition according to claim 1, wherein the bleaching agent composition is exposed. 4. R ¹ and R ² in the formula of the water-soluble polymer are each independently or together, A bleaching composition according to claim 3, characterized in that it is exposed. 5. The formula of the water-soluble polymer, wherein Z ¹ is hydrogen and Z ² is --CH _2-.
The bleaching composition described in. 6. A water-soluble polymer is represented by the following formula: (In the formula, A ¹ and A ² each independently represent hydrogen, a methyl group or —COOX ¹³ , and A ¹ and A ² are simultaneously —
It does not become COOX ¹³ , A ³ represents hydrogen, a methyl group or —CH ₂ COOX ¹⁴ and A ³ is —CH ₂ COO.
In the case of X ¹⁴ , A ¹ and A ² each independently represent hydrogen or a methyl group, and X ¹² , X ¹³ and X ¹⁴ are independently or together hydrogen, a monovalent metal, a divalent metal, an inorganic or organic group. And an R ¹ and R ^{2 each} have the meaning described in claim 5 and n / m is 20/80 to 98/2). The bleaching composition according to claim 5. 7. The bleaching composition according to any one of claims 1 to 6, which contains a surfactant. 8. Each independently or together represent hydrogen, a monovalent metal, a divalent metal, an inorganic or organic ammonium group, and a and b represent an integer of 1 to 7) in the side chain. A bleaching method which comprises bleaching with a peroxide using a water-soluble polymer as a bleaching aid. 9. The water-soluble polymer has the following formula: The bleaching method according to claim 8, which is a water-soluble polymer containing a structural unit represented by: 10. The water-soluble polymer has the following formula: (In the formula, A ¹ and A ² each independently represent hydrogen, a methyl group or —COOX ¹³ , and A ¹ and A ² are simultaneously —
It does not become COOX ¹³ , A ³ represents hydrogen, a methyl group or —CH ₂ COOX ¹⁴ and A ³ is —CH ₂ COO.
In the case of X ¹⁴ , A ¹ and A ² each independently represent hydrogen or a methyl group, and X ¹² , X ¹³ and X ¹⁴ are independently or together hydrogen, monovalent metal, divalent metal, inorganic or organic. And an R ¹ and R ^{2 each} have the above-mentioned meaning, and n / m is 20/80 to 98/2). The bleaching method described in. 11. The bleaching method according to claim 8, wherein the bleaching aid contains a silicic acid agent.