JPH0491271A - Continuous scouring bleaching method using hydrogen peroxide for textile materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved method for bleaching fibers with hydrogen peroxide. That is, the present invention relates to a continuous bleaching method for fibers that have a soft texture, high absorbency, high whiteness, and less generation of creases. This invention relates to a method for preventing strength deterioration. .

[Conventional technology and problems]

Continuous scouring bleaching using hydrogen peroxide is typically carried out in the following steps when treating cotton fibers.

(a) Caustic soda scouring → alkaline hydrogen peroxide bleaching (p
H11-12) Steam treatment at 90°C or higher (b) Alkaline hydrogen peroxide-bath scouring bleaching (pH 11-
12) *Steaming treatment at 90°C or higher (c) Low-temperature alkaline hydrogen peroxide-bath scouring bleaching (pH 1
1,5-12.5) These scouring and bleaching methods do not allow white skin, water absorption,
Each type has its own advantages and disadvantages in terms of texture, creases, contamination, amount of water used, etc. It has a soft texture, high water absorption, and high whiteness, and it also generates less pollution and requires less water for cleaning. There is no bleaching method that satisfies all the conditions, and the industry's demands have become more sophisticated due to the desire for differentiation in recent years, requiring products with high water absorption, high whiteness, high texture (soft texture), and less creases. We are now living in an era where people are becoming more aware of what they are doing, and we are unable to respond to it.

On the other hand, as a method to compete with the hydrogen peroxide continuous scouring bleaching method, a sodium chlorite continuous bleaching method has been carried out using the following steps.However, these bleaching methods are superior to the hydrogen peroxide continuous scouring bleaching method. However, there is a lot of cleaning between each process, which requires a lot of water for cleaning, and also generates a large amount of pollution. Furthermore, since chlorine bleach is used, there is a problem of odor generation, which is unfavorable in terms of environmental hygiene, and it is also difficult to treat wastewater. Also, the surface where creases occur is not perfect. Furthermore, the sodium chlorite bleaching equipment requires expensive titanium as a material, resulting in high equipment costs.

(d) Sodium chlorite bleaching → Weakly alkaline hydrogen peroxide desalination makeup bleaching *Steam treatment at 90°C or higher.

It is applied to items that require high texture and whiteness, such as knitted underwear.

(e) NaOH scouring → Sodium chlorite bleaching → Weakly alkaline hydrogen peroxide desalting Makeup bleaching Umbrella steaming treatment at 90°C or higher.

*Applicable to fabrics that do not require excessive texture, such as cotton woven fabrics, and require high water absorption and high whiteness.

As mentioned above, each of the conventional continuous scouring and bleaching methods has its own drawbacks, and there has been no continuous scouring and bleaching method that can satisfy all of them.

[Problem that the invention seeks to solve]

In view of the problems of the conventional continuous scouring bleaching method described above, the present inventors have conducted extensive research on the continuous scouring bleaching method using hydrogen peroxide, and have found that it has a soft texture, high water absorption, and high A method that achieves high whiteness and less creases, generates less pollution, eliminates washing between scouring and bleaching, shortens the process, and saves water for washing. Heading, Patent application filed earlier (Patent application No. 2-87
542).

However, the cough method has had the problem of deterioration of fiber strength due to factors other than the inherent properties of fibers, such as heavy metal adhesion. The purpose of the present invention is to prevent deterioration of fiber strength due to various causes, including heavy metal adhesion during scouring and bleaching, during scouring and bleaching with hydrogen peroxide.

c. Means for Solving Problems] As mentioned above, the present inventors have developed a new method using hydrogen peroxide as a scouring agent and a bleaching agent, which can solve various problems of the conventional continuous scouring and bleaching method. A patent application (Japanese Patent Application No. 2-87542, hereinafter referred to as Hikari's application) was first applied for the continuous scouring and bleaching method. Treatment) pH
After immersing it in a hydrogen peroxide solution at a temperature of 50 to 100 °C adjusted to 5.0 to 8.5 for at least 5 minutes, and then dehydrating it so that the squeezing rate is 70 to 200% of the fiber weight,
(2) B treatment (later low-temperature alkaline hydrogen peroxide bleaching) The A-treated wet fibers are treated with P in the liquid contained in the fibers.
H is 11.5-12.5 and hydrogen peroxide concentration is 3-4
A method for continuous scouring and bleaching of fibers, which is characterized by adjusting the squeezing rate to 5g/L and 70 to 200% of the weight of the fibers, and then allowing the fibers to stand at a temperature of room temperature to 50°C for 5 hours or more.

[2] The fiber to be treated is subjected to (1) A” treatment (preliminary treatment with hydrogen peroxide solution)p
The wet fibers were passed through a hydrogen peroxide solution adjusted to H5.0 to 8.5 and the hydrogen peroxide solution was absorbed so that the squeezing rate was 70 to 200% of the fiber weight.
(2) B treatment (post-stage low-temperature alkaline hydrogen peroxide bleaching) The wet fibers treated with A are heated to 0.5℃ for at least 5 minutes without washing, until the pH of the liquid contained in the fibers is 11. 5-12.5 and hydrogen peroxide concentration 3-12.5
45 g/L and a squeezing rate of 70 to 200% of the fiber weight, and then left to stand at a temperature of room temperature to 50° C. for 5 hours or more.

That's what it was.

As a result of further research, the present inventors found that when bleaching is performed using the method of the previous application, the presence of a reaction modifier, which will be described later, in the hydrogen peroxide solution is more effective in the following respects. The present invention was completed by discovering that bleaching can be carried out effectively.

■ The presence of a reaction modifier significantly stabilizes the hydrogen peroxide during the pre-treatment with a hydrogen peroxide solution with a pH of 5.0 to 85, allowing hydrogen peroxide to be absorbed after the pre-treatment without reducing the effect of the pre-treatment. As the remaining amount increases, the subsequent low-temperature alkaline hydrogen peroxide bleaching can be performed at a high concentration, allowing textile products with higher whiteness to be produced.

■ In the case of cotton fabrics, etc., a desizing process is performed to remove the size before scouring with hydrogen peroxide and bleaching. However, depending on the conditions of the bleaching factory, scouring or desizing may be carried out before the size is removed completely in the desizing process. Bleaching may be performed, in which case the pH
In the preliminary treatment with a hydrogen peroxide solution of 5.0 to 8.5, there was significant decomposition of hydrogen peroxide, which had the drawback of deteriorating fiber strength.

However, if a reaction modifier is present here, decomposition of hydrogen peroxide is suppressed, and bleaching can be performed without deteriorating fiber strength.

(2) The equipment may occasionally stop due to equipment failure, power outage, etc., and the preliminary treatment using a hydrogen peroxide solution with a pH of 5.0 to 8.5 may take a long time. In that case, there was a drawback that fiber strength deteriorated if the pre-treatment with a hydrogen peroxide solution having a pH of 5.0 to 8.5 took a long time.

However, if a reaction modifier is present here, bleaching can be carried out without degrading the fiber strength even if the treatment is for a long time.

■ Bleaching textile materials contaminated with heavy metals such as iron and copper, which generally degrade hydrogen peroxide significantly, with hydrogen peroxide.
It is known that hydrogen peroxide decomposes significantly in areas contaminated with heavy metals, resulting in a decrease in fiber strength. In that case,
Similar to this example, the method of the previous application also had the drawback of deterioration of fiber strength due to heavy metal contamination. However, if a reaction modifier is present here, strength deterioration due to heavy metal contamination can be significantly prevented.

That is, the present invention provides the following advantages: [1] The fiber to be treated is subjected to (1) A treatment (preliminary treatment with a hydrogen peroxide solution) with a small amount of a compound of group 1 shown below (or at least one compound of group 1 and group ①). In the hydrogen peroxide solution at a temperature of 50 to 100 °C and adjusted to pH 5.0 to 8.5,
Soak for at least 5 minutes, then reduce the squeezing rate to 70 to 70% of the fiber weight.
After being dehydrated to 200%, there is no need to wash it.
(Group 1 of compounds) (1) Contains at least two nitrogen atoms in the molecule, one of the nitrogen atoms serves as a primary or secondary amino group, and the others are primary, secondary or An organic nitrogen compound or a salt thereof, which exists as a tertiary amino group or sulfonamide, and the nitrogen atom is bonded via a hydrocarbon or a hydrocarbon substituted with a heteroatom.

(2) An aminoalkyl phosphoric acid derivative represented by the following general formula.

(X203 P CHI ) t = N (('CH
z )1N-CHz PO3Xz ), -CH,PO
3X2 [wherein X represents hydrogen, ammonium, or an alkali metal, m represents an integer of 2 to 3, and n represents an integer of 0 to 3. (3) Oximes or salts thereof.

(4) Polyphosphoric acids or salts thereof.

(5) An aminocarboxylate organic chelating agent or a salt thereof.

(Compounds of Group II) (1) General formula, CH2OH(CHOH) 1ICH,0
Sugar alcohols represented by H.

[In the formula, n represents an integer of 2 to 6. ] (2) Aldonic acid represented by the general formula, CHz OH (CHOH) mCOOH, a salt thereof, or a lactone thereof.

[In the formula, m represents an integer of 3 to 6. (3) A polymer derived from α-hydroxyacrylic acid represented by the following general formula.

{C(R1・R2)C(OH-COOM)).

[In the formula, R and R may be the same or different and each represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and M represents an alkali metal atom, a hydrogen atom, or an ammonium group. ] (2) B treatment (later low-temperature alkaline hydrogen peroxide bleaching) The A-treated wet fibers are
H is 11.5-12.5 and hydrogen peroxide concentration is 3-4
A method for continuous scouring and bleaching of fibers, which is characterized in that the squeezing rate is adjusted to 5 g/L and 70 to 200% of the weight of the fibers, and then left to stand at a temperature of room temperature to 50°C for 5 hours or more.

[2] The fibers to be treated are subjected to (1) A' treatment (preliminary treatment with a hydrogen peroxide solution) with at least one compound of group 1 shown below, or at least one compound of group 1 and at least one compound of group in the presence of a reaction regulator consisting of
The wet fibers are passed through a hydrogen peroxide solution adjusted to a temperature of 50 to 105° C. for at least 5 minutes so that the reduction ratio is 70 to 200% of the fiber weight, and the wet fibers are heated to a temperature of 50 to 105° C. (Group of compounds) (1) Contains at least two nitrogen atoms in the molecule, one of which serves as a primary or secondary amino group, and the others serve as a primary amino group. , a secondary or tertiary amino group or a sulfonamide, and the nitrogen atom is bonded via a hydrocarbon or a hydrocarbon substituted with a heteroatom, or a salt thereof.

(2) An aminoalkyl phosphoric acid derivative represented by the following general formula.

(X203 P Hz)! =N ((CHz
) -N-CHI PO,x, ) , -CH,PO3
X.

[In the formula, χ represents hydrogen, ammonium, or an alkali metal, m represents an integer of 2 to 3, and n represents an integer of 0 to 3. ] (3) Oximes or salts thereof.

(4) Polyphosphoric acids or salts thereof.

(5) An aminocarboxylate organic chelating agent or a salt thereof.

(Compounds of Group II) (1) General formula, CH, OH (CHOH), CHz OH
Rust alcohols represented by.

In the U formula, n represents an integer of 2 to 6. ] (2) Aldonic acid represented by the general formula CH2OH(CHOH)mCOOH, a salt thereof, or a lactone thereof.

In formula 1, m represents an integer of 3 to 6. ] (3) A polymer derived from α-hydroxyacrylic acid represented by the following general formula.

{C(R1-Rz　)C(OH,COOM)).

[In the formula, R+ and Rz may be the same or different, and each represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and M represents an alkali metal atom, a hydrogen atom,
Or represents an ammonium group.

] (2) B treatment (later low-temperature alkaline hydrogen peroxide bleaching)
H is 11.5-12.5 and hydrogen peroxide concentration is 3-4
This is a continuous scouring and bleaching method for fibers, which is characterized by adjusting the reduction rate to 70 to 200% of the weight of the fibers, and then leaving the fibers at a temperature of room temperature to 50°C for 5 hours or more.

Next, the present invention will be explained in more detail.

[1] A treatment The A treatment in the method of the present invention involves first treating the fibers to be treated at a temperature of 50 to 100°C with the pH adjusted to 5.0 to 8.5, and then treating the fibers with a reaction modifier containing a reaction modifier as described below. Soak in hydrogen oxide solution for at least 5 minutes, then reduce the squeezing rate to 70-20 of the fiber weight.
This is a treatment method that dehydrates the water to 0%, and the pH of the hydrogen peroxide solution used in this case is 5 to 5, as mentioned above.
Adjusted to 8.5. The pH is adjusted to between 5.0 and 8.5 using a common acid or alkali, if necessary. If the pH exceeds 8.5, texture hardening and large amounts of hydrogen peroxide decompose, making the first-stage treatment (A treatment) ineffective, the second-stage treatment (B treatment) unable to achieve satisfactory bleaching, and the high-temperature treatment causing breakage. Wrinkles are likely to occur and the features of the present invention are lost. Furthermore, if the pH is below 5.0, the fibers become brittle due to abnormal decomposition of hydrogen peroxide, and furthermore, the fibers become yellowed and have a hardened texture, which is not preferable.

The hydrogen peroxide concentration in the hydrogen peroxide solution used in the pretreatment of the present invention is generally 1 to 45 g/L, and practically 5 to 30 g/L, and the hydrogen peroxide used therein is commercially available. The various concentrations listed are used as is,
Usually, 35% product is used.

In addition, a surfactant, which is commonly used for bleaching textiles, is used to improve the penetration of chemicals into the textiles. The amount to be used varies depending on the purity concentration and penetrating power of each commercially available product, but it should be used according to the application amount of each commercially available product. Generally, a suitable amount is 0.1 to 2 g/L as a pure content.

In the A treatment, the fiber to be treated is first immersed and retained in a hydrogen peroxide solution containing a reaction modifier and having a specific pH as described above, heated to 50 to 100°C for at least 5 minutes or more, but usually for less than 45 minutes. Perform processing. This treatment is carried out continuously by allowing the fibers to remain in and pass through the hydrogen peroxide solution for a predetermined period of time under normal pressure. At this time, the preferred heating temperature of the hydrogen peroxide solution containing the reaction regulator at a specific pH is 70~
If the temperature is 90°C or lower, the first stage treatment will be insufficient and the object of the present invention will not be achieved. On the other hand lo.

If the temperature is higher than 0.degree. C., boiling will occur, and the decomposition of hydrogen peroxide will be intense, resulting in weakening of the strength of the fibers, which is not preferable. The immersion residence time is 5 to 60 minutes, preferably 10 to 45 minutes; if it is less than 5 minutes, the reaction will be insufficient and the object of the present invention will not be achieved.

Further, heating for more than 60 minutes does not provide any particular effect and is not rational.

The fibers subjected to the above treatment have a reduction ratio of 70% relative to the fiber weight.
Dehydrated to ~200%. In the present invention, the same effect can be obtained by performing the following A° treatment on the fibers to be treated instead of the above-mentioned A treatment.

(2) A' - Treatment A' The treated fibers were first passed through a hydrogen peroxide solution containing the same reaction modifier as in A treatment, whose pH was adjusted to 5.0 to 85, and the reduction rate was adjusted to the fiber weight. A treatment method in which the wet fibers that have absorbed the hydrogen peroxide solution are heated at a temperature of 50 to 105°C for at least 5 minutes; in this case, the pH of the hydrogen peroxide solution is is adjusted in a similar manner. If the pH is less than 5.0 or more than 8.5, the same problems as in the case of A treatment will occur, which is not preferable. The concentration of the hydrogen peroxide solution is generally 1 to 45 g/m, as in the case of A treatment, and practically 5 to 30 g/m
g/L, and the hydrogen peroxide used for this is usually 35% hydrogen peroxide. Also in the case of the A' treatment, as in the case of the A treatment, a surfactant which is normally used for bleaching fibers is used in order to improve the penetration of chemicals into the fibers. The amount used varies depending on the purity concentration and penetrating power of each commercially available product, but it should be used according to the application amount of each commercially available product. Generally, a suitable amount is 0.1 to 2 g/L as a pure content.

Next, the fibers are moistened with a hydrogen peroxide solution containing a reaction modifier at a specific pH and adjusted to have a reduction ratio of 70 to 200% of the fiber weight.
℃ and kept at that temperature for at least 5 minutes, usually 4
It is held for less than 0 minutes.

These steps are usually carried out by contacting the continuously moving fibers with steam at the temperature mentioned above under normal pressure. The preferred heating temperature is 70 to 100"C; if it is below 50°C, the preliminary treatment will be insufficient and the object of the present invention will not be achieved. On the other hand, if it is above 105°C, the decomposition of hydrogen peroxide will be severe and the strength of the fiber will become brittle. Not preferable.Heating time is 5~
The reaction time is 60 minutes, preferably 10 to 30 minutes; if it is less than 5 minutes, the reaction will be insufficient and the object of the present invention will not be achieved. 60 again
Even if it is heated for more than a minute, there is no particular effect and it is not reasonable.

Next, the reaction regulator used in the present invention is at least one of the compounds of group 1 shown below, or a compound consisting of at least one of the compounds of group 1 and at least one of the compounds of group ①.

Group 1 of compounds include: (1) Containing at least two nitrogen atoms in the molecule, one of which serves as a primary or secondary amino group, and the others serve as primary or secondary amino groups. or an organic nitrogen compound or a salt thereof that exists as a tertiary amino group or sulfonamide, and the nitrogen atom is bonded via a hydrocarbon or a hydrocarbon substituted with a heteroatom, and has the following general formula: ■
A compound that is formed by ~■.

■ Hz N-((CH, CHz NH), (X))
.

-NHR alkylene polyamine (wherein: R is a hydrogen atom or -COOHX is CH2 or CH2CH
z, m is O or 1 to 3; when m is O, n is 1 to 6; when m is 1 to 3, X is CH, CH2 and n is 1; when R is C0OH, X is CH , CH, where m is O and n is 1. ) Biguanides represented by R1.

(In the formula: R1 is a hydrogen atom I C1-C4 alkyl group, phenyl group, tolyl group, or R2, R, and R4 are hydrogen atoms, 01-C4
When R1 is an alkyl group, R2-R4 is a hydrogen atom. ) [In the formula: R1 is a hydrogen atom or an alkyl group of 01 to C4, R2 is NHR"(R" is the same as R) or -SO
□NH. ] Types. (In the formula: R is a hydrogen atom or a lower alkyl group.) Benzimidazoles.

(In the formula: R is a hydrogen atom or a lower alkyl group.) Examples of the alkylene polyamine represented by the above general formula (■) include ethylenediamine, diethylenetriamine, triethylenetetramine, trimethylenediamine, hexamethylenediamine, N-carboxyethylenediamine, etc. Examples of aromatic amines or aromatic diamines represented by general 2) include P-phenylenediamine, N,N-dimethyl-P-phenylenediamine, and P-phenylenediamine.
aminobenzenesulfonamide, etc., and the biguanides represented by -i formula (■) include, for example, biguanide, 1
-Methyl biguanide, 1,5 dimethyl biguanide, 1-
Phenylbiguanide, 0-tolylbiguanide, 1.1-
Examples include diethylene biguanide, 1-phenyl-5,5-diethyl biguanide, and the like. Examples of the piperazine represented by the general formula (2) include piperazine and N-N'-dimethylpiperazine. Examples of the benzimidazoles represented by the general formula (2) include 2-methylbenzimidazole. These salts include, for example, alkali metal or alkaline earth metal salts such as sodium salts and potassium salts, mineral acid salts such as sulfates and hydrobromides, and organic acids such as tartrates and maleates. Examples include salt.

(2) An aminoalkyl phosphoric acid derivative represented by the following general formula.

CXt 03 P CHz ) t = N ((CH
z) -N cHz PO3X2), CH
In the 2PO3X2U formula, X represents hydrogen, ammonium, or an alkali metal, m represents an integer of 2 to 3, and n represents 0 to 3.
Indicates an integer of 3. ] Representative examples of these include aminotrimethylenephosphonic acid (ATMP), ethylenediaminepentamethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and propylenediaminetetramethylenephosphonic acid (PDTMP).
, dipropylenetriaminepentamethylenephosphonic acid (
DPTPMP) or its salts, and the salts include alkali metal salts such as sodium salts and potassium salts.

(3) Oximes or salts thereof.

Representative examples of these include ketooximes such as benzoin oxime, phenylpyridyl ketoxime, cyclohexanedione dioxime, dimethylglyoxime, and fructose oxime, and aldoximes such as glucose oxime and salicylaldoxime, or their salts; Examples include alkali metal salts such as potassium salts.

(4) Polyphosphoric acids or salts thereof.

Typical examples of these include birophosphoric acid, tripolyphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, etc., or salts thereof; examples of the salts include alkali metal salts such as sodium salts and potassium salts.

(5) An aminocarboxylate organic chelating agent or a salt thereof.

Typical examples of these include trilotriacetic acid (NTA),
EDTA (ethylenediaminetetraacetic acid), DTPA (
Examples of the salt include alkali metal salts such as sodium salt and potassium salt.

Also, as compounds of group ■, (1) General 2 CH2OH (CHOH), lCH!
Sugar alcohols represented by OH [wherein n represents an integer of 2 to 6]. Typical examples include D-glugit, D-mannitol, D-xylitol, erythromannoffitol, and the like.

Examples include sodium acrylate (SpHA) (2)
General 2 Aldonic acid represented by CH,OH(CHOH)mCOOH, its salt, or its lactone In formula 1, m represents an integer of 3 to 6. Typical examples include D-Mannos, D-Mannos, and D-Mannos.
Examples include aldonic acids obtained from aldoses such as xylose and D-glucose, their water-soluble salts, and lactones of these acids. (3) Polymers derived from α-hydroxyacrylic acid represented by the following general formula (C(R+'Rz)C(OH-COOM))n
[In the formula, RI and R2 may be the same or different, and each represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and M is an alkali metal atom, a hydrogen atom,
Or represents an ammonium group. ] As a typical example, the amount of poly-α-hydroxy reaction regulator used varies depending on the type of fiber and the type of compound, but it is typically 0.05% in hydrogen peroxide solution.
It is used in a proportion of ~20 g/L, preferably 0.1-10 g/L. In addition, these reaction modifiers are generally added to the A treatment or A° treatment solution, but depending on the situation, they can also be added in portions during the latter stage B treatment. , divisional addition may be preferable in some cases.

[3] B treatment Next, the A-treated or A゛-treated fibers are not washed, but an alkaline solution or an alkaline solution containing hydrogen peroxide is added to remove the liquid contained in the fibers. After adjusting the pH to 11.5 to 125, the hydrogen peroxide concentration to 3 to 45 g/L, and the squeezing rate to 70 to 200% of the fiber weight, it is heated at room temperature to 50°C. Bleaching is completed through a leaving step of 5 hours or more and a washing step.

As the alkaline agent used in this B treatment, a strong alkaline agent such as caustic soda or caustic potash is used as the main agent since the pH is high. As an auxiliary agent, a general alkali agent, soda carbonate, sodium metaborate, etc. may be used. The amount of the alkali agent in the alkaline solution is the amount necessary to adjust the pH of the fiber-containing liquid to 11.5 to 12.5. If the pH is lower than 11.5, the bleaching blade of hydrogen peroxide is insufficient, resulting in cotton crumbling residue and insufficient white discoloration. In addition, the scouring effect is lowered and the water absorbency is lowered. At pH 12.5 or higher, hydrogen peroxide decomposes to a large extent, resulting in leftover cotton debris, insufficient whitening, uneven bleaching, and strength embrittlement.

In addition, the hydrogen peroxide concentration is practically adjusted so that the concentration in the fiber-containing liquid is 3 to 45 g/L, but usually the hydrogen peroxide remaining after the first stage treatment (after the A or A' treatment) is (There is little decomposition of hydrogen peroxide in the first stage treatment, and a large amount of hydrogen peroxide remains.) Depending on the desired white skin, or if the amount of hydrogen peroxide after the first stage treatment is small, use An amount is added to the alkaline solution to give a concentration.

Further, in order to further improve the penetration of the drug into the fibers, a surfactant similar to that used in the previous treatment may be used in the alkaline solution, if necessary.

Further, it is preferable to add a silicate or various commercially available hydrogen peroxide stabilizers to the alkaline solution for the purpose of enhancing the stabilizing effect of hydrogen peroxide. In the case of silicate, use No. 3 silica in an amount such that the concentration in the fiber-containing liquid is 1 to 50 g/L, preferably 2.5 to 20 g/L (for example, 1 to 20 g/L).
No. 3 silica, metasilica, potassium silicate, etc.) are added. In the case of commercially available hydrogen peroxide stabilizers, they are used according to the application amount of each commercial product. - For boat fishing, the same amount as No. 3 Keisuke is used.

Furthermore, it is preferable to add Mg ions to the alkaline solution for the purpose of assisting in stabilizing hydrogen peroxide.

The amount of Mg ions is 20 ppm to 200 PPm, preferably 3 opp as the concentration in the liquid contained in the fibers.
m to 80 ppm.

20 FIMg ions include nibutum salt (MgS04
) is preferably added.

In addition, phosphates (sodium orthophosphate,
(sodium pyrophosphate, sodium tripolyphosphate, etc.), their phosphate hydrogen peroxide adducts, sodium percarbonate, sodium percarbonate, persulfates (sodium persulfate, sodium persulfate, ammonium persulfate), or one or more of them. When added, the scouring and bleaching effect is further enhanced. The amount used varies depending on the type and form of fiber, but the concentration in the fiber-containing liquid is usually 0.5~
Add an amount of 10 g/L, preferably 2 to 5 g/L,
These may be used alone or in combination.

In this B treatment, the alkaline solution or the alkaline solution containing hydrogen peroxide can be added to the fibers by spraying the solution or passing it through the solution. For addition and impregnation with a solution, a method of passing through the solution is preferred.

The amount of alkaline hydrogen peroxide bleaching solution impregnated into the fiber varies depending on the type and form of the fiber, but generally the squeezing rate is 70 to 200%, preferably 75 to 175% of the fiber weight.
Adjust so that If it is less than 70%, insufficient bleaching will occur and the object of the present invention will not be achieved. Moreover, if it exceeds 200%, there is no particular effect and it is meaningless.

The wet fiber prepared in this way is left for 5 hours or more under a temperature condition of room temperature to 50° C. without much water evaporation. As for the leaving method under the temperature condition of room temperature to 50°C, the temperature of an alkaline solution or an alkaline solution containing hydrogen peroxide is set to an appropriate temperature of room temperature to 50°C, and the fiber is allowed to pass through, and the wet fiber is placed in a square bath or a trolley. etc.,
Alternatively, roll it up and leave it sealed with a sheet of polyethylene, vinyl chloride, etc. to prevent water from evaporating and the temperature from dropping. Alternatively, the sealed wet fibers are left in a room maintained at an appropriate temperature between room temperature and 50"C.The higher the temperature of the alkaline solution or the alkaline solution containing hydrogen peroxide and the temperature at which it is left, the less effective However, if the temperature exceeds 50"C, the hydrogen peroxide decomposes rapidly, resulting in insufficient bleaching, cotton crumbling residue, and strength deterioration, which is undesirable. Also, due to its own weight and alkali, large and small creases will occur, and the texture will harden. This is not desirable.

The leaving time is preferably 5 to 20 hours, more preferably 1
It is 0 to 15 hours. If the reaction time is less than 5 hours, the object of the present invention will not be achieved due to insufficient reaction, and if the reaction time is more than 20 hours, the effect has already reached its peak, and even if it is left to stand for more than 20 hours, there will be no adverse effect on the fibers, but this is not reasonable. Then, it is efficient in terms of time if this neglect processing is performed using the idle time at night.

The bleaching method of the present invention is completed by continuously washing the fibers after the standing operation is completed, and removing chemicals and impurities remaining in the fibers, as is done in normal continuous bleaching. . In addition, in the bleaching method of the present invention, it is also possible to carry out the B treatment by performing the preliminary treatment (A treatment or A' treatment, followed by washing).

Fibers that can be applied to the bleaching method of the present invention include natural, synthetic, or semi-synthetic fibers other than protein fibers, blends, blends, knits, and other textile products of these fibers. The continuous bleaching apparatus applied to the bleaching method of the present invention does not require any special new equipment, and a commonly used continuous bleaching apparatus for hydrogen peroxide can be applied as is. For example, Rapid J-B o X, L-B o X, U-B o
X, Macchilin steamer, Bentler bleaching machine, Purple Range, etc. And the latter stage (B process) alkaline hydrogen peroxide bleaching equipment is the reaction B of the above bleaching equipment.
All you have to do is replace oX with a square tank, a trolley, or a roll winder. Continuous processing methods include a rope-like method and a spread-sheet method, but when the fibers are woven, knitted, or towel-like, it is preferable to use the spread-like method rather than the rope-like method in view of folding and wrinkling.

〔Effect of the invention〕

Although the bleaching method of the present invention is an improved method of the bleaching method of the earlier application,
As with the previous application, bleaching with less creases, good texture, high whiteness, high water absorption, and less pollution can be achieved, and compared to the current continuous bleaching method, it is less expensive in terms of process, utility costs, and environment. The quality of bleached products can be significantly improved. In particular, according to the present invention, the stability of hydrogen peroxide during the pre-treatment with a hydrogen peroxide solution is significantly improved, and no matter what conditions the fiber material is placed in, it can maintain high quality with less deterioration of fiber strength. You can get bleaching products.

〔Example〕

The present invention will be explained in more detail with reference to Examples below. Here, white discoloration, texture, strength, water absorption, and crease condition were measured based on the following measurement methods. Note that the examples do not limit the method of the present invention ■ Whiteness Tokyo Juishiki Co., Ltd. automatic color computer P
Measurement was performed using L-ab system using C-1500MC. L, a, b indicate the following meanings, b value: lightness, a value:
(+) reddish, (-) greenish, b value: (+) yellowish, (-) bluish. Among these, the b value matches well with visual perception, so white discoloration is b
It was determined by the value. The smaller the b value, the lower the yellowness, that is, the higher the whiteness.

■Texture The texture was measured based on the 6.21 stiffness "45 degree cantilever method" of the Japanese Industrial Standards JIS L 1018-1977 "Knitted Fabric Testing Method". The smaller the number, the softer the texture.

■Strength Tensile strength was measured using Tensilon manufactured by Toyo Baldwin Co., Ltd., and the strength retention rate was calculated using the original sample as 100%.

■ Water absorbency 6.27 of the Japanese Industrial Standards JIS L 1018-1977 "Knitted fabric testing method" Water absorbency "Shen Feng method"
The water absorption rate was measured based on the following. The smaller the value, the better the water absorbency.

■Folded and wrinkled condition The state of occurrence of creases was determined visually.

Example 1 Continuous bleaching of cotton knitted underwear, which requires a soft texture and high whiteness, and which dislikes the occurrence of folds and wrinkles, was carried out in the form of a spread cloth under the following conditions. The results are shown in Table 1.

*Preliminary treatment with hydrogen peroxide solution (A' treatment) The knitted fabric was immersed in the following hydrogen peroxide solution, squeezed to a squeezing rate of 120%, and heated with steam at 95° C. for 30 minutes.

■ P-phenylenediamine ■ Piperazine * Post-stage low-temperature alkaline hydrogen peroxide bleaching (B treatment) After the completion of the above-mentioned first-stage treatment, proceed to the bleaching process without washing, and adjust the condition of the stockinette-containing liquid to the following conditions. ℃
A subsequent bleaching treatment was carried out for 15 hours. Incidentally, the B treatment was carried out using the amount of hydrogen peroxide remaining after the completion of the first stage as it was.

(0.2 g/L each) ■ None ■ 0-tolylbiguanide ■ ATM P ■ Cyclohexanedione dioxime ■ Sodium tripolyphosphate ■ EDTA According to the bleaching method of the present invention, the residual amount after A° treatment is reduced by adding a reaction modifier. The amount of hydrogen peroxide is increased, and hydrogen peroxide bleaching can be performed at a high concentration during B treatment, making it possible to obtain a bleached product with higher whiteness and higher water absorption without impairing the texture. Furthermore, the occurrence of creases is the same as without the reaction modifier, so there is no problem.

Example 2 An expanded cotton woven fabric that had been subjected to a desizing treatment with an enzyme and had not yet been desizing was subjected to continuous bleaching in accordance with the following conditions. The results are shown in Table 2.

*Preliminary treatment with hydrogen peroxide solution (A' treatment) The Kanakin woven fabric was immersed in the following hydrogen peroxide solution, and the squeezing rate was 100.
% and heated with 100°C steam for 20 minutes.

■ None ■ N-carboxyethylenediamine D-mannitol ■ EDTMP Sodium aldonic acid of D-mannose ■ Phenylpyridyl ketoxime SP HA 0.5g/L ■ Sodium hexaphosphate 0.5g/LD-glugit
0.5g/L■ NTA
0.5g/L Glucono δ-Lactone 0.5g/L
0.5g/L 0.5g/L 0.5g/L O,5g/L O,5g/L *Low-stage low-temperature alkaline hydrogen peroxide bleaching (B treatment) Bleach without washing after completing the above-mentioned first-stage treatment The fabric was moved to the process, and the state of the fabric-containing liquid was adjusted to the following conditions, and a post-bleaching treatment was performed at 45° C. for 10 hours.

The hydrogen peroxide residual rate on the cloth after the first stage was as shown in Table 2.

When the bleaching method of the previous application was carried out with insufficient desizing, the decomposition of hydrogen peroxide in the A'' process was significant (Table 2
(■), there is a drawback that the fiber strength deteriorates as the white skin decreases. The presence of a reaction modifier here significantly suppresses the decomposition of hydrogen peroxide in the A' treatment, allowing bleaching to be carried out without deterioration of fiber strength.Example 3 Spreading of Boblin woven fabric for dress shirts treated with enzymes for desizing Continuous bleaching was carried out according to the following conditions. The results are shown in Table 3.

*Preliminary treatment with hydrogen peroxide solution (A treatment) The Boblin woven fabric was immersed and retained in the following hydrogen peroxide solution for 10 hours (assuming a problem with the bleaching equipment), and then dehydrated to a squeezing rate of 110%.

The woven fabric was then transferred to a second stage, and the state of the liquid contained in the woven fabric was adjusted to the following conditions, and a post-bleaching treatment was performed at 25° C. for 20 hours.

■ None ■ 2-Methylbenzimidazole rho-xylit DTMP Sodium aldonic acid of D-mannose ■ Salicylaldoxime pHA ■ Sodium hexametaphosphate erythromannofutite ■ Cy DTA Sodium aldonic acid of D-xylose 2g/L 2g/L 2g/ L 2g/L 2g/L 2g/L 2g/L 2g/L 2g/L 2g/L *Low-stage low-temperature alkaline hydrogen peroxide bleaching (B treatment) After completing the above-mentioned front-stage treatment, bleaching process Table 3 can be carried out without washing. When present, good bleaching can be performed without deterioration of fiber strength.

Example 4 100 enzyme desizing treated cotton contaminated with iron and copper
% broad woven fabric was subjected to continuous bleaching under the following conditions. The results are shown in Table 4.

The iron and copper contaminated cloths were prepared as follows.

In the case of the bleaching method of the previous application, when the A treatment becomes long, there is a yellowing phenomenon as well as a deterioration in strength, and a decrease in white skin occurs at the same time (■ in Table 3).
0.18 mol/L aqueous solution of ferric chloride on a cm sample fabric
．． After uniformly impregnating 2 mL of cloth in a strip of width 0.5 cm in the weft direction to allow sufficient penetration, it was left in an ammonia stream for 30 minutes, washed with hot water, dehydrated and air-dried, and then diluted with 0.5 cm of cupric sulfate.
Impregnate 0.2 mL of the 018 mol/L aqueous solution onto the iron stain and allow it to penetrate thoroughly. This is then immersed in a hot solution containing caustic soda and a reducing side, thoroughly washed with water, and air-dried. Although iron and copper are insolubilized by this operation, the cloth does not deteriorate due to this operation.

*Preliminary treatment with hydrogen peroxide solution (A treatment) The broad woven fabric was immersed and retained in the following hydrogen peroxide solution for 30 minutes,
Thereafter, it was dehydrated to a squeezing rate of 110%.

*Low-stage low-temperature alkaline hydrogen peroxide bleaching (B treatment) After the completion of the above-mentioned first-stage treatment, proceed to the bleaching process without washing, adjust the state of the liquid containing the fabric to the following conditions, and bleach at 45°C for 10 hours. A post-bleaching treatment was performed.

■ None■ D T P M P 5g/L
■ D T P M P 5g/L
D-glucose aldonic acid Na 5g/L D
T P A 5g/L ■ D T
P A 5g/LD-Mannit 5g/L In the bleaching method of the above application, the fiber strength deteriorates due to heavy metal contamination (■ in Table 4), but the presence of a reaction modifier significantly reduces the fiber strength deterioration. It can be prevented.

Claims (1)

[Scope of Claims] [1] The fiber to be treated is subjected to (1) A treatment (preliminary treatment with hydrogen peroxide solution) at least one of the following Group I compounds, or at least one Group I compound and Group II compound. A reaction regulator consisting of at least one compound is present, and the pH is 5.0 to 8.5.
Add hydrogen peroxide solution at a temperature of 50 to 100°C,
Soak for at least 5 minutes, then reduce the squeezing rate to 70 to 70% of the fiber weight.
After dehydration to 200%, without washing, (compounds of group I) (1) Contain at least two nitrogen atoms in the molecule, one of which is primary or secondary. others as primary, secondary or tertiary amino groups or sulfonamides, the nitrogen atom being bonded via a hydrocarbon or a hydrocarbon substituted with a heteroatom. Organic nitrogen compounds or their salts. (2) An aminoalkyl phosphoric acid derivative represented by the following general formula. (X_2O_3PCH_2)_2=N-{(CH_2)
_m-N-CH_2PO_3X_2}_n-CH_2P
O_3X_2 [wherein X represents hydrogen, ammonium, or an alkali metal, m represents an integer of 2 to 3, and n represents 0 to
Indicates an integer of 3. ] (3) Oximes or salts thereof. (4) Polyphosphoric acids or salts thereof. (5) An aminocarboxylate organic chelating agent or a salt thereof. (Compounds of Group II) (1) General formula, CH_2OH(CHOH)_nCH_2
Sugar alcohols represented by OH. [In the formula, n represents an integer of 2 to 6. ] (2) General formula, CH_2OH(CHOH)_mCOOH
Aldonic acid, its salt, or its lactone represented by [In the formula, m represents an integer of 3 to 6. ] (3) A polymer derived from α-hydroxyacrylic acid represented by the following general formula. {C(R_1・R_2)C(OH・COOM)}_n[
In the formula, R_1 and R_2 may be the same or different and each represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and M represents an alkali metal atom, a hydrogen atom, or an ammonium group. ] (2) B treatment (later low-temperature alkaline hydrogen peroxide bleaching)
is 11.5-12.5 and hydrogen peroxide concentration is 3-45.
A continuous scouring and bleaching method for fibers, which is characterized in that the squeezing ratio is adjusted to 70 to 200% of the weight of the fibers, and then left to stand at a temperature of room temperature to 50° C. for 5 hours or more. [2] The fibers to be treated are subjected to (1) A' treatment (preliminary treatment with hydrogen peroxide solution) with at least one of the compounds of Group I shown below, or I
A reaction regulator consisting of at least one compound of Group II and at least one compound of Group II is present, and the pH is 5.0.
The wet fibers were passed through a hydrogen peroxide solution adjusted to a temperature of ~8.5° C., and the wet fibers were heated to a temperature of 50° C. to 105° C. for at least 50° C. so that the reduction ratio was 70% to 200% of the weight of the fibers. (Group I compounds) (1) Contains at least two nitrogen atoms in the molecule, one of which serves as a primary or secondary amino group; is present as a primary, secondary or tertiary amino group or sulfonamide, and the nitrogen atom is bonded via a hydrocarbon or a hydrocarbon substituted with a hetero atom, or an organic nitrogen compound or a salt thereof. . (2) An aminoalkyl phosphoric acid derivative represented by the following general formula. (X_2O_3PCH_2)_2=N-{(CH_2)
_m-N-CH_2PO_3X_2}_n-CH_2P
O_3X_2 [wherein X represents hydrogen, ammonium or an alkali metal, m represents an integer of 2 to 3, and n represents 0 to 3]
indicates an integer. ] (3) Oximes or salts thereof. (4) Polyphosphoric acids or salts thereof. (5) Aminocarboxylate organic chelating agent or its salt. (Compounds of Group II) (1) General formula, CH_2OH(CHOH)_nCH_2
Sugar alcohols represented by OH. [In the formula, n represents an integer of 2 to 6. ] (2) General formula, CH_2OH(CHOH)_mCOOH
Aldonic acid, its salt, or its lactone represented by [In the formula, m represents an integer of 3 to 6. ] (3) A polymer derived from α-hydroxyacrylic acid represented by the following general formula. {C(R_1・R_2)C(OH・COOM)}_n[
In the formula, R_1 and R_2 may be the same or different and each represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and M represents an alkali metal atom, a hydrogen atom, or an ammonium group. ] (2) B treatment (second-stage low-temperature alkaline hydrogen peroxide bleaching) The A'-treated wet fibers are treated so that the pH of the liquid contained in the fibers is 11.5 to 12.5 and the hydrogen peroxide concentration is 3 to 3.
A method for continuous scouring and bleaching of fibers, which is characterized by adjusting the squeezing rate to 45 g/L and 70 to 200% of the weight of the fibers, and then allowing the fibers to stand at a temperature of room temperature to 50° C. for 5 hours or more.