WO2020196902A1 - Liquid reducing agent composition and reducing washing method - Google Patents

Abstract

Provided are: a liquid reducing agent composition that has advantages of reducing sugars such as less decrease of reducing power over time, less odor, and minor impact on the human body and the environment, and can further have good robustness; and a method for reducing and washing a substrate. In one embodiment, provided is a liquid reducing agent composition containing: (A) a reducing sugar; (B) an amphiphilic component that is at least one compound selected from the group consisting of (B1) polyester resins having an aromatic carbon ring, and (B2) compounds represented by general formula (1); and water. In one embodiment, provided is a method for reducing and washing a substrate, the method comprising washing a substrate in the presence of (A) a reducing sugar, and (B) an amphiphilic component that is at least one compound selected from the group consisting of (B1) polyester resins having an aromatic carbon ring, and (B2) compounds represented by general formula (1).

Description

Liquid reducing agent composition and reducing cleaning method

The present invention relates to a liquid reducing agent composition and a reducing cleaning method.

Conventionally, in the dyeing process of fibers, reducing agents such as hydrosulfite, thiourea dioxide, metal salts of formaldehyde sulfoxylic acid, and stannous chloride have been used in various processes. All of these reducing agents are powder solids or crystalline and easily scatter, and if they scatter around the workplace, there is concern about adverse effects on the health of workers and discolor the cloth stored in the vicinity. It also causes various troubles such as being mixed with a separately prepared processing liquid for fiber processing or printing paste and having an adverse effect.

In addition, in recent dyeing and processing factories, a system that automatically weighs and dispenses liquefied dyes or chemicals has become widespread from the viewpoint of aging workers and reducing the number of workers. There is also a demand for a liquid reducing agent.

However, conventional aqueous solutions of reducing agents, for example, aqueous solutions of hydrosulfite, thiourea dioxide, sodium formaldehyde sulfoxylate, etc., can be used as stock solutions, although their effectiveness does not occur if they are used immediately after the reducing agent is dissolved. When stored, there is a problem that the reducing power gradually decreases and the desired reducing power cannot be obtained. Further, the aqueous solution of these reducing agents has a problem in the working environment that an unpleasant odor is generated, and a problem that the influence on the human body and the environment is large.

On the other hand, conventionally, reducing sugars have been known as substances showing reducing properties. For example, Patent Document 1 describes soaping of a polyester / wool mixed fiber dyed product, which comprises a weakly reducing agent (A) such as a reducing saccharide and a polyoxyalkylene-based surfactant (B) having an HLB of 6 or more. A method of treating a polyester / wool mixed fiber dye in a bath with a neutral pH using the agent and the soaping agent is described. Further, Patent Document 2 contains a) a specific compound represented by the formula (I), b) a specific compound represented by the formula (II), and c) other additives in some cases. A method for reducing post-cleaning of dyed or printed polyester-containing fabrics using the mixture is described, and c) other additives may be monosaccharides or disaccharides.

Japanese Unexamined Patent Publication No. 2-91285 Special Table 2000-514879

Reducing sugar is suitable for an automatic liquid preparation system because it is easy to prepare as a liquid reducing agent, and it tends to be easy to store and manage in an aqueous solution because the reducing power in the aqueous solution does not decrease with time. is there. Reducing sugars also have the advantage of having less sulfur odor and less impact on the human body and the environment (for example, good biodegradability). However, the soaping agent described in Patent Document 1 has a problem that the reducing cleaning effect is weaker than that using hydrosulfite as a reducing agent. The main components of the reducing agent described in Patent Document 2 are a) the compound of the formula (I) and b) the compound of the formula (II), and the monosaccharide or the disaccharide is used as an auxiliary. However, there was room for improvement in the stability of the reducing agent over time in the technique described in Cited Document 2.

One aspect of the present invention is a liquid reducing agent composition capable of further obtaining good fastness while obtaining the advantages of reducing sugars such as a decrease in reducing power with time, odor, and less influence on the human body and the environment. It is an object of the present invention to provide a method for reducing and cleaning an object and a substrate.

The present invention includes the following aspects.
[1] (A) Reducing sugar,
(B) (B1) Polyester resin having an aromatic carbon ring and (B2) The following general formula (1):

[During the ceremony
Ar represents an aromatic carbocyclic ring
Y is the following formula (1-1), (1-2) or (1-3):

It is a substituent represented by
R is a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with an OH group or _two NH groups.
m is a number from 0 to 5, p is a number from 0 to 5, but m + p is a number from 0 to 5.
R ¹ represents an alkylene group having 2 to 4 carbon atoms.
n is the average number of moles of alkyleneoxy groups represented by (R ¹ O) and represents a number from 1 to 200. ]
An amphipathic component having an aromatic carbocyclic ring, which is one or more compounds selected from the group consisting of the compounds represented by, and water.
Liquid reducing agent composition containing.
[2] The above-described aspect 1, wherein the (B) amphipathic component is a combination of the polyester resin having the (B1) aromatic carbocycle and the compound represented by the (B2) general formula (1). Liquid reducing agent composition.
[3] The liquid reducing agent composition according to the above aspect 1 or 2, further comprising (C) an anionic compound.
[4] The liquid reducing agent composition optionally contains (C) an anionic compound.
Based on 100% by mass of the liquid reducing agent composition, the amount of the (A) reducing sugar is 10 to 60% by mass, and the total amount of the (B) amphoteric component and the (C) anionic compound is The liquid reducing agent composition according to any one of the above aspects 1 to 3, which is 0.1 to 20% by mass.
[5] The base material,
(A) Reducing sugar, (B) (B1) Polyester resin having an aromatic carbocycle and (B2) The following general formula (1):

[During the ceremony
Ar represents an aromatic carbocyclic ring
Y is the following formula (1-1), (1-2) or (1-3):

It is a substituent represented by
R is a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with an OH group or _two NH groups.
m is a number from 0 to 5, p is a number from 0 to 5, but m + p is a number from 0 to 5.
R ¹ represents an alkylene group having 2 to 4 carbon atoms.
n is the average number of moles of alkyleneoxy groups represented by (R ¹ O) and represents a number from 1 to 200. ]
An amphipathic component, which is one or more compounds selected from the group consisting of the compounds represented by.
A method of reducing cleaning of a substrate, which comprises cleaning in the presence of.

According to one aspect of the present invention, liquid reduction can further obtain good fastness while obtaining the advantages of reducing sugars such as a decrease in reducing power over time, odor, and less influence on the human body and the environment. A method for reducing and cleaning the agent composition and the substrate is provided.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following aspects.

<Liquid reducing agent composition>
One aspect of the present invention provides a liquid reducing agent composition containing (A) a reducing sugar, (B) an amphipathic component, and water. The (B) amphipathic component is (B1) a polyester resin having an aromatic carbocycle and (B2) the following general formula (1):

[During the ceremony,
Ar represents an aromatic carbocyclic ring
Y is the following formula (1-1), (1-2) or (1-3):

It is a substituent represented by
R is a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with an OH group or _two NH groups.
m is a number from 0 to 5, p is a number from 0 to 5, but m + p is a number from 0 to 5.
R ¹ represents an alkylene group having 2 to 4 carbon atoms.
n is the average number of moles of alkyleneoxy groups represented by (R ¹ O) and represents a number from 1 to 200. ]
It is one or more compounds selected from the group consisting of the compounds represented by.

(A) Reducing sugar The liquid reducing agent composition of the present disclosure contains (A) reducing sugar. The reducing sugar (A) is a sugar having a free or hemiacetal-bonded aldehyde group or a ketone group. The reducing sugar (A) has a reducing action on an application target of the liquid reducing agent composition (for example, a surplus dye on the fiber after dyeing) due to the reducing property of the aldehyde group. Reducing sugars have the advantages that the reducing power does not easily decrease with time in an aqueous solution, the biodegradability is good, the effect on the human body and the environment is small, and the odor is low. The reducing sugar (A) can be a monosaccharide or an oligosaccharide (that is, a sugar having a disaccharide or more and generally 10 sugars or less). As the reducing sugar (A), monosaccharides and disaccharides are preferable.

Examples of the reducing sugar include good detergency (that is, unfading (that is, poor reduction) and fading (reduced) excess dye by advancing the desired reduction of the dye in the reduction cleaning of the fiber after the dyeing process. Among the monosaccharides, aldoses such as glyceraldehyde, erythrose, treose, ribose, arabinose, xylose, lixose, allose, from the viewpoint of obtaining good fastness from the viewpoint of obtaining good fastness. Altrose, glucose, mannose, growth, aldose, galactose, and tarose are preferred, and among the disaccharides, maltose, lactose, turanose, and cellobiose are preferred. Among them, monosaccharides are preferable, aldoses are more preferable, xylose and glucose are even more preferable.
These reducing sugars can be used alone or in admixture of two or more.

(B) Amphiphilic component The liquid reducing agent composition of the present disclosure contains (B) amphipathic component. The (B) amphipathic component is represented by (B1) a polyester resin having an aromatic carbocycle (sometimes simply referred to as “(B1) polyester resin” in the present disclosure) and (B1) a general formula (1). It is one or more compounds selected from the group consisting of the compounds. (B) The amphoteric component is present in water together with (A) reducing sugar, so that (A) good contact between the reducing sugar and the object to be reduced (for example, excess dye on the fiber after dyeing) is achieved. It is considered that the reducing action can be secured and the reducing action can be exhibited well. Therefore, when the liquid reducing agent composition of the present disclosure is used for the reduction cleaning of the fiber after the dyeing process, (A) the reducing sugar can be kept in good contact with the undyed dye, and a high reduction cleaning effect (hence, therefore). High fastness) is considered to be obtained.

(B1) Polyester resin (B1) The polyester resin has an aromatic carbocycle. The (B1) polyester resin has anionic groups (unreacted carboxy group, the sulfone group in the case of a polyester resin having a sulfone group, etc.), (poly) alkylene (for example, ethylene, propylene or butylene) as hydrophilic sites. Surfactant having the (poly) alkyleneoxy group, etc. in the case of a polyester resin having an oxy group, and having a moiety other than the hydrophilic moiety (specifically, an aromatic carbocycle, an ester bond, etc.) as a hydrophobic moiety. Since it can be an agent, it functions as an amphipathic component. The (B1) polyester resin is typically a copolymer having a unit derived from a polyhydric alcohol component and a unit derived from a polyvalent carboxylic acid component.

Polyhydric alcohol components include aliphatic diols such as alkylene glycols having 2 or more carbon atoms (for example, ethylene glycol, propylene glycol, etc.) and polymers thereof (for example, oligomers such as diethylene glycol, polymers such as polyethylene glycol having a molecular weight of 150 to 5000). Compounds; aromatic diol compounds such as bisphenol A and bisphenol S; trifunctional or higher functional polyol compounds such as glycerin, trimethylolethane and trimethylolpropane; and the like. Among these, an aliphatic or aromatic diol compound is preferable, an aliphatic diol compound is more preferable, and ethylene glycol, diethylene glycol, and molecular weight are preferable from the viewpoint of cleanability and fastness and ease of viscosity control during polyester resin production. More preferably, 150-5000 polyethylene glycols and neopentyl glycols. These polyhydric alcohols can be used alone or in admixture of two or more.

Examples of the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and diphenoxyetanedicarboxylic acid; and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, maleic acid, and succinic acid. Acid; The aromatic dicarboxylic acid or an ester derivative of the aliphatic dicarboxylic acid (for example, an alkyl ester having 1 to 3 carbon atoms, a phenyl ester, an ester with ethylene glycol, etc.); Trifunctional or higher such as citric acid and benzenetricarboxylic acid. Polycarboxylic acids; sulfocarboxylic acids and salts thereof and ester derivatives thereof; hydroxycarboxylic acids such as β-hydroxyethoxybenzoic acid, p-hydroxybenzoic acid, malic acid; and the like. Examples of the sulfocarboxylic acid and its salts and their ester derivatives include aromatic sulfocarboxylic acids such as sulfoterephthalic acid, 5-sulfoisophthalic acid and 4-sulfophthalic acid, and metal salts and substituents of these sulfocarboxylic acids. Examples thereof include ammonium salts which may be contained, ester derivatives thereof (for example, alkyl esters having 1 to 3 carbon atoms, phenyl esters, esters with ethylene glycol, etc.) and the like. Here, examples of the metal salt include lithium salt, sodium salt, potassium salt, magnesium salt and the like. Examples of the ammonium salt which may have a substituent include an ammonium salt, a monoethanol ammonium salt, a diethanol ammonium salt, a triethanolammonium salt, an N-methylethanolammonium salt and the like. From the viewpoint of detergency and fastness and viscosity control during polyester resin production, the salt is preferably a sodium salt, a potassium salt, or an ammonium salt which may have a substituent.

From the viewpoint of detergency and fastness and ease of viscosity control during polyester resin production, aromatic dicarboxylic acid, sulfocarboxylic acid and salts thereof, and ester derivatives thereof are preferable as the polyvalent carboxylic acid component, and terephthalic acid is preferable. , Isophthalic acid, naphthalenedicarboxylic acid, sulfocarboxylic acid and salts thereof, and ester derivatives thereof are more preferable.

The polyvalent carboxylic acid component can be used alone or in combination of two or more.

In one embodiment, the (B1) polyester resin has a polyhydric alcohol component-derived unit and a polyvalent carboxylic acid component-derived unit, and one of the polyhydric alcohol component-derived unit and the polyvalent carboxylic acid component-derived unit is It is preferably a copolymer having an aromatic component and the other being an aliphatic compound, and more preferably a copolymer having an aliphatic diol component-derived unit and an aromatic dicarboxylic acid component-derived unit.

The (B1) polyester resin has a polyvalent carboxylic acid component selected from sulfocarboxylic acids, salts thereof, and ester derivatives thereof from the viewpoints of detergency and fastness, and (B) ease of polymerization reaction during production of the polyester resin. The moiety derived from is preferably 5 to 80 mol%, more preferably 10 to 50 mol% with respect to 100 mol% of the entire moiety derived from the polyvalent carboxylic acid component. (B1) The amount of the above-mentioned portion in the polyester resin can be confirmed by an NMR (nuclear magnetic resonance) method.

The (B1) polyester resin preferably has a (poly) ethyleneoxy group from the viewpoint of detergency and fastness, and from the viewpoint of reducing foaming during treatment, the (poly) ethyleneoxy group and the (poly) It is preferable to have both a propyleneoxy group. From the viewpoint of detergency and fastness, the (B1) polyester resin preferably contains (poly) ethyleneoxy groups in an amount of 20 to 95% by mass.

From the viewpoint of detergency and fastness, the (B1) polyester resin preferably has a weight average molecular weight of 1,500 to 50,000, and more preferably 1,500 to 20,000. When the weight average molecular weight of the polyester resin is 1,500 or more, the detergency and fastness are better, and when it is 50,000 or less, it is easier to mix with other components when preparing the liquid reducing agent composition. Tends to be.

In the present disclosure, the weight average molecular weight is determined by gel permeation chromatography, detector: RI / HLC-8320GPC (manufactured by TOSOH), column: Asahipak GF-510HQ (Showa Denko), particle size 5 μm, 7.5 ×. Measured using sodium polystyrene sulfonate as a standard substance using 300 mm (inner diameter x length (mm)) and eluent: 0.05 M-NaNO ₃ aqueous solution / acetonitrile = 1/1 as the mobile phase.

(B1) The polyester resin can be used alone or in combination of two or more. (B1) The method for producing the polyester resin is not particularly limited, and a conventionally used method such as a transesterification method or a direct polymerization method can be used.

(B2) Compound represented by the general formula (1) In one embodiment, the (B) amphipathic component is (B2) the general formula (1):

[During the ceremony
Ar represents an aromatic carbocyclic ring
Y is the following formula (1-1), (1-2) or (1-3):

It is a substituent represented by
R is a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with an OH group or _two NH groups.
m is a number from 0 to 5, p is a number from 0 to 5, but m + p is a number from 0 to 5.
R ¹ represents an alkylene group having 2 to 4 carbon atoms.
n is the average number of moles of alkyleneoxy groups represented by (R ¹ O) and represents a number from 1 to 200. ]
Includes compounds represented by. In the compound represented by the general formula (1), the site represented by (Y) _m ((R) _p ) Ar- is a hydrophobic site, and the site represented by-(R ¹ O) _n H is hydrophilic. Since it can be a surfactant as a site, it functions as an amphipathic component.

Ar represents an aromatic carbocycle. The aromatic carbocyclic ring may be a monocyclic ring (that is, a benzene ring) or a polycyclic ring (that is, a condensed ring) (for example, a naphthalene ring or the like), and is preferably a monocyclic ring from the viewpoint of fastness.

Y is a substituent represented by the formula (1-1), (1-2) or (1-3) from the viewpoint of obtaining good detergency and fastness, and is preferably the substituent represented by the formula (1-2). It is a group represented by. When a plurality of Ys are present in the molecule, Y may be the same or different.

R is a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with an OH group or _two NH groups from the viewpoint of obtaining good detergency and fastness. R may be a saturated or unsaturated chain aliphatic hydrocarbon group, a saturated or unsaturated alicyclic group, or an aromatic group. In a preferred embodiment, R is a saturated chain hydrocarbon group having 1 to 30 carbon atoms, an unsaturated chain hydrocarbon group having 2 to 30 carbon atoms (for example, a mono, di or triunsaturated group), or a carbon number of carbon atoms. It is an aromatic group of 6-10. The carbon number of R is more preferably 12 to 24 when R is a chain hydrocarbon group, and more preferably 6 when R is an aromatic group. Particularly preferred examples of R include phenyl groups, saturated or mono, di, or triunsaturated chain hydrocarbon groups having 12 to 18 carbon atoms (particularly preferably 15 carbon atoms).
Each of m and p is 0 to 5 from the viewpoint of obtaining good detergency and fastness, except that m + p is 0 to 5. Further, m + p is preferably 1 to 5, more preferably 2 to 3.

Examples of the alkylene oxide represented by R ¹ O include ethylene oxide and propylene oxide, and (R ¹ O) n is a single adduct of one alkylene oxide or a mixed addition of two or more alkylene oxides. It may be a thing. In the case of a mixed adduct, it may be a block adduct or a random adduct. The compound represented by the general formula (1) preferably has a (poly) ethyleneoxy group from the viewpoint of detergency and fastness, and from the viewpoint of reducing foaming during treatment, (poly) ethyleneoxy. It is preferable to have both a group and a (poly) propyleneoxy group.
n is 1 to 200, preferably 1 to 100, and more preferably 10 to 30 from the viewpoint of obtaining good detergency and fastness.

Among the compounds represented by the general formula (1), from the viewpoint of detergency and fastness, an ethylene oxide adduct of di or tristyrene phenol (that is, the number of ethylene oxide adducts added is 10 to 30 mol (that is, in the general formula (1)) n is 10 to 30)), and ethylene oxide adduct of cardanol (10 to 30 mol of ethylene oxide adduct (that is, n is 10 to 30 in the general formula (1))) is preferable, and ethylene oxide of di or tristyrene phenol is preferable. An adduct (10 to 30 mol of ethylene oxide adduct) is more preferable.

The compound represented by the general formula (1) has the following general formula (2): according to a conventional method.

[In the formula, Ar, Y, R, m and p are the same as those defined in the general formula (1). ]
It can be obtained by adding an average of n mol of the alkylene oxide corresponding to (R ¹ O) in the general formula (1) to 1 mol of the phenols represented by.

The suitable structure of the phenols represented by the general formula (2) is a structure corresponding to the above-mentioned structure as a preferable example of Ar, Y, R, m and p of the general formula (1). As the phenols represented by the general formula (2), phenol, phenylphenol, cumylphenol, naphthol, styrenated phenol (for example, di or tristyrene phenol), cardanol and the like can be preferably mentioned.

The phenols represented by the general formula (2) are prepared according to a conventional method according to the following general formula (3):
(R) _p- Ar-OH (3)
[In the formula, Ar, R and p are the same as those defined in the formula (1). ]
By benzylation, styrenization, or methylstyrene of the compound represented by the above according to the desired structure of Y represented by the formula (1-1), (1-2) or (1-3). Obtainable.
The compound represented by the general formula (1) can be used alone or in combination of two or more.

(B) As the amphipathic component, one kind of compound can be used alone or two or more kinds of compounds can be mixed and used. From the viewpoint of detergency and fastness, it is preferable to use (B1) a polyester resin and (B2) a compound represented by the general formula (1) in combination as the (B) amphipathic component. In that case, the blending ratio in the liquid reducing agent composition is (B1) :( B2) based on the mass, preferably 70:30 to 30:70, and more preferably 60:40 to 40:60.

From the viewpoint of detergency, fastness, and product stability, the blending ratio of (A) reducing sugar and (B) amphipathic component is based on the mass of (A): (B) in the liquid reducing agent composition. ), 99: 1 to 50:50 is preferable, 99: 1 to 70:30 is more preferable, and 99: 1 to 80:20 is even more preferable.

(C) Anionic Compound In a preferred embodiment, the liquid reducing agent composition contains (C) an anionic compound in addition to (A) reducing sugar and (B) amphipathic component from the viewpoint of detergency and fastness. .. The (B) amphipathic component of the present disclosure may be an anionic compound, but the (C) anionic compound of the present disclosure has a structure not included in the (B) amphipathic component (that is, (B) amphipathic component). It is intended to be an anionic compound (different from the component). It is considered that the anionic compound (C) can improve the effect of the component (B) and contributes to good detergency and fastness.

The blending ratio of (A) reducing sugar, (B) amphipathic component and (C) anionic compound is based on the mass in the liquid reducing agent composition from the viewpoint of obtaining good detergency and fastness. (A) + (B)]: In (C), 99: 1 to 50:50 is preferable, 99: 1 to 70:30 is more preferable, 99: 1 to 85:15, 99: 1 to 90:10. Is even more preferable.

The anionic compound (C) is not particularly limited, and is an anionic adduct of a linear or branched alcohol having 4 to 24 carbon atoms or an alkenol, or an alcohol having 4 to 24 carbon atoms in a linear or branched chain or an alkylene of an alkenol. Ionic compounds of oxide adducts, anionic compounds of phenols, anionic compounds of alkylene oxide adducts of phenols, anionic compounds of alkylphenols with 4 to 24 carbon atoms, alkylene oxide adducts of alkylphenols with 4 to 24 carbon atoms. Anionic compounds, alkylene oxide adducts of aliphatic amines having 4-44 carbon atoms in linear or branched chains, anionic compounds of alkylene oxide adducts of fatty acid amides having 4-44 carbon atoms in linear or branched chains, Linear or branched fatty acid salts with 4 to 24 carbon atoms, anionates of alkylene oxide adducts of linear or branched fatty acids with 4 to 24 carbon atoms, polyalkylene glycols and pluronic nonionic compounds (ie, An anionized product of a polyoxypropylene chain and a block copolymer consisting of two polyoxyethylene chains sandwiching the polyoxypropylene chain, and a tetronic nonionic compound (that is, an ethylene oxide adduct of a condensate of propylene oxide and ethylenediamine). Examples thereof include anionic compounds of. Examples of the alkylene oxide include ethylene oxide and propylene oxide. The adduct may be a product to which one kind of compound is added (single adduct) or a product to which two or more kinds of compounds are added (mixed adduct). In the case of a mixed adduct, it may be a block adduct or a random adduct.

Examples of the anionized product include sulfate ester salt, phosphoric acid ester salt, carboxylate and sulfosuccinate. Anionization can be performed according to a conventional method.

Further, as the (C) anionic compound, sulfonates of fats and oils, naphthalene sulfonic acid or a formalin condensate thereof or salts thereof, alkylbenzene sulfonates, polycarboxylic acids, polyacrylates and the like can also be used.

(C) The anionic group of the anionic compound may be at least partially (may be 100%) neutralized or may not be neutralized at all.
As the (C) anionic compound, one type may be used alone, or two or more types may be used in combination.

Among the anionic compounds (C), from the viewpoint of detergency and fastness, (B2) a sulfate ester salt of the compound represented by the general formula (1), an alcohol having 8 to 24 carbon atoms in a straight chain or a branched chain, or Alkenol Sulfate Ester, Linear or Branched Chain Alcohol with 8 to 24 Carbons or Alkenol alkylene Oxide Additive Sulfate Ester, Alkylbenzene Sulfate, Formula:

[In the formula, R represents hydrogen or an alkyl group having 1 to 22 carbon atoms, and X represents Na, K, or an ammonium ion which may have a substituent. ]
Naphthalene sulfonate represented by, or the following formula:

[In the formula, R represents hydrogen or an alkyl group having 1 to 22 carbon atoms, X represents Na, K, or an ammonium ion which may have a substituent, and n is a positive integer. ]
Naphthalene sulfonate formalin condensate represented by, polyalkylene glycol or sulfonic nonionic compound or sulfate ester salt of tetronic nonionic compound is preferable.

(B2) The sulfate ester salt of the compound represented by the general formula (1), the sulfate ester salt of the linear or branched alcohol having 8 to 24 carbon atoms or the alkylene oxide adduct of alkenol, and the alkylbenzene sulfonate. Preferably

(B2) A more preferable example of the structure derived from the sulfate ester salt of the compound represented by the general formula (1) (the structure derived from the compound represented by (B2) general formula (1) in the sulfate ester salt is (B2) general. The compound represented by the formula (1) is the same as described above), a sulfate ester salt of an alcohol or alkenol ethylene oxide adduct having 16 to 18 carbon atoms (preferably 10 to 30 mol of ethylene oxide adduct). Alkylbenzene sulfonates are even more preferred.

(D) Additional Ingredients The liquid reducing agent composition may optionally further contain additional ingredients. Additional components include, for example, (B1) polyester resin, (B2) compounds represented by the general formula (1), and (C) additional surfactants (nonionic surfactants) different from the anionic compounds. Anionic surfactants, cationic surfactants, and amphoteric surfactants). In one embodiment, the (D) additional component is at least one surfactant selected from the group consisting of (D1) cationic surfactants, amphoteric surfactants and nonionic surfactants (hereinafter, ( Includes at least one selected from the group consisting of D1) surfactants) and (D2) reducing agents. The (D1) surfactant preferably contains a cationic surfactant and / or an amphoteric surfactant, and more preferably a cationic surfactant, in that it is particularly advantageous for improving the fastness of the polyester / polyurethane mixed fiber. Agent and / or amphoteric surfactant.

(D1) Surfactant [cationic surfactant]
The cationic surfactant is at least one selected from the group consisting of an amine compound represented by the following general formula (4), a neutralized product (that is, a salt) of the amine compound, and a quaternized product of the amine compound. The species can be exemplified.

[During the ceremony,
R ¹ represents a monovalent hydrocarbon group having 8 to 26 carbon atoms which may be partitioned by at least one group selected from the group consisting of ester groups and amide groups.
R ² and R ³ are each independently: a monovalent hydrocarbon group having 8 to 26 carbon atoms which may be partitioned by at least one group selected from the group consisting of a hydrogen atom; an ester group and an amide group. Or (AO) n groups (in the formula, A represents an alkylene group having 2 to 4 carbon atoms, and n is the average number of moles of an alkylene oxide group represented by (AO), which is an integer of 1 to 100. Yes, but when both R ² and R ³ are (AO) n groups, the sum of the plurality of n is 1 to 100). ]

The neutralized product of the amine compound represented by the general formula (4) is a compound (salt) obtained by neutralizing the above-mentioned amine compound with an acid. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, methyl sulfuric acid, paratoluenesulfonic acid and the like.

The quaternized product of the amine compound represented by the general formula (4) is a compound (that is, a tertiary amine) in which each of R ² and R ³ is a hydrocarbon group or (AO) n group among the above-mentioned amine compounds. ) Is a compound obtained by treating with a quaternizing agent. Examples of the quaternary agent include methyl chloride, dimethyl sulfate, epichlorohydrin and the like.

The carbon number of each of the above-mentioned hydrocarbon groups of the general formula (4) is preferably 10 to 22, more preferably 12 to 22, and particularly preferably 12 to 20.

R ² and R ³ are independently, preferably (AO) n groups or alkyl groups having 1 to 2 carbon atoms. A is preferably an ethylene group.

N is preferably 1 to 50, more preferably 10 to 50. The total of n when a plurality of n are present in the molecule is preferably 1 to 50, more preferably 10 to 50.

[Amphitheater]
Examples of the amphoteric surfactant include alkyl betaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamide carboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactant. Can be mentioned. Of these, alkyl betaine is preferred. In particular, alkyl betaine obtained by treating the compound represented by the above general formula (4) exemplified as a cationic surfactant with sodium chloroacetate is preferable. The carbon number of the hydrocarbon group in the general formula (4) and the preferred embodiments of R ² and R ³ are the same as those described above for the cationic surfactant.

[Nonionic surfactant]
Examples of the nonionic surfactant include alcohols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, fats and oils, and alkylene oxide adducts of polypropylene glycol.

Examples of alcohols include alcohols, alkenols and acetylene alcohols having 8 to 24 carbon atoms in a straight chain or a branched chain.

Examples of amines include fatty acid amines having 8 to 44 carbon atoms in a straight chain or a branched chain.

Examples of amides include fatty acid amides having 8 to 44 carbon atoms in a straight chain or a branched chain.

Examples of fatty acids include straight-chain or branched-chain fatty acids having 8 to 24 carbon atoms.

Examples of polyunsaturated fatty acid esters include condensation reactions of polyunsaturated alcohols with straight-chain or branched-chain fatty acids having 8 to 24 carbon atoms.

Examples of fats and oils include vegetable fats and oils, animal fats and oils, vegetable waxes, animal waxes, mineral waxes and hydrogenated oils.

Examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and 1,4-butylene oxide.

Regarding the above-mentioned nonionic surfactant, the HLB is not particularly limited, but from the viewpoint of detergency, the HLB is preferably 5 to 20, more preferably 10 to 20, and even more preferably 10 to 18.

(D2) Reducing Agent As the reducing agent, a commonly used reducing agent can be exemplified. Specifically, thiourea dioxide, hydrosulfite compounds (sodium hydrosulfite, hydrosulfite calcium, etc.), zinc sulfoxy. Examples thereof include rate aldehyde, sodium sulfoxylate aldehyde, and acidic sodium bisulfite.

In the liquid reducing agent composition, the blending ratio of (A) reducing sugar, (B) amphipathic component, and (D1) surfactant is based on mass [(A) + (B)] :( D1). Therefore, 50:50 to 95: 5 is preferable, and 55:45 to 90:10 is more preferable. Ratios in the above range are particularly advantageous in improving fastness in cleaning polyester / polyurethane mixed fibers.

The liquid reducing agent composition is made uniform by mixing (A) reducing sugar, (B) amphipathic component, and water, and (C) anionic compound and / or (D) additional component as optional components. Can be obtained by Among them, from the viewpoint of (A) the ease of dissolving the reducing sugar in water, after (A) the reducing sugar is dissolved in water, (B) an amphipathic component, and optionally (C) an anionic compound and / Alternatively, (D) it is preferable to add and mix the additional components to make them uniform.

From the viewpoint of detergency, fastness, and product stability, the amount of (A) reducing sugar in the liquid reducing agent composition is 10 to 60% by mass, (B) amphipathic component and (C) anionic compound. The total amount of the above is preferably 0.1 to 20% by mass. When the liquid reducing agent composition having the above composition further contains (D) additional components, the total amount of (D) additional components is preferably 0.1 to 20% by mass.

From the viewpoint of preventing yellowing of the liquid reducing agent composition and from the viewpoint that when the liquid reducing agent composition is added to the reduction cleaning bath, it takes less time to adjust the pH of the reduction cleaning bath, the pH of the liquid reducing agent composition is set. Is preferably 3.0 to 8.0, more preferably 3.0 to 7.0.

The pH of the liquid reducing agent composition may be adjusted using a pH adjuster (alkali or acid). As alkali, hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as sodium carbonate, sodium hydrogencarbonate, potassium carbonate and sodium sesquicarbonate; borates such as potassium borate and sodium borate; sodium hydrogensulfate and sulfuric acid. Hydrogen sulfate such as potassium hydrogen sulfate; inorganic alkali metal salt such as sodium silicate, sodium metasilicate, potassium silicate, potassium metasilicate, zeolite; organic alkali metal salt such as sodium formate, sodium acetate, sodium oxalate; monoethanol Organic amines such as amine, diethanolamine, triethanolamine, triethylamine; ammonia and the like can be mentioned. Among these, hydroxides such as sodium hydroxide and potassium hydroxide are preferable.
Examples of the acid include organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; and inorganic acids such as hydrogen chloride, sulfuric acid and nitric acid.
These pH adjusters may be used alone or in combination of two or more.

The liquid reducing agent composition of the present disclosure is particularly useful as a reducing cleaning agent in, for example, dyeing processing of fibers, but other uses, for example, a cleaning agent for removing stains on a dyeing machine after dyeing, an indigo dye and the like. A reducing agent for making the dye into a leuco type to improve water solubility when dyeing cotton with a vat dye, a discharge printing agent for printing various fibers, and a soaping process for removing unfixed dyes in the printing of polyester fibers. It can also be suitably used for applications such as a reducing agent in.

<Reduction cleaning method for base material>
In one aspect of the present invention, the base material is a group consisting of (A) a reducing sugar, (B) (B1) a polyester resin having an aromatic carbocycle, and (B2) a compound represented by the general formula (1). Provided is a method for reducing and cleaning a substrate, which comprises cleaning in the presence of an amphipathic component, which is one or more compounds selected from the above.

The method for reducing and cleaning the substrate is to clean the substrate in the presence of (A) reducing sugars and (B) amphoteric components, and (C) anionic compounds and / or (D) additional components as optional components. The liquid reducing agent composition of the present disclosure may be used as it is as a reducing washing bath, or the liquid reducing agent composition of the present disclosure may be diluted with water and / or an aqueous medium for reduction. It may be used as a washing bath, or water (A) reducing sugar, (B) amphoteric component and (C) anionic compound and / or (D) additional component as optional components simultaneously or sequentially. And / or may be added to a reducing wash bath containing an aqueous medium. For example, (A) reducing sugar, (B) amphipathic component, and (C) anionic compound and / or (D) additional component as optional components have the above-mentioned composition ratio with respect to the liquid reducing agent composition. As such, they may be added simultaneously or sequentially to a reducing wash bath containing water and / or an aqueous medium.

In one aspect, the reduction cleaning method for the base material can be used for reduction cleaning after dyeing the polyester fiber material. Examples of the polyester fiber material include a polyester fiber material composed of polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polytrimethylene terephthalate and a copolymer thereof, and these polyester fiber materials and other synthetic fiber materials (for example,). Polypropylene fiber materials, etc.) and / or composite fiber materials with natural fiber materials can be mentioned. Examples of the form of the base material (that is, the polyester-based fiber material after dyeing) include yarn, knitting, woven fabric, non-woven fabric, and cotton. For example, in a mixed fiber which is a composite fiber material of a polyester fiber material and a polyurethane fiber material, the ratio of polyester / polyurethane is preferably 50/50 to 99/1, more preferably 70/30 to 97 / on a mass basis. It is 3.

Applicable dyeing machines include commonly used dyeing machines such as Wins dyeing machines, liquid flow dyeing machines, Zicker dyeing machines, cheese dyeing machines, beam dyeing machines, Overmeier dyeing machines, and skein dyeing machines. Can be done. At least (A) reducing sugar and (B) amphipathic component may be added to the dyeing treatment solution after dyeing to form a reduction washing bath, or the dyeing treatment solution is drained and at least (A) reducing sugar and (A) reducing sugar and the new bath are added. (B) A reducing washing bath may be prepared by adding an amphipathic component.

The total amount of (A) reducing sugar, (B) amphipathic component and any (C) anionic compound in the reducing washing bath is preferably 0.1 to 10 g / l, or 0.2 to 0.2 to. It is 5 g / l, or 0.5 to 3 g / l. When the total amount is 0.1 g / l or more, the effect of improving the fastness is good. Even if the total amount is increased by more than 10 g / l, the fastness does not tend to be improved in proportion to the amount used. Therefore, the total amount is preferably 10 g / l or less.

The amount of the (D1) surfactant in the reduction washing bath is preferably 0.01 to 5 g / l, 0.05 to 4 g / l, or 0.1 to 2 g / l. When the above amount is 0.01 g / l or more, the effect of improving the fastness is even better. Even if the amount is increased by more than 5 g / l, the fastness tends not to be improved in proportion to the amount used. Therefore, the amount is preferably 5 g / l or less.

The amount of the (D2) reducing agent in the reducing washing bath is preferably 0.1 to 10 g / l, 0.5 to 10 g / l, or 1 to 10 g / l. When the above amount is 0.1 g / l or more, the effect of improving the fastness is even better. Even if the amount is increased to more than 10 g / l, the fastness tends not to be improved in proportion to the amount used. Therefore, the amount is preferably 10 g / l or less.

From the viewpoint of detergency and fastness, the reduction washing bath preferably contains an alkaline agent of 0.1 g / l to 10 g / l, more preferably 0.5 g / l to 5 g / l. As the alkaline agent, hydroxides such as sodium hydroxide and potassium hydroxide are preferable.

From the viewpoint of detergency and fastness, the reduction washing bath preferably has a pH of 11 to 13.7, more preferably 12 to 13.5. When the pH exceeds 13.7, the performance tends not to be improved in proportion to the amount of alkali, so the pH is preferably 13.7 or less. The pH of the reduction washing bath can be adjusted by using the above-mentioned pH adjuster.

The bath ratio (that is, the ratio of the base material to the reducing washing bath on a mass basis) is preferably 1: 2 to 1:50, more preferably 1: 5 to 1:30, and 1: 5 to 1:20. More preferred.

Suitable blending ratios of (A) reducing sugars, (B) amphipathic components, and any (C) anionic compounds and / or (D) additional components in the reducing cleaning bath are in the reducing cleaning composition. It is the same as the above-mentioned compounding ratio.

From the viewpoint of detergency and fastness, the treatment temperature during reduction cleaning is preferably 60 to 100 ° C, more preferably 85 to 95 ° C. The treatment time is preferably 5 to 30 minutes. From the viewpoint of detergency and fastness, it is preferable to perform the reduction cleaning treatment with hot water and then with water. It is also preferable to carry out acid return.

In addition to (A) reducing sugars, (B) amphipathic components, and any (C) anionic compounds and / or (D) additional components, the reducing wash bath includes, for example, aqueous media, scouring aids, chelates. It is possible to include components such as agents.

As the aqueous medium, a hydrophilic solvent that is miscible with water is preferable. Examples of the hydrophilic solvent include methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, hexylene glycol, glycerin, butyl glycol, butyl diglycol, Solfit, N-methylpyrrolidone, dimethylformamide, and dimethylsulfooxide. And so on.

Examples of the refining aid include phosphoric acid compounds such as orthophosphoric acid, trimetaphosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid, and salts thereof. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and ammonium salt.

Examples of the chelating agent include EDTA, HEDTA, DTPA, and salts thereof; salts such as phosphonic acid such as phytic acid and ethidroic acid and sodium salts thereof; oxalic acid, citric acid, alanine, dihydroxyethylglycine, gluconic acid, and the like. Organic acids such as ascorbic acid, succinic acid, tartaric acid, glutaric acid, malonic acid and salts thereof; polyamino acids such as polyaspartic acid and polyglutamic acid; polycarboxylic acid, polymaleic acid and salts thereof can be mentioned. ..
Among the chelating agents, an organic acid such as sodium citrate or a salt thereof is preferable in consideration of the influence on the environment.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited to these Examples.

<Measurement method>
(1) Weight average molecular weight By gel permeation chromatography, detector: RI / HLC-8320GPC (manufactured by TOSOH), column: Asahipak GF-510HQ (Showa Denko), particle size 5 μm, 7.5 x 300 mm (inner diameter x length) (M)) was used as the mobile phase, and an eluent: 0.05 M-NaNO ₃ aqueous solution / acetonitrile = 1/1 was used, and sodium polystyrene sulfonate was used as a standard substance.

<Material>
(A) Reducing sugar xylose (D- (+) xylose, manufactured by Nacalai Tesque, Inc.)
Glucose (D- (+) glucose, manufactured by Nacalai Tesque, Inc.) was used.

(B1) Polyester resin [Synthesis of polyester resin b]
174.6 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of dimethyl sodium 5-sulfoisophthalate (polyvalent carboxylic acid having a sulfonic acid base), 58 g of ethylene glycol, in a reaction vessel. 816 g of polyethylene glycol having a molecular weight of 2000 and 0.1 g of zinc acetate were charged, and the temperature was raised from 150 ° C. to 230 ° C. over about 3 hours while stirring in a nitrogen gas atmosphere to carry out a transesterification reaction, and methanol was retained outside the system. I let you put it out. Then, 0.1 g of tetrabutyl titanate was added and the pressure was gradually reduced to adjust the internal pressure to about 10 kPa, and the mixture was reacted at 250 ° C. ± 5 ° C. for 2 hours to obtain 1010 g of a polyester copolymer (resin b). The obtained polyester copolymer (resin b) has a polyvalent carboxylic acid having a sulfonic acid base in the polyvalent carboxylic acid component in an amount of 10 mol%, and contains a polyoxyethylene chain in the polyester copolymer. The amount was about 80% by mass, and the weight average molecular weight of the polyester copolymer was about 5500.

[Synthesis of polyester resins a and c to i]
Amount of polyvalent carboxylic acid having a sulfonic acid base in the polyvalent carboxylic acid component, content of polyoxyethylene chain in polyester copolymer, molecular weight of polyoxyethylene chain contained in polyester copolymer, polyester The reaction was carried out in the same manner as in the resin b except that the weight average molecular weight of the copolymer was changed as shown in Table 1 to obtain polyester resins a and c to i.

(B2) Compound 3SP10E represented by the general formula (1): 10 mol of ethylene oxide adduct of tristyrene phenol A compound obtained by reacting phenol with 3 mol of styrene and then reacting with 10 mol of ethylene oxide was used. ..
3SP20E: 20 mol of ethylene oxide adduct of tristyrene phenol The phenol was reacted with 3 mol of styrene and then 20 mol of ethylene oxide was reacted according to the adduct.
3SP30E: 30 mol of ethylene oxide adduct of tristyrene phenol The phenol was reacted with 3 mol of styrene and then 30 mol of ethylene oxide was reacted according to the adduct.
Cardanol 10E: 10 mol of ethylene oxide adduct of cardanol A reaction of 10 mol of ethylene oxide with cardanol according to the standard method was used.
Cardanol 30E: 30 mol of ethylene oxide adduct of cardanol A reaction of 30 mol of ethylene oxide with cardanol according to the adduct formula was used.

(C) Anionic compound The following compound was used. The amount of the (C) anionic compound shown in the table is the amount as a solid content.
O4ES: Sulfate of 4 mol of ethylene oxide adduct of oleyl alcohol (4 mol adduct of ethylene oxide of oleyl alcohol is reacted with sulfamic acid according to a conventional method to obtain an ammonium sulfate ester salt (solid content 40% by mass). did.)
O10ES: Sulfated product of 10 mol of ethylene oxide adduct of oleyl alcohol (ammonium sulfate ester ammonium salt (solid content 40% by mass) obtained in the same manner as O4ES was used).
3SP20E-S: Sulfated product of 20 mol of ethylene oxide adduct of tristyrene phenol (ammonium sulfate ester sulfate obtained in the same manner as O4ES (solid content 40% by mass) was used).
Cardanol 20ES: Sulfate of 20 mol adduct of ethylene oxide of cardanol (ammonium sulfate ester obtained in the same manner as O4ES (solid content 40% by mass) was used).
PEG600-2S: 2 molar sulfated product of polyethylene glycol 600 (ammonium sulfate ester ammonium salt (solid content 40% by mass) obtained in the same manner as O4ES was used).
L64-S: 1 mol sulfated product of Pluronic L-64 (product name, manufactured by ADEKA Co., Ltd.) (Ammonium sulfate ester ammonium salt (solid content 40% by mass) obtained in the same manner as O4ES was used.)
TR704-4S: Tetronic TR-704 (product name, manufactured by ADEKA Co., Ltd.) 4-molar sulfated product (ammonium sulfate ester ammonium salt (solid content 40% by mass) obtained in the same manner as O4E-S was used).
ABS-Na: Neutralized sodium hydroxide of TAYCA Power L121 (alkylbenzene sulfonic acid, manufactured by TAYCA Corporation) (solid content 40%)
MON7: Eleminor MON-7 (soda lauryldiphenylsulfonate, manufactured by Sanyo Chemical Industries, Ltd.)
Naphthalene sulfonic acid (powder): Reagent, Demol N manufactured by Wako Pure Chemical Industries, sodium salt of β-naphthalene sulfonic acid formalin condensate, Palm oil fatty acid salt manufactured by Kao Co., Ltd .: Neutralized sodium hydroxide of palm oil fatty acid (solid content 40) mass%)
PC300: Cellopole PC-300 (soda polycarboxylic acid, manufactured by Sanyo Chemical Industries, Ltd.)
A4Na: Phosphamidon A-4 (butyl acid phosphate, manufactured by SC Organic Chemistry Co., Ltd.), sodium hydroxide neutralized product (solid content 40% by mass)

(D1) Surfactant Cationic surfactant (1):
Epichlorohydrin quaternary product (50% by mass aqueous solution) of 20 mol of ethylene oxide adduct of hardened beef tallow amine (amine ABT-R, manufactured by Nippon Oil & Fat Co., Ltd.)
Cationic surfactant (2):
Dimethyl sulfate quaternary product (50% by mass aqueous solution) of 35 mol adduct of ethylene oxide of hardened beef tallow amine (amine ABT-R, manufactured by Nippon Oil & Fat Co., Ltd.)

Other Compounds O16E: 16 mol of ethylene glycol adduct of oleyl alcohol S40E: 40 mol of ethylene oxide adduct of stearyl alcohol CO43-FA: 43 mol of ethylene oxide adduct of castor oil and polyester with phthalic acid (43 mol of ethylene oxide adduct of castor oil) 1 mol) and phthalic acid (1 mol) were esterified according to a conventional method.)
PEHA700E200P: Ethylene oxide 700 of pentaethylene hexamine 200 mol of propylene oxide Additive Sodium sulfate of stearyl alcohol (Compound obtained by sulfate esterifying stearyl alcohol with chlorosulfonic acid and neutralizing with sodium hydroxide according to a conventional method. It was used.)
Soda stearate (a compound obtained by neutralizing stearic acid with sodium hydroxide was used.)

[Making dyed cloth]
(Examples 1 to 43, Comparative Examples 1 to 12)
Test cloth: After scouring, polyester jersey knit (thread count 150d, basis weight 280g / m ² ) 12.5g
Dye: Disperse black PB-SF 300% 3% o. w. f
Dispersion leveling agent: NICCA SUNSOLT RM-3406 0.5g / l
pH regulator: 80% by mass acetic acid 0.4 g / l
Dyeing machine: MINI-COLOR (Nissen 300ml type)
Bath ratio: 1:12 (bath volume 150 ml)
Dyeing: 60 ° C → (temperature rise 2 ° C / min) → 130 ° C × 40 minutes → cool to 70 ° C and take out → wash with hot water for 5 minutes → wash with water for 5 minutes → dry at 50 ° C (Examples 44 to 52, Comparative Examples 13 to 13) 14)
Test cloth: After scouring, polyester / polyurethane = 85/15 blended knit cloth 12.5g
Dye: Disperse black PB-SF 300% 5% o. w. f
Dispersion leveling agent: NICCA SUNSOLT RM-3406 1g / l
pH regulator: 80% by mass acetic acid 0.4 g / l
Dyeing machine: MINI-COLOR (Nissen 300ml type)
Bath ratio: 1:12 (bath volume 150 ml)
Dyeing: 60 ° C → (temperature rise 2 ° C / min) → 130 ° C x 40 minutes → cool to 70 ° C and take out → wash with hot water 5 minutes → wash with water 5 minutes → dry at 50 ° C

[Reduction cleaning test method]
(Examples 1 to 43, Comparative Examples 1 to 12)
Test cloth: 12.5 g of the above dyed cloth
Liquid caustic soda 48% by mass: 3 g / l
Reducing agent: Liquid reducing agent composition 3 g / l
Dyeing machine: MINI-COLOR (Nissen 300ml type)
Bath ratio: 1:12 (bath volume 150 ml)
Reduction washing: 60 ° C → (temperature rise 3 ° C / min) → 85 ° C × 20 minutes → cool to 70 ° C and take out → wash with hot water for 5 minutes (with or without) → wash with water for 5 minutes → dry at 50 ° C (Example 44- 52, Comparative Examples 13-14)
Test cloth: 12.5 g of the above dyed cloth
Liquid caustic soda (flakes): 2 g / l
Reducing cleaning agent: 5 g / l (as a 50% by mass aqueous solution) of each of the liquid reducing agent compositions of Examples 3, 11 and 13 + cationic surfactant (1) or cationic surfactant (2) 2 g / l. (As a 50% by mass aqueous solution)
Dyeing machine: MINI-COLOR (Nissen 300ml type)
Bath ratio: 1:12 (bath volume 150 ml)
Reduction washing: 60 ° C → (temperature rise 3 ° C / min) → 85 ° C x 20 minutes → cool to 70 ° C and take out → hot water washing 5 minutes (with or without) → water washing 5 minutes → 50 ° C drying

[Example 1]
To 50 parts by mass of water at 40 ° C., 40 parts by mass of xylose as (A) reducing sugar was added and dissolved by stirring. Next, (B) 10 parts by mass of the polyester resin b described above was added as an amphipathic component and dissolved by stirring to (A) 40% by mass of the reducing sugar, (B) 10% by mass of the amphipathic component, and water. A liquid reducing agent composition containing 50% by mass of the above was obtained. This liquid reducing agent composition was left at 20 to 25 ° C. for 1 day.

In a pot of a MINI-COLOR dyeing machine (Nissen 300 ml type), water, the above-mentioned liquid reducing agent composition after being left for 1 day, and a pH adjuster are put and mixed, and the liquid reducing agent composition is mixed at 3 g / l, pH. A uniform reducing wash bath containing 2 g / l of 48 mass% sodium hydroxide as a regulator was prepared. Next, the polyester jersey knit dyed above was put into a reduction washing bath so that the bath ratio was 1:12, and the reduction washing bath was heated from 60 ° C. to 85 ° C. at 3 ° C./min. , Reduction washing was performed at 85 ° C. for 20 minutes. Then, the mixture was cooled to 70 ° C., washed with hot water for 5 minutes and washed with water for 5 minutes, and then dried at 50 ° C. to obtain a reduction washing cloth. In addition, a reduction cleaning cloth was also prepared when the reduction cleaning was not performed with hot water.
The solvent fastness of the obtained reduction cleaning cloth was evaluated according to the following criteria.

Evaluation item (1) Solvent fastness The reduction cleaning cloth was cut into 1 cm squares and placed on a 5A filter paper. Five drops of acetone were dropped on the dropper using a dropper, and immediately sandwiched with a petri dish larger than 5A filter paper for 10 seconds from above and below. After 10 seconds, the petri dish was removed, and the concentration of the dye developed together with acetone on the filter paper was graded by a gray scale for contamination (JIS L 0805: 2005).
When the evaluation is in the middle of the grade, for example, when it is in the middle of the 3rd and 4th grade, it is displayed as 3-4. When the performance was slightly good, a "+" was added to the grade, and when the performance was slightly inferior, a "-" was added to the grade.

Evaluation item (2) Product stability test The liquid reducing agent composition used in Examples and Comparative Examples is placed in a glass container with a lid and stored at room temperature (20 to 25 ° C) away from direct sunlight for one day. Later, the appearance and odor at the time of opening were confirmed.

[Examples 2-43, Comparative Examples 1-10]
Regarding (A) reducing sugar, (B) amphipathic component, (C) anionic compound, hydrosulfite and other compounds, the types and amounts used (parts by mass) were changed as shown in Tables 2 to 6. The same operation as in Example 1 was carried out to obtain a reducing cleaning treated cloth. The solvent fastness of the obtained reduction cleaning cloth was evaluated in the same manner as in Example 1.

[Comparative Examples 11 to 12]
The reduction cleaning treatment cloth was operated in the same manner as in Example 1 except that the liquid reducing agent composition obtained by using hydrosulfite and other compounds as shown in Table 6 was used immediately without being left for one day. Got The solvent fastness of the obtained reduction cleaning cloth was evaluated in the same manner as in Example 1.

[Examples 44 to 52, Comparative Examples 13 to 14]
Table 7 (the amount of the liquid reducing agent composition and the cationic surfactants (1) and (2) used in the reduction washing bath g / l) and Table 8 (the amount shown in Table 7 is shown as the solid content ratio of each component. The polyester / polyurethane blended knitted cloth was reduced-washed using a reducing-washing bath containing each component in the amount shown in (1) to obtain a reducing-washing treated cloth. The solvent fastness of the obtained reduction cleaning cloth was evaluated in the same manner as in Example 1.

[Comparative Example 15]
A reducing cleaning treated cloth was obtained in the same manner as in Comparative Example 13 except that the liquid reducing agent composition was used immediately without being left for one day. The solvent fastness of the obtained reduction cleaning cloth was evaluated in the same manner as in Example 1.

[Comparative Example 16]
A reducing cleaning treated cloth was obtained in the same manner as in Comparative Example 14 except that the liquid reducing agent composition was used immediately without being left for one day. The solvent fastness of the obtained reduction cleaning cloth was evaluated in the same manner as in Example 1.

The liquid reducing agent compositions used in Examples 1 to 43 and Comparative Examples 3 to 10 did not change in appearance or generate odor after 1 day.
The liquid reducing agent compositions used in Comparative Examples 1 and 2 were slightly yellowed after 1 day, although there was no separation in appearance, and an odor was generated, and a large deterioration in performance was observed.
The liquid reducing agent compositions used in Comparative Examples 11 to 12 did not change in appearance and generated almost no odor.
From the comparison between Examples 1 to 14 and Comparative Examples 3 to 10, (A) a reducing sugar and (B1) a polyester resin or (B2) a specific amphipathic compound which is a compound represented by the general formula (1). By using in combination with, the fastness can be improved as compared with the case where (A) reducing sugar is used in combination with (B1) polyester resin or (B2) a compound other than the compound represented by the general formula (1). Do you get it.
From Examples 15 to 20, it was found that the fastness was further improved by using (B) a polyester resin and (B2) a compound represented by the general formula (1) in combination as an amphipathic component. It was.
Further, from Examples 21 to 43, by further using (C) an anionic compound in addition to (A) reducing sugar and (B) amphipathic component, the fastness is further improved, and hydro as a reducing agent is used. It was found that the robustness was comparable to that when Sulfite was used.

From the comparison of Examples 44 to 46, Examples 47 to 49 and 50 to 52, and Comparative Examples 13 and 14, by using (A) a reducing sugar and (B) an amphipathic component in combination, a polyester / polyurethane mixed fiber was used. It was found that the fastness in washing was better than that when hydrosulfite was used as a reducing agent. Further, when a cationic surfactant as (D1) surfactant is further used in addition to (A) reducing sugar and (B) amphipathic component, as compared with the case where the cationic surfactant is not used, it is compared with the case where the cationic surfactant is not used. It was found that the fastness of the polyester / polyurethane mixed fiber in cleaning was further improved.

The liquid reducing agent composition of the present invention can be easily applied to an automatic liquid preparation system, and since the reducing power does not decrease and odor is not generated over time, it is easy to store and manage. Further, in one embodiment, the liquid reducing agent composition obtains a fastness comparable to that of a conventional reducing cleaning agent using, for example, hydrosulfite as a reducing agent while using a reducing sugar as the reducing agent. Can be done. Further, the liquid reducing agent composition has little influence on the human body and the environment, has good biodegradability, and can reduce the wastewater load. Therefore, the liquid reducing agent composition of the present invention is extremely useful in each step of dyeing processing of fibers, for example.

Claims (5)

1. (A) Reducing sugar,
   (B) (B1) Polyester resin having an aromatic carbon ring and (B2) The following general formula (1):
   

   

   [During the ceremony
   Ar represents an aromatic carbocyclic ring
   Y is the following formula (1-1), (1-2) or (1-3):
   

   

   It is a substituent represented by
   R is a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with an OH group or _two NH groups.
   m is a number from 0 to 5, p is a number from 0 to 5, but m + p is a number from 0 to 5.
   R ¹ represents an alkylene group having 2 to 4 carbon atoms.
   n is the average number of moles of alkyleneoxy groups represented by (R ¹ O) and represents a number from 1 to 200. ]
   An amphipathic component having an aromatic carbocyclic ring, which is one or more compounds selected from the group consisting of the compounds represented by, and water.
   Liquid reducing agent composition containing.
2. The liquid reduction according to claim 1, wherein the (B) amphipathic component is a combination of the polyester resin having the (B1) aromatic carbocycle and the compound represented by the (B2) general formula (1). Agent composition.
3. The liquid reducing agent composition according to claim 1 or 2, further comprising (C) an anionic compound.
4. The liquid reducing agent composition optionally contains (C) an anionic compound.
   Based on 100% by mass of the liquid reducing agent composition, the amount of the (A) reducing sugar is 10 to 60% by mass, and the total amount of the (B) amphoteric component and the (C) anionic compound is The liquid reducing agent composition according to any one of claims 1 to 3, which is 0.1 to 20% by mass.
5. Base material,
   (A) Reducing sugar, (B) (B1) Polyester resin having an aromatic carbocycle and (B2) The following general formula (1):
   

   

   [During the ceremony
   Ar represents an aromatic carbocyclic ring
   Y is the following formula (1-1), (1-2) or (1-3):
   

   

   It is a substituent represented by
   R is a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with an OH group or _two NH groups.
   m is a number from 0 to 5, p is a number from 0 to 5, but m + p is a number from 0 to 5.
   R ¹ represents an alkylene group having 2 to 4 carbon atoms.
   n is the average number of moles of alkyleneoxy groups represented by (R ¹ O) and represents a number from 1 to 200. ]
   An amphipathic component, which is one or more compounds selected from the group consisting of the compounds represented by.
   A method of reducing cleaning of a substrate, which comprises cleaning in the presence of.