JP7332286B2 - Textile treatment method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for treating textile products and a composition for treating textile products for heat treatment.

Bleaching agents used for bleaching textile products such as clothing are roughly classified into chlorine bleaching agents and oxygen bleaching agents. Chlorine-based bleaches are difficult to use for colored fabrics because of restrictions on usable fibers, but they have high bleaching performance. Oxygen-based bleaching agents have advantages such as a weak odor and being able to be applied directly to stains. Known oxygen-based bleaching agents include liquids containing hydrogen peroxide and solids containing percarbonates that release hydrogen peroxide in water.

Bleaching treatment of textile products at home is generally carried out by incorporating it into the washing process. However, when it is found that the dirt has not been sufficiently removed after washing, the textile product is often washed again, or else the textile product is used with the dirt left as it is. From this point of view, it would be a desirable method for users if only the dirty part could be simply treated without washing the entire textile product again without removing the color of the textile product itself.

U.S. Pat. No. 5,300,000 discloses a method for treating a patchy spotted fabric having a first side and a second side comprising (a)(i) a predetermined surfactant; , (ii) a glycol ether solvent, (iii) a bleaching agent, and (iv) water, respectively, in predetermined ranges, and applying a stain removing composition to the spotted and stained portion of the fabric; (b) contacting an absorbent stain receptacle on a first side of the fabric about the stained area; (c) a second side of the fabric on the stained area; (d) optionally concurrently with step (a) or subsequent to step (a), contacting the perimeter of the stained portion of the fabric with a treatment member; and (e) optionally applying an aqueous rinse solution around the stained portion of the fabric.

Japanese Patent Publication No. 2002-527646

INDUSTRIAL APPLICABILITY The present invention provides a method for treating textile products, such as bleaching, deodorizing, and sterilizing organic stains, without affecting colored articles.

The present invention applies an aqueous composition containing hydrogen peroxide, an organic radical forming agent and water to a textile product,
heat-treating the textile product to which the aqueous composition is applied at 80° C. or higher and 250° C. or lower;
to a method for treating textiles.

The present invention also relates to a textile treatment composition for heat treatment containing hydrogen peroxide, an organic radical forming agent and water.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a method for treating textile products, such as bleaching, deodorizing, and sterilizing organic stains, without affecting colored articles. Further, according to the present invention, there is provided a textile treatment composition for heat treatment used in such a method.

In the present invention, hydrogen peroxide [hereinafter sometimes referred to as component (A) or hydrogen peroxide (A)], an organic radical forming agent [hereinafter sometimes referred to as component (B) or organic radical forming agent (B) ] and an aqueous composition containing water (hereinafter also referred to as the aqueous composition of the present invention) is applied to the textile product. The aqueous composition of the present invention is described below.

The aqueous composition of the present invention preferably contains hydrogen peroxide (A) in an amount of 0.01% by mass or more, more preferably 0.5% by mass or more, and preferably Less than 2% by mass, more preferably 1% by mass or less.

In the present invention, high effects such as bleaching, sterilization, and deodorization can be obtained by performing heat treatment at a predetermined temperature in a state in which hydrogen peroxide and an organic radical forming agent coexist. The reason for this is not necessarily clear, but is presumed as follows. When heat treatment is performed at a predetermined temperature in a state in which hydrogen peroxide and an organic radical forming agent coexist, hydrogen peroxide generates hydroxyl radicals with relatively high hydrophilicity. It is believed that this hydroxy radical acts on the organic radical forming agent (B) to generate an organic radical. Since the generated organic radicals contain organic groups, they are relatively more hydrophobic than hydroxyl radicals. It is presumed that it efficiently decomposes staining pigments because it easily acts on highly hydrophobic pigments such as.

The organic radical former (B) may be a source of organic radicals, preferably hydrophobic organic radicals.

Examples of the organic radical-forming agent (B) include compounds that react with hydroxyl radicals generated from hydrogen peroxide to form radicals when heated in the presence of hydrogen peroxide.

Examples of the organic radical forming agent (B) include fatty acids having 3 to 14 carbon atoms, lactate esters having 4 to 10 carbon atoms, formic acid esters having 3 to 10 carbon atoms, and 3 carbon atoms. one or more compounds selected from acetic esters having 10 or less carbon atoms, ketones having 3 or more and 5 or less carbon atoms, and aldehydes having 3 or more and 5 or less carbon atoms.

The organic radical forming agent (B) is preferably a compound having an oxidation-reduction potential of 0.9 eV or more, preferably 1.0 eV or more, and preferably 2.3 eV or less, more preferably 2.0 eV or less. Here, the oxidation-reduction potential of the organic radical forming agent (B) is according to the measurement method in Examples described later. Hereinafter, the term "oxidation-reduction potential" refers to the measurement method in Examples unless otherwise specified.

The organic radical forming agent (B) preferably produces organic radicals having a redox potential close to that of hydroxyl radicals produced from hydrogen peroxide. According to the measurement method in Examples described later, the oxidation-reduction potential of hydroxyl radicals is 2.4 eV. With respect to this value, the redox potential of the organic radical forming agent (B) preferably has a redox potential difference of -1.5 eV or more and -0.1 eV or less. When the difference in the oxidation-reduction potential of the organic radical forming agent (B) with respect to the oxidation-reduction potential of hydroxy radicals is within the above range, organic radicals are easily generated.

Furthermore, the organic radical-forming agent (B) of the present invention is effective against hydrophobic stains such as stains derived from sebum because the organic radicals it generates are more hydrophobic. It is preferable because it does not affect the base or dye. In the present invention, ClogP, which is generally known as an index of hydrophobicity, can be used. Specifically, the ClogP of the organic radical-forming agent (B) is preferably a positive number, more preferably 0.01 or more, and still more preferably 0.1 or more, and is added to the aqueous composition. From the viewpoint of solubility or dispersion stability, the compound is preferably 8.0 or less, more preferably 7.0 or less.

For ClogP values, see, for example, Daylight Chemical Information Systems, Inc. (Daylight CIS), etc., logP values of many compounds are listed and can be referred to. If there is no logP value actually measured, it can be calculated using the program "CLOGP" (DaylightCIS) or the like. Among others, calculation using the program "CLOGP" is preferable due to its high reliability.
In the program "CLOGP", the value of "calculated logP (ClogP)" calculated by the fragment approach of Hansch, Leo is output along with the measured value of logP, if any. The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bonds (A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammens, J. Am. B. Taylor and C. A. Ramsden, Eds., p.295, Pergamon Press, 1990). Since this ClogP value is currently the most common and reliable estimate, it is preferable to use the ClogP value instead in the absence of actual logP values for compound selection. In the present invention, either the actual logP value or the ClogP value calculated by the program "CLOGP" may be used.

As for the organic radical forming agent (B), since the oxidation-reduction potential is not affected by the number of carbon atoms in the compound as described above, it can be expressed as a roughly constant numerical value if the structure such as the presence or absence of functional groups is determined. Therefore, the compound includes a saturated fatty acid (1.6 eV), a lactate ester (1.7 eV) that is an ester compound of a lactate ester and an aliphatic alcohol, a formic acid, or a formic acid ester that is an ester of an acetic acid and an aliphatic alcohol. Acetate ester (1.3 eV), ketone (0.9 eV) represented by RC(=O)-R' [wherein R and R' are alkyl groups] and R-CHO [wherein R is alkyl group] and one or more compounds selected from aldehydes (1.1 eV) represented by the group].

Further, the organic radical-forming agent (B) of the present invention preferably contains a saturated fatty acid having 6 to 14 carbon atoms (oxidation-reduction potential: 1.0 to 1.5) because of the problem of hydrophobic conditions and base odor as described above. 6 eV, ClogP: 1.9 to 6.2), lactate ester having 4 to 10 carbon atoms (oxidation-reduction potential: 1.7 eV, ClogP: −0.2 to 3.0), 3 or more carbon atoms 10 or less formic acid, an acetate ester having 3 to 10 carbon atoms (redox potential: 1.3 eV, ClogP: 0.3 to 4.0), a ketone having the above structure having 3 to 5 carbon atoms (redox potential: 0.9 eV, ClogP: -0.2 to 0.9), and an aldehyde of the above structure having 3 to 5 carbon atoms (redox potential: 1.1 eV, ClogP: -0.2 1 or more compounds selected from 1.9).

The organic radical forming agent (B) is more preferably a saturated fatty acid having 8 to 14 carbon atoms, a lactate ester having 4 to 6 carbon atoms, a formic acid ester having 3 to 10 carbon atoms, and a carbon One or more compounds selected from acetic esters having a number of 3 or more and 10 or less can be mentioned. Examples of saturated fatty acids having 8 to 14 carbon atoms include octanoic acid (redox potential: 1.6 eV, ClogP: 3.0), pelargonic acid (redox potential: 1.6 eV, ClogP: 3.5), and capric acid. (redox potential: 1.6 eV, ClogP: 4.0), lauric acid (redox potential: 1.6 eV, ClogP: 5.1), myristic acid (redox potential: 1.6 eV, ClogP: 6.2 ). Examples of lactate esters having 4 to 6 carbon atoms include methyl lactate (redox potential: 1.7 eV, ClogP: −0.2) and ethyl lactate (redox potential: 1.7 eV, ClogP: 0.3). , propyl lactate (redox potential: 1.7 eV, ClogP: 0.9), and butyl lactate (redox potential: 1.7 eV, ClogP: 1.4). Examples of the formate or acetate having 3 to 10 carbon atoms include ethyl formate (redox potential: 1.3 eV, ClogP: 0.3), butyl formate (redox potential: 1.3 eV, ClogP: 0.3 eV), 8), ethyl acetate (redox potential: 1.3 eV, ClogP: 0.7), propyl acetate (redox potential: 1.3 eV, ClogP: 1.2), butyl acetate (redox potential: 1.3 eV, ClogP: 1.8) and pentyl acetate (redox potential: 1.3 eV, ClogP: 2.3).

The organic radical former (B) is even more preferably one or more compounds selected from capric acid, lauric acid, myristic acid, methyl lactate, ethyl lactate and butyl lactate.

In the aqueous composition of the present invention, the organic radical forming agent (B) is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, and preferably The content is 1% by mass or less, more preferably 0.5% by mass or less.

In the aqueous composition of the present invention, the mass ratio of the content of hydrogen peroxide (A) to the content of the organic radical forming agent (B) is the content of hydrogen peroxide (A)/organic radical forming agent ( The content of B) is preferably 0.01 or more, more preferably 0.5 or more, and preferably 40 or less, more preferably 20 or less, and still more preferably 5 or less, from the viewpoint of organic radical generation efficiency. be.

By adding an amide compound represented by the following general formula (1) [hereinafter sometimes referred to as component (C) or amide compound (C)] to the aqueous composition of the present invention, the melanin decomposition rate is further improved. Therefore, it is preferable. Due to its structure, the low-molecular-weight amide compound can form a non-covalent complex with hydrogen peroxide (A) to promote the generation of hydroxyl radicals, and as a result, the generation rate of organic radicals is improved. .
X—C(═O)—N(R ¹ )(R ² ) (1)
[Wherein, R ¹ and R ² are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X is -R ¹ , -N(R ³ )(R ⁴ ), phenyl group or benzyl wherein R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group or a benzyl group, wherein R ³ and R ⁴ are both a phenyl group or a benzyl group isn't it. ]

The amide compound (C) is believed to promote cleavage by forming a ^hydrogen bond with ^—OH of hydrogen ^peroxide to facilitate the generation of radicals ^. Compounds in which one of them is a hydrogen atom are preferred. Further, in the formula, X is a hydrogen atom, a methyl group, —N(R ³ )(R ⁴ ) or a phenyl group, and at least one of R ¹ , R ² , R ³ and R ⁴ is a hydrogen atom and the rest are hydrogen atoms, methyl groups or phenyl groups.

As the compound of general formula (1), urea, formamide, benzamide, N,N-dimethylformamide and acetanilide are preferred, and urea is more preferred from the viewpoint of home use and cost.

The aqueous composition of the present invention preferably contains 0.1% by mass or more, more preferably 1% by mass or more, and , preferably 5% by mass or less, more preferably 2% by mass or less.

Furthermore, in the aqueous composition of the present invention, the mass ratio of the content of hydrogen peroxide (A) to the content of the amide compound (C) represented by the general formula (1) is the content of hydrogen peroxide (A) / The mass ratio of the content of the amide compound (C) is preferably 0.002 or more, more preferably 0.1 or more, and more preferably 10 or less, more preferably from the viewpoint of highly efficient productivity improvement of organic radicals. is 4 or less.

The aqueous composition of the present invention can contain components other than hydrogen peroxide (A), an organic radical forming agent (B), and any amide compound (C) represented by the general formula (1). . For example, surfactants, sequestering agents, hydrotropic agents, excipients, preservatives, antibacterial agents, perfumes, deodorant base materials, etc. can be contained within a range that does not impair the effects of the present invention.

As the surfactant [hereinafter sometimes referred to as component (D) or surfactant (D)], nonionic surfactants, cationic surfactants, amphoteric surfactants and anionic surfactants can be blended. However, in the present invention, it is preferable to incorporate a nonionic surfactant in order to solubilize the hydrophobic radical forming agent in water.

Nonionic surfactants include polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, sucrose fatty acid esters, sorbitan fatty acid esters, fatty acid alkanolamides, and alkyl glycosides. etc. From the viewpoint of storage stability, it is preferable to contain a nonionic surfactant represented by the following general formula (2).
R ²¹ -Y-[(EO) _n (PO) _m ]—R ²² (2)
(In the formula, R ²¹ is a hydrocarbon group, -Y- is -O- or -COO-, and R ²¹ -Y- has a total carbon number of 8 to 22. EO is an ethyleneoxy group, PO is represents a propyleneoxy group, n and m represent the average number of added moles, n is a number of 5 to 30, and m is a number of 0 to 5. R ²² is a hydrogen atom or a carbon atom having 1 to 3 carbon atoms; is a hydrogen group. EO and PO can be either randomly or block bonded.)

In general formula (2), the hydrocarbon group represented by R ²¹ may be straight chain, branched chain, primary or secondary, and preferably straight chain primary. From the viewpoint of cleaning performance, R ²¹ -Y- preferably has 10 to 20 carbon atoms, more preferably 12 to 18 carbon atoms, still more preferably 12 to 16 carbon atoms, and particularly preferably 12 to 14 carbon atoms. R ²² is preferably a hydrogen atom. n is preferably 8-20. m is preferably 0.

In the aqueous composition of the present invention, the content of the surfactant (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 5% by mass or less, more preferably It is 3% by mass or less.

The aqueous composition of the present invention contains a sequestering agent [hereinafter referred to as component (E) or a sequestering agent (E )] is preferably contained. In some cases, the sequestering agent (E) is already blended with the hydrogen peroxide solution commercially available. Examples of sequestering agents (E) include (1) phosphoric acid compounds such as phytic acid, alkali metal salts or alkanolamine salts thereof, (2) ethane-1,1-diphosphonic acid, ethane-1, 1,2-triphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid (ethane-1-hydroxy-1,1-diphosphonic acid) and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane- Phosphonic acids such as 1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid, or alkali metal salts or alkanolamine salts thereof, (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane -Phosphonocarboxylic acids such as 2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid, or alkali metal salts or alkanolamine salts thereof, (4) amino acids such as aspartic acid, glutamic acid, glycine, or alkalis thereof metal salts or alkanolamine salts; (5) aminopolyacetic acids such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, and diencolic acid; or alkali metal salts or alkanolamine salts thereof, (6) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid , organic acids such as carboxymethyltartaric acid or alkali metal salts or alkanolamine salts thereof, (7) alkali metal salts or alkanolamine salts of aluminosilicic acid represented by zeolite A, (8) aminopoly(methylenephosphonic acid) or its Mention may be made of alkali metal or alkanolamine salts, or polyethylenepolyamine poly(methylenephosphonic acid) or its alkali metal or alkanolamine salts.
Among these, at least one selected from the group consisting of the above (2), (5), (6) and (7) is preferred, and at least one selected from the group consisting of the above (2) is more preferred.

In the aqueous composition of the present invention, the content of the sequestering agent (E) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 5% by mass or less, more preferably is 2% by mass or less.

The aqueous composition of the present invention contains a hydrotrope agent [hereinafter referred to as component (F) or a hydrotrope agent for the purpose of improving solution stabilization and freeze recovery at low temperatures and preventing liquid separation at high temperatures. (F)] is preferably blended. Hydrotrope agents (F) include short-chain alkyl (preferably having 1 to 3 carbon atoms) benzenesulfonates represented by toluenesulfonates, xylenesulfonates and the like, ethanol, propanol and the like having 1 to 4 carbon atoms. alkanol compounds, alkylene glycol compounds having 2 to 4 carbon atoms such as ethylene glycol, propylene glycol and hexylene glycol, and glycerin. The hydrotrope agent is preferably a short-chain alkyl (preferably having 1 to 3 carbon atoms) benzenesulfonate, an alkylene glycol compound having 2 to 4 carbon atoms, and more preferably ethylene glycol or propylene glycol. The hydrotrope agent can be blended in the composition in an amount of 0.1 to 10% by mass. From the viewpoint of the stability of hydrogen peroxide (A), the alkanol compound content in the composition is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1.5% by mass or less.

Excipients can include polymers known as glues. For example, poly(meth)acrylic acid, polystyrenesulfonic acid, polyvinyl alcohol, and the like can be mentioned, but those having less influence on hydrogen peroxide and radical generation are preferred.

Examples of preservatives include isothiazoline compounds such as 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, which are commercially available under the name Proxel, 1,2-benzo Benzoisothiazoline compounds such as isothiazol-3-one, and benzoic acid can be mentioned.

As the perfume, it is preferable to use a perfume that can be blended into an aqueous composition containing an oxidizing agent having a bleaching action such as hydrogen peroxide. As perfumes, for example, JP-A-2015-17236, JP-A-2014-58755, JP-A-2005-239770, JP-A-2009-144028, JP-A-50-74581 and JP-A-62 -205200 can be referred. It is preferable that these perfume ingredients are selected after not only configuring the perfume composition in consideration of the influence of hydrogen peroxide and other ingredients, but also confirming the influence on organic radicals. Aldehyde, ketone, and ester perfumes can be expected to act as organic radical forming agents by increasing their blending amounts, but it is preferable to use the specific organic radical forming agents described above as component (B).

The present invention differs from known bleaching processes that use metal catalysts to generate radicals, rather the aqueous compositions used in the present invention contain metals such as those used in metal catalysts, especially transition metals. Substantially, it is preferable not to mix them. That is, it is preferred that the aqueous composition of the present invention does not substantially contain a metal catalyst. While the metal catalyst exhibits strong bleaching power, it may not only impair the stability of the hydrogen peroxide in the aqueous composition of the present invention, but also cause damage to textile products and bleaching of dyes. When the aqueous composition contains a very small amount of metals derived from the raw material water, the influence can be suppressed by adding a chelating agent such as polycarboxylic acid or organic phosphonic acid.

The aqueous composition of the present invention contains water as the balance. Water is used in such an amount that the total aqueous composition is 100% by weight. It is preferable to use deionized water as water.

The aqueous composition of the present invention has a pH at 20°C of preferably 1 or more, more preferably 3 or more, and preferably 7 or less, more preferably 4 or less.
pH is measured at 30°C according to item 8.3 of JIS K 3362; 2008.
The pH can be adjusted with a pH adjuster such as an alkaline agent or an acid agent. Examples of alkaline agents include aqueous solutions of ammonium salts and alkali metal hydroxides. As the acid agent, an aqueous solution of an organic acid such as maleic acid, fumaric acid or citric acid or an inorganic acid such as hydrochloric acid or sulfuric acid can be used.

The viscosity of the aqueous composition of the present invention at 25° C. is preferably 15 mPa·s or less, more preferably 10 mPa·s or less, and still more preferably 5 mPa·s from the viewpoint of sprayability in a spray container when spraying. and is preferably 1 mPa·s or more, more preferably 1.5 mPa·s or more, still more preferably 2 mPa·s or more. In the aqueous composition of the present invention, if the viscosity at 25°C is 15 mPa·s or less, the spray pattern will be appropriate. When the aqueous composition is applied or immersed, the pressure is preferably 200 mPa·s or less, more preferably 100 mPa·s or less.
Viscosity was measured using a No. B-type viscometer (model type BM) manufactured by Tokyo Keiki Co., Ltd. Attach a rotor according to the measured viscosity of 1 to 3, fill the aqueous composition into a glass tall beaker with a capacity of 200 mL, prepare it at 25 ± 0.3 ° C. in a water bath, and rotate the rotor at 60 r / min. 60 seconds after starting measurement.

The aqueous composition of the present invention is also the textile treatment agent composition for heat treatment of the present invention. Matters described with respect to the aqueous composition of the present invention can be appropriately applied to the textile treatment agent composition for heat treatment of the present invention.

In the method for treating textiles of the present invention, the aqueous composition of the present invention is applied to textiles. It is preferable to bring the aqueous composition of the present invention into contact with textiles. More preferably, the aqueous composition of the present invention is applied to and brought into contact with textiles by spraying, painting, dipping, and combinations thereof. Spraying, coating, and immersion can each be carried out by employing known methods and means for applying a liquid composition to textile products.

In the method for treating a textile product of the present invention, the aqueous composition of the present invention is preferably sprayed onto the textile product in an amount of 1% by mass or more and 100% by mass or less with respect to the mass of the clothing.

The aqueous composition of the present invention is stored at, for example, around room temperature before being applied to textile products. You may apply to a textile product as it is at the temperature. Specifically, in the method for treating textile products of the present invention, the temperature of the aqueous composition of the present invention applied to textile products is preferably 5°C or higher, more preferably 10°C or higher, from the viewpoint of storage stability of the composition. °C or higher, and from the viewpoint of the stability of hydrogen peroxide, it is preferably 50°C or lower, more preferably 40°C or lower. In the treatment method of the present invention, the aqueous composition may be preheated to a temperature equal to or higher than the storage temperature before applying it to the textile product, to an extent that does not impair its stability. It is preferable to bring the textile product into contact with the aqueous composition in the temperature range of 1.5 h, and then heat-treat the textile product at the temperature described later.

In the method for treating a textile product of the present invention, the textile product to which the aqueous composition of the present invention is applied is heat-treated at 80°C or higher and 250°C or lower.
The heat treatment is performed at least on the portion of the textile product to which the aqueous composition of the present invention is applied.
The heat treatment can be performed on the textile product retaining the aqueous composition of the present invention.

In the method for treating a textile product of the present invention, the heat treatment is preferably carried out by contacting the textile product with a high temperature body of 80° C. or more and 250° C. or less.
The hot body may be liquid, solid or gas.
As the liquid high-temperature body, it is possible to use oil, silicone oil, glycerin, ethylene glycol, and other high-boiling water-soluble organic solvents, and wax, which are liquefied by heating. The object treated with a high-temperature liquid may be washed away with water, an organic solvent, or a solution containing a surfactant. good.
Solid hot bodies include heated metals, ceramics, stones or sand and clay, as well as flexible or hard plastics and macromolecular polymers. Although the shape and size of the solid high-heat body do not matter, for example, it can be appropriately set in consideration of treatment in general households. A solid hot object, such as a heated metal, may be an implement such as an iron.
Steam, heated steam, heated air, and the like can be used as the gaseous high-heat body. Heated steam is preferable because a high temperature exceeding 100° C. can be set. On the other hand, the temperature is, for example, 100° C. or lower, and a heat dryer can also be used, although the treatment time is long.

The temperature of the heat treatment is 80° C. or higher, preferably 120° C. or higher, more preferably 140° C. or higher, and still more preferably 160° C. or higher from the viewpoint of organic radical generation efficiency. °C or lower, preferably 200 °C or lower.

The heat treatment time is set considering the influence of the temperature of the object to be treated. Also, it varies depending on the processing temperature and the medium of high heat. When a solid high-heat body such as an iron used at home or a laundry shop is brought into contact with an object, the temperature of the high-heat body is preferably set to 140° C. or higher, more preferably 160° C. or higher, and the contact time is preferably set. It is set to 3 seconds or more, more preferably 5 seconds or more, and preferably 30 seconds or less, more preferably 20 seconds or less. When using heated steam or heated liquid, the treatment temperature and treatment time can be set as a reference.

If the heat treatment temperature is 100° C. or higher and 140° C. or lower, it can be handled by setting the treatment time longer than the above range, while considering the environment and energy consumption that do not affect the object. May be set. For example, at this heat treatment temperature, the heat treatment time is preferably 30 seconds or more, more preferably 60 seconds or more, and preferably 80 minutes or less, more preferably 60 minutes or less.

On the other hand, in the case of low-temperature treatment using a dryer, steam, or the like, the heat treatment temperature is preferably set to 80°C or higher, preferably 90°C or higher and lower than 100°C. When the heat treatment temperature is less than 100 (low temperature)° C., the heat treatment time is preferably 1 minute or more, more preferably 5 minutes or more, and preferably 120 minutes or less, more preferably 80 minutes or less. When the contact medium is gas, the heat treatment temperature is preferably 15 seconds or more, more preferably 1 minute or more, and the heat treatment time is preferably 120 minutes or less, more preferably 80 minutes or less.

In order to prevent residual hydrogen peroxide from remaining, in addition to high temperature treatment, heated gas is brought into contact with the air to promote the vaporization of hydrogen peroxide. may be removed by a method such as washing away the

In addition, before the heat treatment, the textile product to which the aqueous composition of the present invention is applied may be left to stand in order to allow the aqueous composition of the present invention to sufficiently absorb stains and odors in the fibers. For example, it can be left at 25° C. or more and 40° C. or less for 30 minutes or more and 120 minutes or less.

Depending on the treatment method, the textile product that has undergone the heat treatment may be used as it is, or may be subjected to further treatments such as drying and ironing. It can be washed.

As an example of the method for treating a textile product of the present invention, an aqueous composition containing hydrogen peroxide, an organic radical forming agent and water is brought into contact with a textile product, and then the textile product is heat-treated at 80° C. or more and 250° C. or less. and a method for treating textile products.

As another example of the method for treating textile products of the present invention, after spraying an aqueous composition containing hydrogen peroxide, an organic radical forming agent and water onto a textile product, the textile product is treated at 80° C. or higher and 250° C. or lower. A method of treating textiles, including heat treatment. Spraying is preferably carried out using a spray container containing the aqueous composition of the present invention.

The textile treatment method of the present invention is suitable for, but not limited to, partial treatment of textiles such as collars and sleeves.

The textile treatment method of the present invention is not limited, but may be, for example, a textile cleaning method. In this case, cleaning may involve not only removal of dirt but also other effects such as removal of offensive odors and sterilization.

<Method for measuring oxidation-reduction potential>
The oxidation-reduction potential of the component (B) of the present invention was calculated using quantum chemical calculation software TURBOMOLE ver7.2 and graphical user interface TmoleX ver4.3 for TURBOMOLE. The free energy of each component in the following formulas (5) and (6) is approximated by the sum of quantum energy and zero point vibration energy.
For example, the quantum energy and zero-point vibrational energy of a carboxylic acid such as a fatty acid and its carboxylic acid radical were calculated using a continuum model with the dielectric constant of water being 57.01 (95° C.). After structural optimization, normal vibration analysis was performed to calculate the values in water at 95°C. The conditions for the DFT calculations were DFTsurasshubp86/def2-TZVP and the RI approximation was used. The default values of TmoleX were used as they were for parameters such as atomic radii required for the calculation.

(Calculation example) Estimation of oxidation-reduction potential of carboxylic acid Assuming the half-reaction shown in the formula (1) as the reaction of carboxylic acid, the oxidation-reduction potential is estimated.

When a standard hydrogen electrode is used as the reference electrode, the reaction of formula (2) occurs at the electrode. This electrode potential is defined as 0 V when the hydrogen ion activity is 1 (corresponding to pH=0).
H ⁺ + e ⁻ → (1/2) H ₂ (gas) (2)
Therefore, the standard oxidation-reduction potential E ⁰ of the formula (1) when pH=0 is in the relationship of the standard free energy change ΔG ⁰ of the reaction shown in the formula (3) and the relation of the formula (4).

E ⁰ = -ΔG ⁰ /F (4)
Also,
ΔG ⁰ = G _COOH − G _COO· − 1/2G _H2 (5)
can be written as Here, G _COOH , G _COO· , and G _H2 are the free energies of carboxylic acid, carboxylic acid radical, and hydrogen, respectively.
Also, the oxidation-reduction potential at pH=7 is represented by the formula (6).
E ⁰ = -1/F (G _COOH - G _{COO ·} - 1/2 G _H2 - RTln10 ^-7 ) (6)
The half-reaction of the lactate ester assumes the hydrogen atom of the hydroxyl group, and the ketone and ester compounds assume the hydrogen atom of the allylic position.

<Evaluation method>
(I) Measurement of Melanin Decomposition Rate As a method for confirming the bleaching effect by adding an organic acid, the degradability of synthetic melanin was confirmed by the following method. Table 1 shows the results.
(reagent)
Synthetic melanin: manufactured by Sigma-Aldrich,
(experimental method)
(1) Preparation of melanin aqueous solution: Synthetic melanin was dissolved in water at pH 11 (adjusted with NaOH) to a final concentration of 2.5%. Then, the pH was adjusted to 7 (adjusted with HCl) to prepare a synthetic melanin aqueous solution.
(2) After adjusting the temperature to 95° C., the absorbance (650 nm) of the prepared synthetic melanin aqueous solution was measured using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2700, Shimadzu Corporation).
(3) Each component shown in Table 1 was mixed to prepare a textile treatment composition for heat treatment (hereinafter sometimes referred to as an aqueous composition). The pH (20° C.) was adjusted to 3.5 using aqueous HCl.
(4) 3 ml of the synthetic melanin aqueous solution was placed in a screw tube, and 3 ml of the aqueous composition shown in Table 1 was added.
(5) Reaction was performed at 95° C. for 10 minutes using a water bath.
(6) The absorbance (650 nm) after the reaction was measured using the same UV-visible spectrophotometer as in (2).
(7) The melanin degradation rate was calculated as a relative value when the absorbance before the reaction measured in (2) was taken as 100%. It can be judged that the larger the value, the higher the bleaching effect.

(II) Evaluation of Inhibition of Decolorization of Dyes The effect of organic radicals generated from each organic radical-forming agent (B) on the dyes of textile products was investigated as follows.
(Test cloth)
Among the test cloths used in bleach fastness tests in Europe for colored garments, the European Association of Soaps and Detergents (AISE) test cloths, as test cloths susceptible to bleaching, No. 7 (Orange Azoic dye) was selected and cut to 10 cm x 10 cm for use.

(experimental method)
The aqueous composition shown in Table 1 was filled into a commercially available Spray Keeping (manufactured by Kao Corporation) container that had been thoroughly washed. 50% o.d. w. f. (Spraying 50 parts by mass with respect to 100 parts by mass of the test cloth), the aqueous composition was sprayed. After spraying, heat treatment was performed by pressing with an iron at 160° C. (medium iron temperature) for 15 seconds. Decolorization after heat treatment was investigated.
Decolorization was evaluated by measuring the color difference (ΔE) before and after treatment at a fixed point using a handy colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd.), and evaluated as follows. Table 1 shows the results.
◯: No decoloration is observed.
(triangle|delta): Decolorizes a little.
x: decolorized.

Various components used in the preparation of the textile treatment composition for heat treatment in Table 1 are shown below.
(A) Component (a1) Hydrogen peroxide (using a 45% aqueous solution, manufactured by ADEKA Co., Ltd.) (Table 1 shows the active ingredient concentration.)

(B) component (b1) propyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.)
(b2) Butyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.)
(b3) octanoic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
(b4) Lauric acid (manufactured by Wako Pure Chemical Industries, Ltd.)
(b5) myristic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
(b6) butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.)
(b7) butyl formate (manufactured by Tokyo Chemical Industry Co., Ltd.)

(C) component (c1) urea (manufactured by Wako Pure Chemical Industries, Ltd.)
(D) component (d1) nonionic surfactant: polyoxyethylene (ethylene oxide average added mole number 10) lauryl ether water: deionized water

From the above, it is clear that the treatment method and the textile product treatment composition for heat treatment of the present invention have an excellent sebum stain bleaching effect without affecting the textile products.
Furthermore, the textile product treatment composition for heat treatment disclosed in the present example has a deodorizing effect and a sterilizing effect on textile products by applying the treatment method of the present invention to textile products such as clothing and bedding. It gives

Claims (9)

applying to textiles an aqueous composition comprising hydrogen peroxide, an organic radical former and water;
heat-treating the textile product to which the aqueous composition is applied at 80° C. or higher and 250° C. or lower;
A method for treating a textile product, comprising:
The organic radical forming agent is one or more selected from lactate esters having 4 to 10 carbon atoms, formic esters having 3 to 10 carbon atoms, and acetic esters having 3 to 10 carbon atoms. , a compound having an oxidation-reduction potential of 0.9 eV or more and 2.3 eV or less,
The aqueous composition contains 0.01% by mass or more and 2% by mass or less of hydrogen peroxide,
The aqueous composition contains 0.05% by mass or more and 2% by mass or less of an organic radical forming agent.
How to treat textiles. 2. The method of treating textiles according to claim 1, wherein the organic radical forming agent is one or more compounds selected from propyl lactate, butyl lactate, butyl acetate and butyl formate. 3. The method of treating textiles according to claim 1 or 2, wherein the aqueous composition is substantially free of metal catalysts. The method for treating a textile product according to any one of claims 1 to 3, wherein the heat treatment is performed by contacting the textile product with a high-temperature body of 80°C or higher and 250°C or lower. The method for treating textiles according to any one of claims 1 to 4, wherein the aqueous composition is applied to the textiles by spraying, coating, dipping or combinations thereof. The method for treating textile products according to any one of claims 1 to 5, wherein the aqueous composition contains 0.01% by mass or more and 1% by mass or less of hydrogen peroxide. The method for treating textile products according to any one of claims 1 to 6, wherein the aqueous composition contains 0.05% by mass or more and 1% by mass or less of the organic radical former. The method for treating textile products according to any one of claims 1 to 7, wherein the aqueous composition further contains 0.1% by mass or more and 5% by mass or less of an amide compound represented by the following general formula (1).
X—C(═O)—N(R ¹ )(R ² ) (1)
[Wherein, R ¹ and R ² are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X is -R ¹ , -N(R ³ )(R ⁴ ), phenyl group or benzyl wherein R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group or a benzyl group, wherein R ³ and R ⁴ are both a phenyl group or a benzyl group isn't it. ] The method for treating textiles according to claim 8, wherein the amide compound is urea.