JP2008002024A - Liquid treating agent composition for textile product and method for treating textile product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid treating agent composition for textile products, which has excellent deodorizing effect and improved dispersion stability of metal oxide particles in the composition and provide a method for treating textile products. <P>SOLUTION: The liquid treating agent composition for textile products contains (A) at least one kind of metal oxide particle having an average particle diameter of ≥0.1 nm and <1,000 nm and having physical deodorizing action and chemical deodorizing action, (B) a cationic polymer and (C) an alkylene oxide adduct of a higher alcohol, a higher alkylamine or a higher fatty acid having an HLB value of 6-16. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid treatment composition for textiles that is excellent in the deodorizing effect of textiles such as clothing and has improved the dispersion stability of metal oxide particles in the composition, and a method for treating textiles.

  Conventional deodorization technologies using metal oxides include deodorization (physical deodorization) using adsorption of substances such as magnesium oxide and deodorization (chemical deodorization) using photocatalytic action such as titanium oxide. ) Has been reported. Physical deodorization technology is often used mainly in the cosmetics field such as antiperspirants, but even in the textile field, functional particles such as zinc oxide and silicon dioxide are more than a certain size in water. That is, a deodorant composition containing a base prepared by granulating and aggregating to 0.1 mm or more has been reported (for example, see Patent Document 1).

  On the other hand, chemical deodorization technology is also used in the field of textile products. Titanium oxide, which has been most studied for its photocatalytic action, absorbs ultraviolet rays UV-B (290 to 320 nm) on the short wavelength side, which has a particularly high energy, and exhibits a photocatalytic action. However, there is a possibility that the fiber is deteriorated by irradiating with ultraviolet rays. In order to solve this problem, a fiber treatment agent (for example, see Patent Documents 2 and 3) of a compound obtained by impregnating a layered material such as clay mineral or aluminosilicate or a porous material with a photocatalyst (for example, Patents 2 and 3) Reference 4) has been reported. However, since the particle diameters of the obtained fiber treatment agent and cleaning agent are on the order of micrometers, the composition remains in the fiber product, and the dark fiber product may be whitened.

  In addition, in the composition using physical deodorization technology, there is a limit to the adsorption of bad odor, and in the composition using chemical deodorization technology, the effect of the photocatalyst is decomposed as long as sunlight (ultraviolet rays) continues to hit. However, in general, fiber products with bad odors are not necessarily irradiated with sunlight (ultraviolet rays).

Further, as a liquid deodorant composition for textiles containing metal oxide particles and a polyether compound (Patent Document 5), zinc oxide / polyether-modified silicone (HLB5) / cationic polymer / POE alkyl ether (trie EO 40 mol adduct of decyl alcohol, HLB18) combined system, titanium oxide / magnesium oxide / polyoxyethylene hydrogenated castor oil (EO 20 mol adduct, HLB9) / cationic polymer / POE alkyl ether (EO40 of tridecyl alcohol) A composition comprising a molar adduct, HLB 18) has been proposed, but none of them guarantees the dispersion stability of the metal oxide particles.
On the other hand, a liquid finishing composition for textiles containing a mixture of metal oxide particles and a cationic surfactant (Patent Document 6), a yellowing inhibitor for washing clothes (Patent Document 7), and a method for UV-protecting a textile material ( Patent Document 8), cleaning agent (Patent Document 9), textile product treating agent composition, detergent composition, textile product treating method (Patent Document 10), etc. have been reported, all of which are metal oxides based on cationic substances. It does not describe the effect of improving the dispersion stability of the particles. Also disclosed is a transparent or translucent liquid softener composition (Patent Document 11) using a silicone compound having a polyether group and a water-soluble polymer compound having a cationic property in a specific ratio, and further using silica fine particles. However, the deodorizing effect was insufficient.

JP, 2001-198202, A Claims 1 JP 2000-355872 A paragraph 0025 JP, 2001-303434, A Example 1 JP 2002-12891 A JP 2005-207002 A JP 2006-63499 A JP 2003-176495 A JP-T-2004-528486 JP 2005-82708 A Japanese Patent Laid-Open No. 2005-154921 JP 2006-77336 A

  An object of the present invention is to provide a liquid treating agent composition for textiles which has an excellent deodorizing effect and has improved dispersion stability of metal oxide particles in the composition, and a method for treating textiles.

The present invention is (A) metal oxide particles having an average particle size of 0.1 nm to less than 1000 nm, and at least one metal oxide particle having both a physical deodorizing action and a chemical deodorizing action, And (B) a water-soluble polymer having cationic properties, and (C) a higher alcohol or higher alkylamine having an HLB value of 6 to 16, or an alkylene oxide adduct of a higher fatty acid. A liquid treating agent composition is provided.
The present invention also provides (A) metal oxide particles having an average particle size of 0.1 nm or more and less than 1000 nm, and at least one metal oxide particle having both a physical deodorizing action and a chemical deodorizing action. And (B) a water-soluble polymer having a cationic property, and (C) a fiber product using a treatment liquid containing an alkylene oxide adduct of a higher alcohol or higher alkylamine or higher fatty acid having an HLB value of 6 to 16. A method for treating a textile product is provided.

  The liquid treating agent composition for textiles and the textile processing method of the present invention can provide an excellent deodorizing effect and improved dispersion stability.

(A) Metal oxide particles (A) Metal oxide particles that can be used in the present invention are those having a physical deodorizing action. (A-1) Chemicals such as zinc oxide, magnesium oxide and calcium oxide (A-2) Titanium oxide, zinc oxide, tungsten oxide, bismuth oxide, indium oxide, etc. are mention | raise | lifted as what has a deodorizing effect. These can be used alone or in combination of two or more. When using together, it is preferable to use combining 1 or more types chosen from the group of (a-1), and 1 or more types chosen from the group of (a-2). In particular, when zinc oxide is used alone, it is preferable because a high deodorizing effect can be obtained when magnesium oxide and titanium oxide are used in combination. Most preferably, zinc oxide is used alone. When one or more selected from the group (a-1) is used in combination with one or more selected from the group (a-2), the total of the groups (a-1) and (a-2) ) Ratio to the total of the group ((a-1) / (a-2)), in terms of mass ratio, the lower limit is 10/90 or more, more preferably 20/80 or more, and particularly preferably 40/60. The upper limit is 90/10 or less, more preferably 80/20 or less, and particularly preferably 60/40 or less.

  The metal oxide particles that can be used in the present invention have an average particle size (hereinafter referred to as an average particle size) observed with an electron microscope, and the lower limit is 0.1 nm or more, preferably 0.2 nm or more. Preferably it is 0.5 nm or more, particularly preferably 1 nm or more, more particularly preferably 10 nm or more, and the upper limit is less than 1000 nm, preferably less than 500 nm, more preferably less than 300 nm, particularly preferably less than 200 nm. . It is preferable for the average particle diameter to fall within such a range because the metal oxide particles can be prevented from aggregating in the composition, and the adsorptive power to the fiber product surface is improved.

  The average particle diameter of the metal oxide is such that the metal oxide particles are dispersed in an ethanol solution of 99% by volume or more using a homogenizer capable of rotating at a rotation speed of 10,000 rpm or more, air-dried on a sample stage, It can be measured by a scanning electron microscope that can be used at a magnification of 100,000 times. More specifically, 200 mL of 99.5 vol% ethanol is added to 5 g of the sample, and after stirring and dispersing for 5 minutes at a rotation speed of 10,000 rpm using a powerful homogenizer DIAX900 (shaft generator 18F) manufactured by Heidorf, the sample is immediately placed on the sample stage. Drop a few drops and air dry. The air-dried sample is vapor-deposited with platinum palladium, preferably platinum, and the average particle diameter is measured at a magnification of 100,000 using a Hitachi scanning transmission electron microscope apparatus H-8010. In the case of 50,000 times, 20 particles are measured, and in the case of 100,000 times, the particle diameter of 10 particles is measured, and the average value is obtained. However, it is desirable to increase the magnification of the electron microscope if the particle diameter is less than 10 nm, and decrease the magnification if it exceeds 100 nm. In addition, when using the metal oxide particle used by this invention after surface-treating so that it may mention later, an average particle diameter means the particle diameter after surface treatment.

  The metal oxide particles that can be used in the present invention have both a physical deodorizing action and a chemical deodorizing action. Here, the physical deodorizing action refers to an action of deodorizing a metal oxide by adsorbing a malodorous substance by van der Waals force, hydrogen bonding, or the like. The chemical deodorizing action refers to an action of deodorizing by decomposing malodorous substances by the photocatalytic action of metal oxide. In the present invention, the physical deodorizing action and the chemical deodorizing action are defined as follows.

Physical deodorizing action Physical deodorizing action can be measured by the following method. That is, 0.05% owf of 0.1% solution obtained by dispersing metal oxide particles in 99.5% by volume of ethanol was adhered to 0.1 g of a synthetic fiber cloth, and the room temperature was 25 ° C., humidity What was dried for 12 hours in a 65% RH room is used as an evaluation cloth. The metal oxide dispersion is allowed to adhere to 0.05% owf as it is. Moreover, let the cloth prepared on the same conditions except not having made metal oxide particle adhere as a blank cloth. Put the evaluation cloth and the blank cloth into 20 mL vials, add 0.1 ppm of malodorous substances to the volume of each vial, seal tightly and leave at 40 ° C. for 1 hour with light shielding. The malodorous substance is measured by GC-MS.

Chemical deodorizing action The chemical deodorizing action can be measured by the following method. That is, each of the evaluation cloth and blank cloth prepared as described above was put into a 20 mL vial, and after adding an equivalent of 0.1 ppm of malodorous substance to the volume of the vial, it was sealed and sealed at 40 ° C. and 2 mW / cm. ^The sample is allowed to stand for 1 hour while irradiating the ultraviolet ray ² and the head space malodorous substance is measured by GC-MS.

Deodorization rate calculation From the peak area of the mass chromatogram of m / Z = 60 from the total ion gas chromatogram measured in the above physical deodorization and chemical deodorization, the deodorization is calculated from the following calculation formula (1). Find the rate.

Deodorization rate (%) = 100− (peak area of evaluation cloth) × 100 / (peak area of blank cloth) (1)

  The metal oxide particles of the component (a) that can be used in the present invention have a deodorization rate of 30% or more, preferably 50% or more, more preferably 70% or more, in particular, a physical deodorizing action against bad odors. Preferably it is 80% or more.

  The metal oxide particles of component (a) that can be used in the present invention have a deodorization rate of 50% or more, preferably 70% or more, more preferably 80% or more, in particular, a chemical deodorizing action against bad odors. Preferably it is 90% or more.

Surface treatment of metal oxide particles The metal oxide particles that can be used in the present invention have a hydrophobic organic compound (fatty acid, silicone), various surfactants (cationic surfactants, nonionic surfactants, etc.) It can be treated with a water-insoluble inorganic compound. The surface treatment is preferable because the stability of particles in water, aggregation suppression, and fiber adsorption can be further improved.
Specifically, as the fatty acid, a linear or branched saturated or unsaturated fatty acid having 8 to 18 carbon atoms, preferably 12 to 18 carbon atoms can be used. The fatty acid may be a dibasic acid and may be substituted with a hydroxyl group or the like. As the fatty acid, those synthesized by a known method may be used, or commercially available ones may be used. For example, what is obtained by using palm oil as a raw material and processing by a conventional method can be used. As a commercial item, it is sold with the brand name coconut fatty acid DC from Shin Nippon Rika Co., Ltd., for example.
As the silicone, for example, a silicone having a Mw (weight average molecular weight) of 3000 to 200,000 and a repeating unit of 40 to 2700 can be used. For example, methicone (methyl polysiloxane) can be used.
As the cationic surfactant, a monoalkyl cation, a dialkyl cation, or the like can be used.
As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, or the like can be used.
Further, the metal oxide particles may be used in a form dispersed in a solvent. Examples of the solvent include water and ethanol. The dispersion concentration is preferably from 0.01 to 30% by mass, and more preferably from 0.1 to 20% by mass. Such metal oxide particles are commercially available from Sumitomo Osaka Cement Co., Ltd. under the trade names ZE-143 and ZW-143, for example.

The ratio (mass ratio) of the surface treatment agent to the metal oxide particles is preferably metal oxide particles: surface treatment agent = 99.9: 0.1-60: 40, more preferably 99: 1-90: 10. It is preferable to be within the range. Within such a range, stability of particles in water, aggregation suppression, and fiber adsorption are further increased, which is preferable.
The surface treatment method of the metal oxide particles can be performed as follows, for example.
A solution or dispersion containing the surface treatment substance is prepared in an aqueous or organic medium. This solution or dispersion is mixed with the metal oxide particles or sprayed onto the metal oxide particles to coat the surface of the metal oxide particles, and then concentrated, filtered, dried or sintered, Treated metal oxide particles can be obtained.
The metal oxide particles that can be used in the present invention desirably have a solubility in 100 g of water at 25 ° C. of less than 0.5 g. In this case, the deodorizing effect is not lost by maintaining the crystal structure of the metal oxide particles in the composition, which is preferable.

  As the metal oxide particles that can be used in the present invention, commercially available particles can be used. For example, zinc oxide is commercially available from Teika under the trade name MZ300. Magnesium oxide is commercially available from Ube Materials under the trade name gas phase high purity magnesia.

  These metal oxide particles (A) usually have a lower limit of 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.6% by mass or more, based on the whole composition. The upper limit is preferably 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less. When the blending amount of the component (A) is less than 0.1% by mass, the effects such as the deodorizing effect may not be sufficient, and when it exceeds 20% by mass, the dispersion Stability may be reduced.

(B) Water-soluble polymer having cationic property The component (B) of the present invention is a water-soluble polymer having cationic property that has the effect of adsorbing the metal oxide particles of the component (A) to the fiber. The water-soluble polymer compound having a cationic property is preferably a water-soluble polymer compound having one or more cationic groups selected from an amino group, an amine group, and a quaternary ammonium group. In the present invention, the water-soluble polymer means that when 1 g of the water-soluble polymer compound is added to 100 g of water at 25 ° C., the liquid is not turbid and transparent.

The water-soluble polymer having a cationic property as component (B) preferably has a cationization degree of 0.1% or more, and preferably 2.5% or more. When the degree of cationization satisfies these conditions, the effect of adsorbing the coexisting silicone compound on the fiber can be made excellent, and a large amount of compounding is required to prevent an economical case. be able to. The upper limit of the degree of cationization is preferably 35 or less, and more preferably 15.
Here, the degree of cationization means that a polymer compound is a polymer of a cationic monomer, a copolymer of a cationic monomer and a nonionic monomer, and a part of a nonionic polymer modified or substituted with a cationic group. In the case of (cationized cellulose, etc.), the polymer compound is a copolymer of a cationic monomer and an anionic monomer, and a copolymer of a cationic monomer, an anionic monomer and a nonionic monomer. In the case of coalescence, it is defined as a value calculated by the following formula (3).

Cation degree (%) = X × Y × 100 Formula (2)
[X: atomic weight of a cationized atom (such as nitrogen) in the cationic group of the polymer compound Y: number of moles of the cationic group contained in 1 g of the polymer compound]

Cationization degree (%) = X × (Y−Z) × 100 Formula (3)
[X: atomic weight of a cationized atom (such as nitrogen) in a cationic group of a polymer compound Y: number of moles of a cationic group contained in 1 g of the polymer compound Z: anion contained in 1 g of the polymer compound The number of moles of the functional group (an anionic group of Z includes, for example, a carboxyl group and a sulfonic acid group contained in the monomer unit in the polymer chain. Specific examples include a carboxylic acid in acrylic acid. However, the counter ion of the cationic group is not included.)]

As an example of calculating the degree of cationization, the case of MERQUAT280 (made by calgon) represented by the following formula (I) is shown.
X: 14 (atomic weight of nitrogen atom)
Y: 4.95 × 10 ⁻³ (weight per 1 g of the cationic group: calculated from 0.8 g and the molecular weight of the cationic group)
Z: 2.78 × 10 ⁻³ (weight per 1 g of anionic group: calculated from 0.2 g and molecular weight of the anionic group)
From equation (2)
Cation degree (%) =
14 × (4.95 × 10 ⁻³ −2.78 × 10 ⁻³ ) × 100 = 3.0
It is.

Mass ratio of dimethyldiallylammonium chloride to acrylic acid = 80: 20
Therefore, according to the cationization degree calculation method described above, the cationization degree of the nonionic monomer polymer or the anionic monomer polymer is zero.

  The cationic polymer as the component (B) preferably has a weight average molecular weight of 1,000 to 5,000,000 as measured by gel permeation chromatography using polyethylene glycol as a standard substance. Preferably it is 3,000-1,000,000, More preferably, it is 5,000-500,000. As a result, it is possible to satisfactorily prevent odor and to suppress the increase in viscosity and to improve the usability.

  Examples of the component (B) include MERQUAT100 (Calgon), Adeka thioace PD-50 (Asahi Denka Kogyo Co., Ltd.), Daidol EC-004, Daidoru HEC, Daido Kasei Kogyo Co., Ltd. Polymers of dimethyldiallylammonium chloride such as MERQUAT550 JL5 (manufactured by Calgon), dimethyldiallylammonium chloride / acrylamide copolymer such as MERQUAT280 (manufactured by Calgon), dimethyldiallylammonium chloride / acrylic acid copolymer such as MERQUAT280 (manufactured by Calgon), Leogard KGP , Cationized cellulose such as Leogard MLP (manufactured by Lion), imidazolinium chloride such as LUVIQUAT-FC905, LUVIQUAT-FC370, LUVIQUAT-FC550 (manufactured by B.A.S.F) Nylpyrrolidone copolymer, polyethyleneimine such as LUGALVAN-G15000 (manufactured by B, A, S, F), cationized polyvinyl alcohol such as Poval CM318 (manufactured by Kuraray Co., Ltd.), natural system having amino group such as chitosan And a copolymer with a vinyl monomer having a hydrophilic group to which diethylaminomethacrylate / ethylene oxide or the like is added. Any polymer compound that is cationic when dissolved or dispersed in water may be used. It is not limited to examples.

  In order to give a high degree of cationization, the main chain of the water-soluble polymer having a cationic property that can be used in the present invention is efficiently composed of a monomer having a cationic group. From this viewpoint, it is preferably composed of monomers such as dimethyldiallylammonium salt, methacrylamidopropylammonium salt, and vinylimidazolium salt.

  A particularly preferable polymer is a cationic polymer obtained by polymerizing a dimethyldiallylammonium salt represented by the following general formula (II). The structure of this polymer is usually represented by the following general formula (III) or the following general formula (IV). Moreover, both the structural unit of general formula (III) and the structural unit of general formula (IV) may be contained.

(In the formula, c and d are average polymerization degrees, respectively, preferably in the range of 6 to 30000, more preferably in the range of 20 to 6000, still more preferably in the range of 30 to 3000.)

Examples of such a polymer include MERQUAT100 (Calgon), Adekathioace PD-50 (Asahi Denka Kogyo Co., Ltd.), Daidole EC-004, Daidole HEC, Daido Kagaku Kogyo Co., Ltd. Manufactured) and the like.
As the component (B) of the present invention, the above cationic polymer compound may be used alone or as a mixture.
The cationic polymer as the component (B) usually has a lower limit of 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass with respect to the entire composition. % Or more, particularly preferably 1% by mass or more, and the upper limit value is 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. Is preferred. When the blending amount of the component (B) is less than 0.1% by mass, the effect of promoting the adsorption of the metal oxide particles as the component (A) is insufficient, and the effects such as the deodorizing effect are sufficient. If the amount exceeds 20% by mass, the viscosity of the composition may increase, which may be inconvenient in terms of usability.

Optimum ratio of component (A) and component (B) In the treating agent composition for textiles of the present invention, the mass ratio of component (A): component (B) is in the range of 99: 1 to 50:50. It is. Preferably it is 95: 5-60: 40, More preferably, it is the range of 90: 10-70: 30. By setting the ratio within such a range, it is possible to improve the adsorptivity of the metal oxide particles (A) to the fibers.

  Moreover, the treatment composition for textiles of the present invention is used in such an amount that the concentration of the component (A) is 5 ppm to 500 ppm with respect to the total amount of water used when the textile product is actually subjected to soft finishing. More preferably, it is used in an amount such that it is 10 ppm to 300 ppm, and the concentration of the component (B) is preferably used in such an amount that it is 0.5 ppm to 100 ppm, more preferably 3 ppm to 30 ppm. Used in such an amount.

(C) Alkylene oxide adduct of higher alcohol or higher alkylamine or higher fatty acid Component (C) of the present invention is an alkylene oxide adduct of higher alcohol or higher alkylamine or higher fatty acid having an HLB value of 6 to 16. .
Usually, the lower limit of the HLB value is 6 or more, preferably 7 or more, more preferably 8 or more, and the upper limit is preferably 16 or less, preferably 15 or less, more preferably 14 or less, and the HLB value is By being in this range, it becomes possible to improve dispersion stability, and the structure is not particularly limited.
The “HLB value of the nonionic surfactant” in the present invention is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Industrial Book Co., Ltd.) Company, 1991, page 234).

  As the component (C), specifically, the following can be used. That is, the hydrocarbon chain may be branched or linear and may be unsaturated. There may also be a distribution in the hydrocarbon chain. The hydrocarbon chain preferably has 6 to 20 carbon atoms, more preferably 8 to 18 carbon atoms. When the carbon chain is a straight chain, those having 6 to 16 carbon atoms are preferred, more preferably 8 to 14, and most preferably 11 to 13. When the carbon chain is a branched chain, those having 6 to 18 carbon atoms are preferred, more preferably 9 to 18, and most preferably 13.

  (C) As the raw material of the component, Exar Chemical's EXSAR, BASF's LUTENSOL series, Kyowa Hakko Kogyo's Oxocol, HoechstAG's GENAPOL series, Shell's DOBANOL series, Sasol's SAFOL series, ECOGREEEN's ECOROL series, CO series and TA series manufactured by P & G Chemicals can be used. In particular, in the case of an alkylene oxide adduct of alcohol, a primary alcohol or a secondary alcohol can be used, but the dispersibility of the treating agent composition is better when the primary alcohol is used. The tridecyl alcohol having 13 carbon atoms is produced, for example, using dodecene as a raw material, but the starting material may be butylene or propylene. On the other hand, when the carbon chain contains an unsaturated group, those having 18 carbon atoms are particularly preferred, and the stereoisomeric structure of the unsaturated group may be a mixture of both, even if it is a cis isomer or a trans isomer. However, it is particularly preferable that the ratio of cis isomer / trans isomer is 25/75 to 100/0 (mass ratio). The alkylene oxide is preferably ethylene oxide (EO), but may be one in which propylene oxide (PO) or butylene oxide (BO) is added together with ethylene oxide. The average added mole number of EO is preferably 2 to 30 mol, more preferably 3 to 20 mol, and particularly preferably 5 to 15 mol. Moreover, 1-5 are suitable as an average addition mole number of PO or BO added with EO, More preferably, it is 1-3 mol. At this time, PO or BO may be added after adding EO, or EO may be added after adding PO or BO.

(C) Component commercial products include Japan Emulex Series, Sanyo Kasei Emalmin Series, Lion TDA Series, Esomin Series, Nippon Shokubai Softanol Series, BASF LUTENSOL Series, P & G Chemicals CO series etc. can be used.
Among the components (C), polyoxyalkylene alkyl ethers having at least one alkyl group or alkenyl group having 8 to 20 carbon atoms are preferred, and those having an average of 2 to 30 moles of oxyalkylene groups are preferred. Furthermore, a nonionic surfactant represented by the following general formula (C-1) is preferable.
^{R 1 -T - [(R 2} O) p -H] q (C-1)
(Wherein R ¹ is an alkyl group or alkenyl group having 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, and R ² is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. Is the average number of moles added, and represents a number of 2 to 30, preferably 3 to 20, particularly preferably 5 to 15. T represents —O—, —N—, —NH—, —N (C ₂ H ₄ OH) -, - CON -, - CONH- , or _{CON (C 2 H 4 OH)} - and is, T is -O -, - NH -, - N (C 2 H 4 OH) -, - CONH-, or In the case of —CON (C ₂ H ₄ OH) —, q is 1, and in the case where T is —N— or —CON—, q is 2.)

Specific examples of the compound represented by the general formula (C-1) include compounds represented by the following general formulas (C-2) and (C-3).
R ¹ —O— (C ₂ H ₄ O) _r —H (C-2)
(In the formula, R ¹ has the same meaning as described above, and r represents the average number of added moles, which is 2 to 30, preferably 5 to 15.)
R ¹ —O— (C ₂ H ₄ O) _s (C ₃ H ₆ O) _t —H (C-3)
(Wherein R ¹ has the same meaning as described above, s and t are average added mole numbers, s is a number of 2 to 30, preferably 5 to 15, and t is 1 to 5, preferably 1) It is a number of ~ 3. (C ₂ H ₄ O) and (C ₃ H ₆ O) may be random or block adducts.

  The blending amount of the higher alcohol or higher alkylamine or higher fatty acid alkylene oxide adduct as the component (C) used in the present invention is not particularly limited, but from the viewpoint of dispersion stability, it is usually the lower limit for the entire composition. Is 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and the upper limit is 20% by mass or less, preferably 15% by mass. % Or less, more preferably 12% by mass or less, particularly preferably 10% by mass or less. As a result, it is possible to improve the dispersion stability, and it is possible to suppress the excessive addition when the effect reaches saturation and to achieve economic efficiency.

  Furthermore, in order to ensure the storage stability of the processing agent composition for textiles, in this invention, it is more preferable to contain a silicone compound and a water-soluble solvent in addition to the said component.

The silicone compound is preferably a silicone compound having a polyether group, and may contain an organic functional group such as an amino group, an alkyl group, a carboxyl group, or an epoxy group as long as it has a polyether group. The molecular structure of the silicone compound may be linear or branched or cross-linked. The modified silicone compound may be modified with one kind of organic functional group or may be modified with two or more kinds of organic functional groups.
The silicone compound can be used as an oil or as an emulsion dispersed with any emulsifier. In particular, a silicone compound containing no amino group is preferred in order to prevent yellowing of the treated textile product. Furthermore, the silicone compound is preferably nonionic from the viewpoint of enhancing the effect of adsorbing the component (A) on the fibers, and more preferable examples include epoxy polyether-modified silicone, alkyl polyether-modified silicone, and polyether. A modified silicone is mentioned.

  Among these, particularly preferable silicone compounds include polyether-modified silicones from the viewpoint of improving dispersion stability. Preferred polyether-modified silicones include copolymers of alkyl (C1 to C3) siloxane and polyoxyalkylene (preferably having 2 to 5 carbon atoms of an alkylene group). Among these, a copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, random or block copolymer of ethylene oxide and propylene oxide, etc.) is preferable. Examples of such compounds include compounds represented by the following general formula (V) or (VI).

(In the formula, M, N, a and b are average polymerization degrees, and R represents hydrogen or an alkyl group.)
Here, M is 10 to 10000, preferably 50 to 1000, more preferably 100 to 300, N is 1 to 1000, preferably 5 to 300, more preferably 5 to 50, and M> N. , A is 2 to 100, preferably 5 to 50, more preferably 5 to 20, and b is 0 to 50, preferably 0 to 10. R is hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen.
The polyether-modified silicone represented by the general formula (V) is generally an organohydrogenpolysiloxane having a Si—H group and a polycarbon having a carbon-carbon double bond at the end, such as a polyoxyalkylene allyl ether. It can be produced by addition reaction with oxyalkylene alkyl ether.

(In the formula, A, B, h, and i are average polymerization degrees, R represents an alkyl group, and R ′ represents hydrogen or an alkyl group.)
Here, A is preferably 5 to 10,000, B is preferably 2 to 10,000, h is preferably 2 to 100, and i is preferably 0 to 50. R is preferably an alkyl group having 1 to 5 carbon atoms. R ′ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms. The weight average molecular weight of the block copolymer represented by the formula (VI) is preferably 15,000 to 100,000,000 from the viewpoint of dispersion stability.
The linear polysiloxane-polyoxyalkylene block copolymer is obtained by reacting a polyoxyalkylene compound having a reactive end group with a dihydrocarbylsiloxane having an end group that reacts with the reactive end group of the compound. Can be manufactured.

  Specific examples of the polyether-modified silicone oil used in the present invention include SH3772M, SH3775M, SH3748, SH3749, SF8410, SH8700, BY22-008, SF8421, Shin-Etsu Chemical (manufactured by Toray Dow Corning Silicone) KF352A, KF6008, KF615A, KF6016, KF6017, GE Toshiba Silicone Co., Ltd. TSF4450, TSF4452, Nippon Unicar Co., Ltd. SILWET L-7002, SILWET L-7602, SILWET L-7602, SILWET L -7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1-009-01, ABN SILWET FZ-F1-009-02, ABN SILWET FZ-F1-009-03, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1- 009-09, ABN SILWET FZ-F1-009-11, ABN SILWET FZ-F1-009-13, ABN SILWET FZ-F1-009-54, ABN SILWET FZ-2222, and the like. Or it can use as a mixture of 2 or more types.

  The compounding amount of the silicone compound used in the present invention is not particularly limited, but from the viewpoint of dispersion stability and the viscosity of the composition, the lower limit is usually 1% by mass or more, preferably 2% by mass or more, based on the entire composition. More preferably 3% by mass or more, particularly preferably 5% by mass or more, and the upper limit is 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. It is preferably included in an amount. Thereby, the dispersion stability can be improved, and the usability can be improved by suppressing the increase in viscosity.

  In the liquid treatment agent composition for textiles of the present invention, the mass ratio of the silicone compound and the component (B) is 99: 1 to 50:50, preferably 95: 5 to 60:40, and more preferably 90:10. It is good in the range of ~ 70: 30. By setting the ratio within such a range, functions having excellent texture such as flexibility and smoothness can be obtained for clothing such as polyester and cotton. In addition, when the ratio of the component (B) is within this range, the adsorptivity of silicone to fibers can be improved.

Water-soluble solvent The water-soluble solvent is selected from ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and water-soluble solvents represented by the following general formula It is preferable to mix a solvent component.
_{R3-O- (C 2 H 4} O) y - (C 3 H 6 O) z -H
(Wherein R3 is an alkyl or alkenyl group having 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms. Y and z are the average number of moles added, and y is 2 to 50, preferably 2 to 30, z represents a number of 0 to 50, preferably 0 to 20.)
Among them, preferred examples include ethanol, ethylene glycol, butyl carbitol, propylene glycol, diethylene glycol monopropylene glycol monobutyl ether [C ₄ H ₉ (C ₃ H ₆ O) (C ₂ H ₄ O) ₂ H] and the like. .
These water-soluble solvents usually have a lower limit of 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, and particularly preferably 3% by mass or more with respect to the entire composition. The upper limit is preferably 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 12% by mass or less.

Furthermore, this invention can contain the following components as needed.
Perfume In the present invention, a perfume can be added for the aroma of the composition. A list of perfume ingredients used can be found in various publications such as “Perfume and Flavor Chemicals”, Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic fragrance chemistry and commercial knowledge", Motoichi Into, Chemical Industry Daily (1996) and "Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allred Pub. Co. (1994) and "Encyclopedia of Scents", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Performer Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower Oils". , Danute Lajaujis Anonis, Allured Pub. Co. (1993), etc., each of which is incorporated herein by reference.
These fragrances usually have a lower limit of 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass with respect to the entire composition. The upper limit is 3% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

Dye In the present invention, a dye can be added for coloring the composition. The dye is not particularly limited, but is preferably a water-soluble dye from the viewpoint of ease of addition, and among these, one or more water-soluble dyes selected from acidic dyes and direct dyes are preferable. Specific examples of dyes that can be added include, for example, the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, issued July 20, 1969, Maruzen Co., Ltd.), Dye Note 22nd Edition (Shokusha Co., Ltd.), Legal Dye Handbook (Japan Cosmetic Industry Federation edited, issued on November 28, 1988, Yakuho Nippo Co., Ltd.) and the like, which are incorporated herein by reference.
These dyes usually have a lower limit of 0.01 ppm or more, preferably 0.02 ppm or more, more preferably 0.05 ppm or more, particularly preferably 0.1 ppm or more with respect to the entire composition. It is preferably contained in an amount of 50 ppm or less, preferably 40 ppm or less, more preferably 30 ppm or less, particularly preferably 20 ppm or less.
By setting it as such a compounding quantity, it can prevent that the color colored by the processing agent composition for textiles becomes very thin, and can make a coloring effect sufficient, On the other hand, processing for textiles It can prevent that the color colored to the agent composition becomes too dark.

Antioxidant In the present invention, an antioxidant can be added to improve the aroma stability and color tone stability of the composition. As the antioxidant, generally known natural antioxidants and synthetic antioxidants can be used. Specifically, a mixture of ascorbic acid, ascorbyl palmitate, propyl gallate, BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, hydroquinone, tertiary butylhydroquinone Natural tocopherol compounds, long-chain esters of gallic acid (C8 to C22) such as dodecyl gallate, irganox compounds available from Ciba Specialty Chemicals, citric acid and / or isopropyl citrate, 1- Hydroxyethylidene-1,1-diphosphonic acid (etidronic acid), 4,5-dihydroxy-m-benzenesulfonic acid / sodium salt, dimethoxyphenol, catechol, methoxyphenol, carotenoid, furans, amino acids, etc. That.
Among these, BHT (butylated hydroxytoluene), methoxyphenol, tocopherol compounds and the like are preferable from the viewpoint of the appearance and storage stability of the treating agent composition for textile products.
These antioxidants usually have a lower limit of 0.00001% by mass or more, preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and particularly preferably 0.01% by mass relative to the whole composition. The upper limit is 3% by mass or less, preferably 2.5% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less. In addition, when used, it may be added in any number of times, such as before and after the production of the composition, in any place within the range not impeding the effects of the present invention.

Preservative In the present invention, one or more of the following compounds can be used in combination for the purpose of enhancing the antiseptic and bactericidal power of the composition.
1) As the isothiazolone-based organic sulfur compound, a compound containing a 3-isothiazolone group is preferable. These compounds are disclosed, for example, in US Pat. No. 4,265,899. Examples include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, 2-phenyl-3-isothiazolone, 2-methyl. -4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof. A more preferred antiseptic / disinfectant is an aqueous mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, more preferably about 77% by mass. Water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and about 23% by weight of 2-methyl-4-isothiazolin-3-one. Commercially available products such as Ron &Haas's Caisson CG / ICP (approximately 1.5 mass% aqueous solution) and Junside series such as Junsei 5 manufactured by Junsei Kagaku can be used.
2) Benzisothiazoline-based organic sulfur compounds include 1,2-benzisothiazoline-3-one, 2-methyl-4,5-trimethylene-4-isothiazoline-3-one, dithio-2,2-bis (benz Methylamide) and the like can be used, and they can be used in any mixing ratio. Examples of such compounds include Proxel series [BDN (effective content 33% by mass), BD20 (effective content 20% by mass), XL-2 (effective content 10% by mass), GXL (effective content) manufactured by Avicia Co., Ltd. 20 mass%), LV (effective mass 20 mass%), TN (effective mass 60 mass%)], and commercially available products such as Denide BIT / NIPA.
3) 5-Bromo-5-nitro-1,3-dioxane or 2-bromo-2-nitropropane-1,3-diol or 5-chloro-5-nitro-1,3-dioxane or 2-chloro-2-nitropropane -1,3-diol and the like can be used. Commercially available products such as Bronidox L from Henkel, Bronopol from Inolex, Bronopol from Yoshitomi Pharmaceutical, Myrside BT from Boots, Myrside Pharma BP from BASF, etc. can be used.
4) Benzoic acids or phenol compounds include benzoic acid or a salt thereof, salicylic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, paraoxy Use of benzyl benzoate, 3-methyl-3-isopropylphenol, o-phenylphenol, 2-isopropyl-5-methylphenol, resorcin, cresol, 2,6-di-tert-butyl-p-cresol, etc. it can.

  The compound of 1) -3) is mix | blended 0-0.1 mass% with respect to a composition. A preferable compounding amount is 0.00001 to 0.03% by mass, more preferably 0.00005 to 0.02% by mass. The compound 4) is blended in an amount of 0 to 3% by weight based on the composition. A preferable compounding amount is 0.01 to 1.5% by mass. Moreover, antiseptic | preservative power and bactericidal power can be strengthened by using together 2 or more types of the said compound of 1) -4), It is also possible economically to reduce the usage-amount of the said compound. It is particularly preferable to use two or more of Caisson CG / ICP, Proxel series BDN, Myaside BT, and benzoic acid, and the blending amount is preferably 0.00001 to 2% by mass. More preferably, it is 0.00002-1 mass%, More preferably, it is 0.00005-0.5 mass%. The above compounds 1) to 3) may be added together with metal ions such as zinc, copper, calcium and magnesium for stabilization, or added to the composition as an ethylene glycol, propylene glycol or dipropylene glycol solution. preferable.

Antifoaming agent In this invention, an antifoaming agent can be mix | blended. Examples of the antifoaming agent include silicone-based antifoaming agents, alcohol-based antifoaming agents, ester-based antifoaming agents, mineral oil-based antifoaming agents, vegetable oil-based antifoaming agents, and synthetic oil-based antifoaming agents. A silicone-based antifoaming agent is preferred from the viewpoint of improving foamability by suppressing foaming during measurement of the softening agent. Examples of silicone-based antifoaming agents include oil-type antifoaming agents, compound-type antifoaming agents, self-emulsifying antifoaming agents, emulsion-type antifoaming agents, powder-type antifoaming agents, and solid-type antifoaming agents. Of these, self-emulsifying antifoaming agents and emulsion antifoaming agents are preferred.
The blending amount of the antifoaming agent is not particularly limited, but usually the lower limit is 0.1 ppm or more, preferably 0.2 ppm or more, more preferably 0.5 ppm or more, particularly preferably 1 ppm or more based on the whole composition. The upper limit is preferably 1% by mass or less, preferably 0.8% by mass or less, more preferably 0.7% by mass or less, and particularly preferably 0.5% by mass or less.

pH adjuster Although pH of the liquid processing agent composition for textiles of this invention is not specifically limited, It is preferable that it is the range of 5-10, and it is more preferable that it is the range of 6-8. As necessary, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, paratoluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethanediphosphonic acid, phytic acid, ethylenediaminetetraacetic acid, PH adjustment of short chain amine compounds such as triethanolamine, diethanolamine, dimethylamine, N-methylethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, and alkali metal silicates An agent can be used. In the present invention, the pH is measured at a solution temperature of 20 ° C. according to JIS K3622-1998.

Ciba Specialty Chemicals as an ultraviolet absorber UV absorber Co. Ciba (R) TINOSORB (R) FR, FD, etc. CIBAFAST (registered trademark) can be blended 0.01 to 5 mass%.

  In the liquid treatment composition for textiles of the present invention, additives that are used in ordinary household cleaning agents or finishing agents can be used as long as the effects of the present invention are not hindered. Specific examples of such additives include anionic surfactants, cationic surfactants, nonionic surfactants other than the above component (C), partially esterified products of hexanoic acid and glycerin or pentaerythritol, Water-soluble salts such as ammonium chloride, calcium chloride, magnesium chloride and potassium chloride, oils such as liquid paraffin and higher alcohols, nonionic polymers such as urea, hydrocarbons, anionic polymer compounds and nonionic cellulose derivatives Examples thereof include compounds, fluorescent brighteners, enzymes, emulsions, fluorescent brighteners, silica fine particles such as colloidal silica, and the like.

  In addition, when blending an anionic surfactant and an anionic polymer compound, considering the adsorption effect of the metal oxide particles as the component (A), the polymer compound having a cationic property as the component (B) It is preferable to blend in an amount lower than the content.

  The liquid processing agent composition for textiles of the present invention contains the above components (A) to (C) and optional components, and the balance is usually water. The liquid treatment agent composition for textiles according to the present invention can be produced by filling each of the above components in a container, sufficiently stirring the mixture, and then adding water and stirring sufficiently until uniform. . These components can be added together or in any order. For example, after the components (A) and (C) are added and stirred, water is added and stirred, and then the components ( By adding and stirring B), the processing agent composition for textiles of this invention can be manufactured. The stirrer / disperser used for the production is not particularly limited, but can be prepared by stirring using a homogenizer, an ultrasonic disperser, a bead mill or the like.

  The liquid treatment agent composition for textiles of the present invention is not particularly limited in its dosage form and method of use. The treatment agent liquid composition for textile products of the present invention is used after being diluted to an appropriate concentration. The method of use is not particularly limited, but the laundry is usually washed, and the composition of the present invention is dissolved in the rinse water at the rinsing stage, and the composition of the present invention is used using a container such as a tub. Examples include a method in which an object is dissolved in water, and further, clothing is added to perform immersion treatment. The fiber product may be treated by any method, but the bath ratio (the ratio of the treatment liquid to the fiber product) is preferably 3 to 100 times, particularly preferably 5 to 50 times. When diluted and used in this way, it is preferable to use the liquid composition or the liquid composition as a packaging type in which the liquid composition is individually packaged with a water-soluble film, sheet or the like. When the treatment composition for textile products is diluted and used in water, it is preferably prepared so that the concentration of the metal oxide particles is preferably 0.1 to 100 ppm, more preferably 1 to 10 ppm.

  It is also possible to fill a trigger container or aerosol container and spray directly on the textile product. In the case where the fiber product treating agent liquid composition is directly sprayed onto the fiber product, the concentration of the metal oxide particles as the component (a) is preferably 0.004 to 4% owf, more preferably 0.04 to 0. It is prepared by adding water, ethanol or the like as appropriate so that it becomes 4% owf. Further, a sheet material such as a nonwoven fabric can be impregnated with the composition of the present invention in an amount of, for example, 60 to 80% by mass, and the obtained sheet material can be put into a dryer and used.

  The composition of the present invention can be used regardless of whether the raw material of the textile product is a natural fiber or a synthetic fiber, but it effectively adsorbs metal oxide particles when used for natural fibers such as cotton. This is preferable because it can effectively deodorize malodors.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in more detail, this invention is not limited to this. “%” Indicates “% by mass” unless otherwise specified, and the ratio indicates a mass ratio. Unless otherwise indicated, the component amounts in Table 2 indicate mass% of the pure component.
Table 1 shows the metal oxide particles used in Examples and Comparative Examples. In addition, none of A-1 to A-7 in Table 1 is subjected to surface treatment.

The average particle size was measured as follows. After adding 200 mL of 99.5 vol% ethanol to 5 g of metal oxide particles and stirring and dispersing for 5 minutes at a rotational speed of 10,000 rpm using a powerful homogenizer DIAX900 (shaft generator 18F) manufactured by Heidorf, several drops immediately on the sample stage. It is an average value of 10 particles obtained by hanging and air-drying, depositing an air-dried sample with platinum, and measuring the particle diameter at a magnification of 100,000 using a Hitachi scanning transmission electron microscope apparatus H-8010.
The physical deodorization rate and the chemical deodorization rate were measured by the following methods.

Preparation of Evaluation Cloth and Blank Cloth 1 kg of a new polyester jersey cloth is used in a two-tank washing machine (Mitsubishi Electric Corporation, CW-C30A1-H). The product was treated under conditions of 7.5 g, washed for 15 minutes, rinsed for 15 minutes and dehydrated for 1 minute × 8 times, and dried in a room at room temperature of 25 ° C. and humidity of 65% RH. The dried cloth was cut into 2 cm × 2 cm (0.1 g), 50 μL of 0.1% metal oxide particles / ethanol dispersion was added, and 0.05% owf (mass% relative to the mass of the target fiber) was added as the metal oxide. ) Was attached to the cloth and dried for 12 hours in a room with a room temperature of 25 ° C. and a humidity of 65% RH. In addition, on the said conditions, what was created similarly except not adding a metal oxide particle was used as the blank cloth.

Measurement and evaluation of physical deodorization rate Each cloth and blank cloth were put into a 20 mL vial, and after adding an aqueous solution of isovaleric acid in an amount of 0.1 ppm at 40 ° C. for 1 hour, sealed and light-shielded at 40 ° C. It left still in a thermostat for 1 hour, and the head space was extracted for 10 minutes with the solid phase micro extraction SPME (Fiber: Stable Flex CW / DVB, 70 μm film) manufactured by Spelco. The extracted SPME was measured by using a GC-MS apparatus (HP6890 Series GC System + Mass Selective Detector) manufactured by HEWLETT PACKARD, column: HP-INNOWAX (30 m × 0.2 mm × 0.2 μm), measuring temperature 80 to 180 ° C. Temperature rate 10 ° C./min. , Carrier gas: helium, injection port 250 ° C., injection method: splitless measurement.

Chemical deodorization rate measurement Evaluation cloth or blank cloth is put in a 20 mL vial, respectively, and after adding an aqueous solution of isovaleric acid in an amount of 0.1 ppm at 40 ° C. for 1 hour, tightly plugged, Toshiba black light ( EFD15BLB) was allowed to stand in a constant temperature bath at 40 ° C. for 1 hour while irradiating ultraviolet light of 365 nm at ² mW / cm ^2, and the headspace was solid phase microextraction SPME (Fiber: Stable Flex CW / (DVB, 70 μm film) for 10 minutes. The extracted SPME was measured by using a GC-MS apparatus (HP6890 Series GC System + Mass Selective Detector) manufactured by HEWLETT PACKARD, column: HP-INNOWAX (30 m × 0.2 mm × 0.2 μm), measuring temperature 80 to 180 ° C. Temperature rate 10 ° C./min. , Carrier gas: helium, injection port 250 ° C., injection method: splitless measurement.

About physical deodorization rate and chemical deodorization rate, the deodorization rate was calculated | required from the following formula from the peak area of the mass chromatogram of m / Z = 60 of the total ion gas chromatogram measured by said method.
Deodorization rate = 100− (peak area of evaluation cloth) × 100 / (peak area of blank cloth)
In addition, the solubility with respect to 100 g of water of 25 degreeC water of the metal oxide particle of Table 1 is 5 * 10 <^-4> g, 3 * 10 <^-4> g, insoluble, insoluble, 9 * 10 <^-4> g in order from A-1. 7 × 10 ⁻⁴ g and 5 × 10 ⁻⁴ g.

The preparation method and evaluation method of the treatment composition for textile products are shown below.
Preparation method of textile agent treatment composition (A) Metal oxide particles described in Table 1, and silicone, nonionic surfactant, butyl carbitol, ethanol, fragrance, and optionally dichloride Decyldimethylammonium was charged into a 500 mL beaker, and this was sufficiently stirred using a stirring blade. Next, with stirring, ion-exchanged water was added, and while further stirring, (B) the polymer having a cationic property described in Table 2 was added and stirred, and then sufficiently stirred until it became uniform. A fiber treatment agent composition was prepared. All compositions had a pH of 6-8. In addition, the compounding quantity of each component was based on the composition shown in Table 2.
About each processing agent composition (Examples 1-10 and Comparative Examples 1-4) obtained in this way, according to (1) deodorizing evaluation and (2) dispersion stability evaluation described below, The odor effect and dispersion stability were evaluated.

(1) Deodorization evaluation
Preparation of test cloth 5 new 100% cotton skin shirts or 10 new 100% polyester lace curtains 30cm x 60cm 10 pieces of granular detergent "Top" for commercial clothing (manufactured by Lion Corporation, ingredients: surfactant (alpha (Sulfo fatty acid ester sodium, fatty acid sodium, polyoxyethylene alkyl ether), water softener, alkali agent, dissolution accelerator, enzyme, fluorescent whitening agent), a two-tank washing machine for home use (Mitsubishi Electric Corporation, CW- Washing using C30A1-H) for 15 minutes (detergent using standard amount, 30 times bath ratio, 45 ° C. tap water) → Dehydration 5 minutes after repeating 2 cycles, rinse with running water 15 minutes → Dehydration 5 minutes Was repeated 5 times, and the air-dried fabric was used as a test cloth.

Deodorization Evaluation 1—Evaluation of Physical Deodorization Action 14 cotton shirts subjected to the above treatment were cut in half, and a granular detergent for commercial clothing “Top” (manufactured by Lion Co., Ltd., component: surfactant (alphasulfo Fatty acid ester sodium, fatty acid sodium, polyoxyethylene alkyl ether), water softener, alkali agent, dissolution accelerator, enzyme, fluorescent whitening agent), a two-tank washing machine for home use (Mitsubishi Electric Corporation, CW-C30A1) -H) (detergent used standard amount, bath ratio 30 times, 20 ° C. tap water used, 10 minutes), only for one side of half-cut skin shirt, rinse in the second time in Table 2 10 mL of the textile product treating agent compositions of the examples and comparative examples shown were added to 30 L of water to perform treatment (30 times the bath ratio, use of tap water at 20 ° C., 3 minutes). Thereafter, it was naturally dried under the conditions of 20 ° C. and 40% RH. The skin shirts after drying were sewn together, and 14 test subjects wore them for 1 day. After the wearing, the skin shirts that had been sewn together were pulled apart to make an evaluation cloth, and the following evaluations were performed. The results are also shown in Table 2.

Deodorant Evaluation 2—Evaluation of Chemical Deodorizing Action 10 lace curtains subjected to the above treatment were cut in half, and a granular detergent for commercial clothing “Top” (manufactured by Lion Corporation, component: surfactant (alphasulfo fatty acid) Ester sodium, fatty acid sodium, polyoxyethylene alkyl ether), water softener, alkali agent, dissolution accelerator, enzyme, fluorescent whitening agent), a two-tank washing machine for home use (Mitsubishi Electric Corporation, CW-C30A1- H) (detergent used standard amount, bath ratio 30 times, 20 ° C. tap water used, 10 minutes) 10 mL of the fiber product treating agent compositions of Examples and Comparative Examples were added to 30 L of water to perform treatment (30 times bath ratio, use of tap water at 20 ° C., 3 minutes). Thereafter, it was naturally dried under the conditions of 20 ° C. and 40% RH. Each dried lace curtain was placed in a sealed container containing a cigarette for 3 seconds, irradiated with ultraviolet light of ² mW / cm ² of 365 nm at room temperature of 25 ° C. for 24 hours, and evaluated as follows. . The results are also shown in Table 2.

Evaluation method The odor of the above-mentioned evaluation cloth is judged by 10 expert panelists, "Sensory inspection handbook in industry" (edited by Nikka Tech Ren Sensory Inspection Committee, published by Nikka Tech Ren Publishing Co., 1963), pages 300-309. Measured according to the method described. That is, according to Scheffe's paired comparison method, if there is a clear difference in odor between the two evaluation cloths, +2 points will be given to the evaluation cloth that does not smell, and -2 points will be given to the evaluation cloth that smells. When there was a difference, +1 point and -1 point were given respectively, and when there was no difference, 0 point was given to both. The score thus obtained was statistically processed by a computer and evaluated according to the following evaluation criteria. The results are also shown in Table 2.

Evaluation criteria

(2) Dispersion stability evaluation The treatment agent composition prepared as described above was placed in a 100 mL bottle with a lid, left in a thermostatic chamber at 25 ° C. for 1 month, and the dispersion state was visually determined. The results are also shown in Table 2.

Evaluation criteria

The meanings and details of the abbreviations in Table 2 are as follows.
B-1: Dimethyl diallyl type polymer, Trade name: MERQUAT100 (Calgon, cationization degree 8.7)
B-2: Dimethyl diallyl type polymer, trade name: Adeka thioace PD-50 (manufactured by Asahi Denka Kogyo Co., Ltd.)
C-1: POE tridecyl ether, trade name: TAG-90 (manufactured by Lion Corporation, EO = 7 mol addition, HLB = 12)
C′-2: POE tridecyl ether, trade name: Leocoal TDA400-75 (manufactured by Lion Corporation, EO = 40 mol addition, HLB = 18)
Didecyldimethylammonium chloride: Trade name: ARCARD 210-80E (manufactured by Lion Akzo)
Silicone: Polyether-modified silicone, trade name SH3749 (manufactured by Toray Dow Corning Silicone)
Butyl carbitol: Product name: Butyl dioxitol (95) (manufactured by Shell Chemicals)
Ethanol: Reagent perfume A: Perfume composition A described in Table 6 of JP-A No. 2004-131895
Fragrance B: Fragrance composition B described in Table 6 of JP-A No. 2004-131895

Claims (3)

(A) metal oxide particles having an average particle size of 0.1 nm to less than 1000 nm, and having at least one kind of metal deodorizing action and physical deodorizing action;
(B) a water-soluble polymer having cationic properties, and (C) a textile product characterized by containing an alkylene oxide adduct of a higher alcohol, a higher alkylamine, or a higher fatty acid having an HLB value of 6 to 16. Liquid treatment agent composition.   The liquid treatment agent composition for textiles according to claim 1, wherein the metal oxide particles have a physical deodorizing action of 70% or more and a chemical deodorizing action of 70% or more. (A) metal oxide particles having an average particle size of 0.1 nm to less than 1000 nm, and having at least one kind of metal deodorizing action and physical deodorizing action;
Using a treatment liquid containing (B) a water-soluble polymer having cationic properties, and (C) a higher alcohol or a higher alkylamine or an alkylene oxide adduct of a higher fatty acid having an HLB value of 6 to 16, a fiber product is obtained. A method for treating a textile product, characterized by comprising: