JP6171202B2 - Textile processing method - Google Patents

Description

  The present invention relates to a method for treating textile products.

  It is known to add a fragrance to textiles using a spray (Patent Document 1). By using a spray, the strength of the scent can be adjusted. However, on the other hand, it has the disadvantage that it does not leave much scent after a while.

JP 2010-90330 A

  An object of the present invention is to provide a fiber product processing method and a fiber product treating agent kit in which a scent remains in a fiber product even after a lapse of time.

According to the present invention, Step 1: After treating a fiber product with a fiber treatment agent 1 containing (A) a highly branched cyclic dextrin and (B) a cationic surfactant or an amine compound,
Step 2: dehydrate,
Step 3: A method for treating a textile product is provided, which comprises a step of treating the dehydrated textile product with (C) a fiber treatment agent 2 containing a fragrance composition.
The present invention also provides a fiber treatment agent 1 containing (A) a highly branched cyclic dextrin and (B) a cationic surfactant or an amine compound,
(C) Provided is a fiber product treatment agent kit comprising at least a fiber treatment agent 2 containing a fragrance composition, and containing each in a separate container.

  According to the present invention, fragrance can be strengthened even after a long time has elapsed after the treatment.

[Component (A)]
The component (A) contained in the fiber treatment agent 1 of the present invention is a glucan having an inner branching cyclic structure part and an outer branching structure part and having a polymerization degree in the range of 50 to 10,000, wherein the inner branching The cyclic structure portion is a cyclic structure portion formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond, and the outer branched structure portion is bonded to the inner branched cyclic structure portion. It is a glucan which is an acyclic structure part. Such a glucan is also called a highly branched cyclic dextrin, and the component (A) is also referred to as “highly branched cyclic dextrin” in this specification. The component (A) may be contained in the fiber treatment agent 2.
The highly branched cyclic dextrin contained in the fiber treatment agent 1 of the present invention has a molecular weight of about 30,000 to 1,000,000, has one cyclic structure in the molecule, and a large number of glucan chains bonded to the cyclic portion. It mainly contains dextrin having a weight average degree of polymerization of about 2500.
The highly branched cyclic dextrin of the highly branched cyclic dextrin contained in the fiber treatment agent 1 of the present invention is composed of about 10 to 100 glucoses, and the inner branched cyclic structure portion includes a large number of non-cyclic branched glucan chains. The outer branching structure part which consists of is couple | bonded.
For example, the degree of polymerization of the highly branched cyclic dextrin contained in the fiber treatment agent 1 of the present invention is in the range of 50 to 5000.
For example, the polymerization degree of the inner branched cyclic structure portion of the highly branched cyclic dextrin contained in the fiber treatment agent 1 of the present invention is in the range of 10-100.
For example, the degree of polymerization of the outer branched structure portion of the highly branched cyclic dextrin contained in the fiber treatment agent 1 of the present invention is 40 or more.
For example, the polymerization degree of each unit chain of the outer branched structure portion of the highly branched cyclic dextrin contained in the fiber treatment agent 1 of the present invention is 10 to 20 on average.

The highly branched cyclic dextrin contained in the fiber treatment agent 1 of the present invention is produced, for example, by using starch as a raw material and an enzyme called a branching enzyme. The starch, which is a raw material, is composed of amylose in which glucose is linearly bound by α-1,4-glucoside bonds and amylopectin having a structure branched in a complex manner by α-1,6-glucoside bonds. It is a macromolecule with many connected structures. Branching enzyme, an enzyme used, is a glucan chain transferase widely distributed in animals, plants, and microorganisms. It acts on the seam portion of the cluster structure of amylopectin and catalyzes the reaction of cyclizing it.
More specifically, the highly branched cyclic dextrin contained in the fiber treatment agent 1 of the present invention has an inner branched cyclic structure portion and an outer branched structure portion described in JP-A-8-134104, and has a polymerization degree of 50 to 10,000. It is a glucan in the range. In the present specification, the highly branched cyclic dextrin can be understood in consideration of the description in JP-A-8-134104.
The highly branched cyclic dextrin contained in the fiber treatment agent 1 of the present invention has a specific structure as described above and has a high degree of polymerization (weight average molecular weight), α-cyclodextrin (n = 6), This is different from general cyclodextrins in which 6 to 8 glucoses are bound, such as β-cyclodextrin (n = 7) and γ-cyclodextrin (n = 8).
Specific examples of the highly branched cyclic dextrin contained in the fiber treatment agent 1 of the present invention include “Cluster Dextrin” (registered trademark) manufactured by Glico Nutrition Foods, Inc.

In addition, instead of highly cyclic branched dextrin, 6-8 glucoses such as α-cyclodextrin (n = 6), β-cyclodextrin (n = 7), γ-cyclodextrin (n = 8) are generally bonded. Even if a typical cyclodextrin is blended in the fiber treatment agent 1, an excellent effect of improving the remaining fragrance property similar to that of the fiber treatment agent 1 of the present invention cannot be obtained.
In the fiber treatment agent 1 of the present invention, the blending amount of the component (A) is not particularly limited, but when used as a softener composition, it is preferably 0.01 to 10% by mass with respect to the total mass of the entire composition, More preferably, it is 0.03-5 mass%, More preferably, it is 0.05-3 mass%. When the blending amount of the component (A) is more than 0.01% by mass, an excellent residual fragrance improving effect can be exhibited. When the blending amount of the component (A) is more than 10% by mass, the effect of improving the residual fragrance property is not particularly improved, the stability at high temperature storage may be deteriorated, the liquid viscosity of the composition is increased, and the handling property is increased. May decrease.

[Component (B)]
The component (B) contained in the fiber treatment agent 1 of the present invention is a cationic surfactant or an amine compound. The component (B) may be contained in the fiber treatment agent 2. For example, the amine compound used as the component (B) in the present invention may be a hydrocarbon group having 10 to 26 carbon atoms (hereinafter referred to as “long-chain hydrocarbon group”) which may be separated by an ester group or an amide group. ) In the molecule, for example, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylamino And propylamide. The cationic surfactant used as the component (B) of the present invention may be at least one compound selected from the group consisting of salts of the amine compounds and quaternized products thereof. Among the components (B), an acid salt of a tertiary amine or a quaternized product thereof having at least one hydrocarbon group having 10 to 26 total carbon atoms, which may be separated by an ester group or an amide group in the molecule. preferable. This compound is usually used as a softening base for softening compositions. However, the cationic surfactant that can be used as the component (B) of the present invention is not limited to a soft base.
When used for the fiber treatment agent 1 of the present invention, the component (B) is an amine having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms which may be separated by ester groups or amide groups. It is preferably at least one compound selected from the group consisting of a compound, a salt thereof and a quaternized product thereof. In particular, the carbon number of the long chain hydrocarbon group is 10 to 26, preferably 16 to 26, and more preferably 18 to 24. When the carbon number of the long-chain hydrocarbon group is 10 or more, the flexibility is good, and when it is 26 or less, the handling property is good.

When used for the fiber treatment agent 2 of the present invention, the component (B) is an amine compound having two hydrocarbon groups having 10 to 14 carbon atoms which may be separated by an ester group or an amide group, and a salt thereof. And a quaternized product thereof, and an amine compound having one hydrocarbon group having 10 to 18 carbon atoms which may be separated by an ester group or an amide group in the molecule, a salt thereof, and a quaternized product thereof. At least one compound is preferred. Especially, the amine compound which has two C10-14 hydrocarbon groups which may be divided | segmented by the ester group or the amide group in a molecule | numerator, its salt, and its quaternization thing are especially preferable.
The long chain hydrocarbon group may be saturated or unsaturated. When the long chain hydrocarbon group is unsaturated, the position of the double bond may be at any position.
The long chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group containing a ring in the structure, and is preferably a chain hydrocarbon group. The chain hydrocarbon group may be linear or branched. As the chain hydrocarbon group, an alkyl group or an alkenyl group is preferable.
The long chain hydrocarbon group may be separated by an ester group (—COO—) or an amide group (—NHCO—). That is, the long-chain hydrocarbon group has at least one kind of splitting group selected from the group consisting of an ester group and an amide group in the carbon chain, and the carbon chain is split by the splitting group. May be. Having the splitting group is preferable from the viewpoint of improving biodegradability.

When it has this dividing group, the number of the dividing groups which one long-chain hydrocarbon group has may be one, or may be two or more. That is, the long chain hydrocarbon group may be divided at one place by a dividing group, or may be divided at two or more places. When having two or more splitting groups, each splitting group may be the same or different.
In addition, when it has a splitting group in a carbon chain, the carbon atom which a splitting group shall count to carbon number of a long-chain hydrocarbon group.
The long-chain hydrocarbon group is usually an unhydrogenated fatty acid derived from beef tallow, which is used industrially, a fatty acid obtained by hydrogenation or partial hydrogenation of an unsaturated part, palm-derived palm oil, oil palm-derived It is introduced by using a hydrogenated fatty acid or fatty acid ester, or a fatty acid or fatty acid ester obtained by hydrogenation or partial hydrogenation of an unsaturated portion.
As the amine compound in the component (B) contained in the liquid treating agent composition for textiles of the present invention, a secondary amine compound or a tertiary amine compound is preferable, and a tertiary amine compound is more preferable.
More specifically, examples of the amine compound in the component (B) include compounds represented by the following general formula (B1).

[Wherein, R ^{1 to} R ³ are each independently a hydrocarbon group having 10 to 26 carbon atoms, —CH ₂ CH (Y) OCOR ⁴ (Y is a hydrogen atom or CH ₃ , and R ⁴ is 7 carbon atoms. to 21 is a hydrocarbon _{group), -.. (CH 2} ) n NHCOR 5 (n is 2 or 3, R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms), a hydrogen atom, the number of carbon atoms 1 to 4 alkyl group, —CH ₂ CH (Y) OH, or — (CH ₂ ) _n NH ₂ , and at least one of R ^{1 to} R ³ is a hydrocarbon group having 10 to 26 carbon atoms. , —CH ₂ CH (Y) OCOR ⁴ , or — (CH ₂ ) _n NHCOR ⁵ . ]
Wherein the carbon number of the hydrocarbon group having 10 to 26 carbon atoms in R ¹ to R ³ is preferably 17 to 26, 19 to 24 is more preferable. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably an alkyl group or an alkenyl group.
In —CH ₂ CH (Y) OCOR ⁴ , Y is a hydrogen atom or CH ₃ , and a hydrogen atom is particularly preferable.

R ⁴ is a hydrocarbon group having 7 to 21 carbon atoms, preferably 15 to 19 carbon atoms. When R ⁴ is more present in the formula may be R ⁴ of said plurality of mutually identical, may be different.
Hydrocarbon group R ⁴ is a residue obtained by removing a carboxy group from a fatty acid having 8 to 22 carbon atoms (R ⁴ COOH) (fatty acid residues), R ⁴ Nomoto become fatty (R ⁴ COOH) is Saturated fatty acids or unsaturated fatty acids may be used, and straight-chain fatty acids or branched fatty acids may be used. Of these, saturated or unsaturated linear fatty acids are preferred. In order to impart good water absorption to the soft-treated garment, the saturated / unsaturated ratio (mass ratio) of the fatty acid serving as R ⁴ is preferably 90/10 to 0/100, and 80/20 to 0 / 100 is more preferable.
When R ⁴ is an unsaturated fatty acid residue, a cis isomer and a trans isomer are present, and the mass ratio of the cis isomer / trans isomer is preferably 40/60 to 100/0, and 70/30 to 90/10. Particularly preferred.
Specific examples of fatty acids used as R ⁴ include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), partial Examples include hydrogenated beef tallow fatty acid (iodine value of 10 to 60). Among them, a fatty acid prepared by combining two or more selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid in predetermined amounts to satisfy the following conditions (a) to (c) It is preferable to use a composition.

(A) The ratio (mass ratio) of saturated fatty acid / unsaturated fatty acid is 90/10 to 0/100, more preferably 80/20 to 0/100.
(B) The ratio (mass ratio) of cis isomer / trans isomer is 40/60 to 100/0, more preferably 70/30 to 90/10.
(C) The fatty acid having 18 carbon atoms is 60 mass% or more, preferably 80 mass% or more, the fatty acid having 20 carbon atoms is less than 2 mass%, and the fatty acid having 21 to 22 carbon atoms is less than 1 mass%. .
In — (CH ₂ ) _n NHCOR ⁵ , n is 2 or 3, and 3 is particularly preferable.
R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms, preferably 15 to 19 carbon atoms. When R ⁵ is more present in the formula may be R ⁵ of said plurality of mutually identical, may be different.
Examples of R ⁵ include the same as R ⁴ .

Of R ^{1 to} R ³ , at least one is a long chain hydrocarbon group, and preferably two are long chain hydrocarbon groups.
When one or two of R ^{1 to} R ³ are long-chain hydrocarbon groups, the remaining two or one is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, —CH ₂ CH (Y) OH or — (CH ₂ ) _n NH ₂ , preferably an alkyl group having 1 to 4 carbon atoms, —CH ₂ CH (Y) OH, or — (CH ₂ ) _n NH ₂ . Among these, as a C1-C4 alkyl group, a methyl group or an ethyl group is preferable, and a methyl group is especially preferable. Y in —CH ₂ CH (Y) OH is the same as Y in —CH ₂ CH (Y) OCOR ⁴ . _{N in} — (CH ₂ ) _n NH ₂ is the same as n in — (CH ₂ ) _n NHCOR ⁵ .
Preferable examples of the compound represented by the general formula (B1) include compounds represented by the following general formulas (B1-1) to (B1-8).

[Wherein, R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms. R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 7 to 21 carbon atoms, and a linear or branched alkyl group or alkenyl group having 15 to 17 carbon atoms is particularly preferable. ]
Examples of the hydrocarbon group for R ⁷ and R ⁸ include the same hydrocarbon groups as those having 10 to 26 carbon atoms for R ^{1 to} R ³ .
Examples of the hydrocarbon group having 7 to 21 carbon atoms in R ⁹ and R ¹⁰ include those similar to the hydrocarbon group having 7 to 21 carbon atoms in R ⁴ . When R ⁹ is more present in the formula, R ⁹ of the plurality of may be the same as each other, it may be different.
The salt of an amine compound is obtained by neutralizing an amine compound with an acid. The acid used for neutralization of the amine compound may be an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, and methyl sulfuric acid. Neutralization of the amine compound can be performed by a known method.
A quaternized product of an amine compound is obtained by reacting the amine compound with a quaternizing agent. Examples of the quaternizing agent used for the quaternization of the amine compound include alkyl halides such as methyl chloride and dialkyl sulfates such as dimethyl sulfate. When these quaternizing agents are reacted with an amine compound, the alkyl group of the quaternizing agent is introduced into the nitrogen atom of the amine compound, and a salt of a quaternary ammonium ion and a halogen ion or a monoalkyl sulfate ion is formed. . The alkyl group introduced by the quaternizing agent is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The quaternization of the amine compound can be performed by a known method.

The component (B) contained in the fiber treatment agent 1 or the fiber treatment agent 2 of the present invention is at least one selected from the group consisting of the compound represented by the general formula (B1), a salt thereof, and a quaternized product thereof. Is preferable, and at least one selected from the group consisting of the general formulas (B1-1) to (B1-8), salts thereof and quaternized compounds thereof is more preferable, (B1-4) to (B1-6), More preferred is at least one selected from the group consisting of salts and quaternized products thereof. Two or more quaternized compounds (B1-4) to (B1-6) are even more preferable. In the formula, at least two of quaternized compounds (B1-4) to (B1-6) in which R9 is a linear or branched alkyl group or alkenyl group having 15 to 17 carbon atoms are particularly preferable.
As the compound represented by the formula (B1), a salt thereof, and a quaternized product thereof, a commercially available product may be used, or a product produced by a known method may be used.
For example, a compound represented by the general formula (B1-2) (hereinafter “compound (B1-2)”) and a compound represented by the general formula (B1-3) (hereinafter “compound (B1-3)”) are: The fatty acid composition, or a fatty acid methyl ester composition obtained by replacing the fatty acid in the fatty acid composition with a methyl ester of the fatty acid, and methyldiethanolamine can be synthesized. At that time, from the viewpoint of improving flexibility, the abundance ratio represented by “compound (B1-2) / compound (B1-3)” is synthesized such that the mass ratio is 99/1 to 50/50. It is preferable to do.
Furthermore, when the quaternized product is used, it is more preferable to use dimethyl sulfate as a quaternizing agent. At that time, from the viewpoint of flexibility, the abundance ratio represented by “a quaternized compound (B1-2) / a quaternized compound (C1-3)” is 99/1 to 50/50 in mass ratio. It is preferable to synthesize.

Compound represented by general formula (B1-4) (hereinafter “compound (B1-4)”), compound represented by general formula (B1-5) (hereinafter “compound (B1-5)”), general formula The compound represented by (B1-6) (hereinafter “compound (B1-6)”) can be synthesized by a condensation reaction of the fatty acid composition or fatty acid methyl ester composition and triethanolamine. At that time, the content ratio of each component to the total mass of the compounds (B1-4), (B1-5), and (B1-6) is 1 to 60 masses of the compound (C1-4) from the viewpoint of flexibility. %, The compound (B1-5) is preferably 5 to 98% by mass, the compound (B1-6) is preferably 0.1 to 40% by mass, the compound (B1-4) is 30 to 60% by mass, the compound ( More preferably, B1-5) is 10 to 55% by mass, and compound (B1-6) is 5 to 35% by mass.
In addition, when using the quaternized product, it is more preferable to use dimethyl sulfate as a quaternizing agent in that the quaternization reaction proceeds sufficiently. The abundance ratio of each quaternized compound (B1-4), (B1-5), or (B1-6) is a mass ratio from the viewpoint of flexibility, and the quaternized compound (B1-4) is 1 to 4. 60% by mass, the quaternized compound (B1-5) is preferably 5 to 98% by mass, and the quaternized compound (B1-6) is preferably 0.1 to 40% by mass. ) Is 30 to 60% by mass, the quaternized compound (B1-5) is 10 to 55% by mass, and the quaternized compound (B1-6) is 5 to 35% by mass. preferable. In addition, when the compounds (B1-4), (B1-5), and (B1-6) are quaternized, esteramine that is not quaternized generally remains after the quaternization reaction. At that time, the ratio of “quaternized product / non-quaternized ester amine” is preferably in the range of a mass ratio of 70/30 to 99/1.

  The compound represented by the general formula (B1-7) (hereinafter “compound (B1-7)”) and the compound represented by the general formula (B1-8) (hereinafter “compound (B1-8)”) are as described above. From the adduct of fatty acid composition, N-methylethanolamine and acrylonitrile, JOrg. Chem. , 26, 3409 (1960), by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized by a known method. In that case, it is preferable to synthesize | combine so that the abundance ratio represented by "compound (B1-7) / compound (B1-8)" may be 99 / 1-50 / 50 by mass ratio. When the quaternized product is used, it is preferable to use methyl chloride as a quaternizing agent, which is expressed as “a quaternized compound (B1-7) / a quaternized compound (B1-8)”. It is preferable to synthesize the abundance ratio such that the mass ratio is 99/1 to 50/50.

In the fiber treatment agent 1 of the present invention, the component (B) has an action of enhancing the adsorption of the component (A), and is blended for imparting flexibility to the treated cloth.
In the fiber treatment agent 1 or the fiber treatment agent 2 of the present invention, the blending amount of the component (B) is not particularly limited, but is preferably 0.01 to 30% by mass with respect to the total mass of the entire composition.
When used for the fiber treatment agent 1 of the present invention, the amount of the component (B) is not particularly limited, but is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, based on the total mass of the entire composition. More preferably, it is 8-22 mass%. When it is 5% by mass or more, a sufficient flexibility imparting effect can be obtained. Storage stability is favorable in it being 30 mass% or less.
When used for the fiber treatment agent 2 of the present invention, the amount of the component (B) is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.03%, based on the total mass of the entire composition. It is -8 mass%, More preferably, it is 0.05-5 mass%.
The mass ratio of the component (A) / component (B) of the present invention is not particularly limited, but when used for the fiber treatment agent 1, it is preferably 1/300 to 2/3, more preferably 1/25 to 2/3, More preferably, it is 1/15 to 2/3, and when used for the fiber treatment agent 2, it is preferably 1/1000 to 1000/1, more preferably 1/80 to 200/1, still more preferably 1/10 to 100. / 1.

[Component (C)]
The component (C) contained in the fiber treatment agent 2 of the present invention is a fragrance composition. Component (C) may be included in the fiber treatment agent 1.
The fragrance composition used in the present invention is a fragrance composition containing at least one fragrance component generally used in a textile product treating agent composition, for example, a textile product finish composition or a softener composition. is there. In general, a softening agent composition such as clothing sets the pH as low as 2 to 3 in order to keep the cationic surfactant contained as a softening base stable. Therefore, the fragrance | flavor component added to a softening agent composition is restricted to the compound which can exist stably even in such low pH. However, the fiber treatment agent 1 of the present invention includes a softener composition as one of its embodiments, but is not limited thereto, and even when the fiber treatment agent 1 is used as a softener composition, Since the perfume component is contained in the fiber treatment agent 2 separately from this, the perfume component can be used without such limitation.
Specific examples of the perfume ingredients having low pH and low stability include methylpample mousse, phenoxyethyl isobutyrate, fluoropearl, allyl amyl glycolate, ligustral and the like. When the pH of the fiber treatment agent 1 is 2 to 3, it is preferable to mix methylpample mousse, phenoxyethyl isobutyrate, fluoropearl, allyl amyl glycolate, and ligustral into the fiber treatment agent 2.
Specific examples of the perfume component are not particularly limited and may be appropriately selected depending on the purpose. For example, aldehydes, phenols, alcohols, ethers, esters, hydrocarbons, ketones, lactones , Musks, fragrances having a terpene skeleton, natural fragrances, animal fragrances and the like.
The aldehydes are not particularly limited and may be appropriately selected depending on the intended purpose. For example, undecylenaldehyde, lauryl aldehyde, aldehyde C-12MNA, miracaldehyde, α-amylcinnamic aldehyde, cyclamenaldehyde, citral Citronellal, ethyl vanillin, heliotropin, anisaldehyde, α-hexylcinnamic aldehyde, octanal, ligustral, lyial, rilal, tripral, vanillin, helional and the like.
There is no restriction | limiting in particular as said phenols, According to the objective, it can select suitably, For example, eugenol, isoeugenol, etc. are mentioned.
The alcohol is not particularly limited and may be appropriately selected depending on the intended purpose.For example, bacdanol, citronellol, dihydromyrcenol, dihydrolinalool, geraniol, linalool, nerol, sandalol, santarex, Examples include terpineol, tetrahydrolinalol, and phenylethyl alcohol.

There is no restriction | limiting in particular as said ether, According to the objective, it can select suitably, For example, cedula bar, glycalva, methyl eugenol, methyl isoeugenol etc. are mentioned.
The esters are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cis-3-hexenyl acetate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, p-cresate. Dil acetate, pt-butyl cyclohexyl acetate, amyl acetate, methyl dihydrojasmonate, amyl salicylate, benzyl salicylate, benzyl benzoate, benzyl acetate, cedryl acetate, citronellyl acetate, decahydro-β-naphthyl acetate, dimethylbenzyl Carvinyl acetate, Ericapropionate, ethyl acetoacetate, Erica acetate, geranyl acetate, geranyl formate, hedion, linalyl acetate, β-phenylethyl acetate Hexyl salicylate, styryl acetate, terpinyl acetate, tiviberyl acetate, ot-butylcyclohexyl acetate, manzanate, allyl heptanoate, and the like.
There is no restriction | limiting in particular as said hydrocarbon, According to the objective, it can select suitably, For example, d-limonene, (alpha) -pinene, (beta) -pinene, myrcene etc. are mentioned.
The ketones are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α-ionone, β-ionone, methyl-β-naphthyl ketone, α-damascon, β-damascon, and δ-damascon. Cis-jasmon, methylionone, allylionone, cashmerelan, dihydrojasmon, iso-Esuper, belt fix, isolone diforanone, coabon, rosephenone, raspberry ketone, dynascon and the like.

The lactone is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include γ-decalactone, γ-undecalactone, γ-nonalactone, γ-dodecalactone, coumarin, and ambroxan. It is done.
There is no restriction | limiting in particular as said musk, According to the objective, it can select suitably, For example, cyclopentadecanolide, ethylene brush rate, galaxolide, musk ketone, tonalid, nitromusk etc. are mentioned.
The fragrance having the terpene skeleton is not particularly limited and may be appropriately selected depending on the intended purpose.For example, geraniol (gelaniol), nerol, linalool, citral, citronellol, menthol, mint, citronellal, myrcene, pinene, Examples include limonene, terpineol, carvone, yonon, camphor, and borneol.
The natural perfume is not particularly limited and may be appropriately selected depending on the intended purpose. For example, orange oil, lemon oil, lime oil, petitgren oil, yuzu oil, neroli oil, bergamot oil, lavender oil, lavandin oil , Abies oil, anise oil, bay oil, bored rose oil, ylang ylang oil, citronella oil, geranium oil, peppermint oil, peppermint oil, spearmint oil, eucalyptus oil, lemongrass oil, patchouli oil, jasmine oil, rose oil, cedar oil , Essential oils such as vetiver oil, galvanum oil, oak moss oil, pine oil, camphor oil, sandalwood oil, mellow oil, turpentine oil, clove oil, clove leaf oil, cassia oil, nutmeg oil, cananga oil, thyme oil, etc. .
There is no restriction | limiting in particular as said animal fragrance | flavor, According to the objective, it can select suitably, For example, a scent, a ghost cat scent, a sea scent incense, a dragon scent, etc. are mentioned.

In the fiber treatment agent 2 of the present invention, it is preferable to use a fragrance composition containing a fragrance component having a ClogP value of 5.0 or less as the component (C), and 10% by mass or more based on the total mass of the fragrance composition, More preferably 30% by mass or more, still more preferably 50% by mass or more, and particularly preferably 70% by mass or more.
Moreover, in the fiber treatment agent 2 of this invention, it is preferable to use the fragrance | flavor composition containing the fragrance | flavor component which has a cyclic structure in a structure as (C) component, and is 10 with respect to the gross mass of a fragrance | flavor composition. It can be contained in an amount of at least 20% by mass, more preferably at least 20% by mass, even more preferably at least 35% by mass, particularly preferably at least 60% by mass.
More preferably, in the fiber treatment agent 2 of the present invention, a fragrance composition containing a fragrance component having a ClogP value of 5.0 or less or having a cyclic structure in the structure is used.
The fragrance component having a ClogP value of 5.0 or less or having a cyclic structure in the structure is 30% by mass or more, more preferably 50% by mass or more, and further preferably 65% by mass with respect to the total mass of the fragrance composition. As mentioned above, it can contain 80 mass% or more especially preferably.
Even more preferably, in the fiber treatment agent 2 of the present invention, a fragrance composition having a ClogP value of 5.0 or less and containing a fragrance component having a cyclic structure is used.
More particularly preferably, in the liquid treatment composition for textiles according to the present invention, a fragrance composition having a ClogP value of 5.0 or less and a fragrance component having a cyclic structure of 20% by mass or more, particularly preferably a ClogP value. Is a fragrance composition containing 5.0% by mass or more of a fragrance component having a cyclic structure.
The cyclic structure referred to here may be, for example, a hydrocarbon ring structure or a heterocyclic structure, which may be monocyclic or polycyclic, and may be a condensed polycyclic structure, a bridged ring structure, a spiro structure, or the like. It may be a ring structure, a saturated ring structure or an unsaturated ring structure. Examples of the hetero atom contained in the heterocycle include O, S, N, and P.

Specific examples of the cyclic structure include monocyclic compounds such as benzene and condensed ring compounds such as naphthalene. Further, the element forming the cyclic structure may be a carbocyclic compound or a heterocyclic compound. The ring size may be a 5-membered ring compound such as cyclopentane or furan, a 6-membered ring compound such as cyclohexane or benzene, or the like.
In the fiber treatment agent 2 of the present invention, as a fragrance component in the component (C) that is preferably used, specifically, ISOEsuper (ClogP4.7, with a cyclic structure), ethyl vanillin (ClogP1.8, Cyclic structure), γ-undecalactone (ClogP3.8, with cyclic structure), eugenol (ClogP2.4, with cyclic structure), β damascon (ClogP4.7, with cyclic structure), helional (ClogP1. 4, with cyclic structure), benzyl salicylate (ClogP4.2, with cyclic structure), cachemelan (ClogP4.0, with cyclic structure), coumarin (ClogP1.4, with cyclic structure), dimethylbenzylcarbinyl acetate (ClogP1.9, with cyclic structure), terpineol (ClogP2.6, with cyclic structure), damasenone (ClogP4.3, with cyclic structure), tripral (ClogP2.4, with cyclic structure), phenylethyl alcohol (ClogP1.2, with cyclic structure), hexyl Synthetic aldehyde (ClogP4.9, with cyclic structure), β-ionone (ClogP3.8, with cyclic structure), Hedion (ClogP2.4, with cyclic structure), Beltfix (ClogP5.0, with cyclic structure) ), Methylionone (ClogP4.2, with a cyclic structure), limonene (ClogP4.4, with a cyclic structure), lilar (ClogP2.2, with a cyclic structure), lilial (ClogP3.9, with a cyclic structure), Examples include phenoxyethyl isobutyrate (ClogP3.0, with a cyclic structure), fluoropearl (ClogP3.1, with a cyclic structure), ligustral (ClogP2.9, with a cyclic structure) and the like. The fragrance | flavor component made is not limited to this. More preferred are isoether super, ethyl vanillin, γ undecalactone, eugenol, β damascone, helional, benzyl salicylate, phenoxyethyl isobutyrate, fluoropearl, and ligustral. More preferred are eugenol, β damascone, helional, benzyl salicylate, phenoxyethyl isobutyrate, fluoropearl and ligustral.

The ClogP value is a value representing a 1-octanol / water partition coefficient P representing a ratio of equilibrium concentrations in 1-octanol and in water in the form of logarithmic logP with respect to the base 10 for a chemical substance. The ClogP value can be determined by decomposing the chemical structure of a compound into its constituents by the f-value method (hydrophobic fragment constant method) and integrating the hydrophobic fragment constants and f values possessed by each fragment (for example, Clog 3 Reference Manual Daylight Software 4.34, Albert Leo, David Weininger, Version 1, March 1994).
In general, since the fragrance is more hydrophobic as the ClogP value is larger, the fragrance composition containing more fragrance components having a smaller ClogP value is more hydrophilic than the fragrance composition containing more fragrance components having a larger ClogP value. You can say that.
In the fiber treatment agent 2 of the present invention, a fragrance component having a ClogP value of 1.0 or more and 8.0 or less is 30% by mass with respect to the total mass of the fragrance composition, from the viewpoint of fresh fragrance and palatability. More preferably, the content is 45% by mass or more, more preferably 50% by mass or more, particularly preferably 80% by mass or more, and still more preferably 90% by mass or more.

In the fragrance composition used in the present invention, a solvent generally used for a textile product treating agent composition, for example, a textile product finishing composition or a softener composition, may be blended. Examples of the fragrance solvent include acetin (triacetin), MMB acetate (3-methoxy-3-methylbutyl acetate), sucrose diacetate hexaisobutyrate, ethylene glycol dibutyrate, hexylene glycol, dibutyl sebacate, deltil extra ( Isopropyl myristate), methyl carbitol (diethylene glycol monomethyl ether), carbitol (diethylene glycol monoethyl ether), TEG (triethylene glycol), benzyl benzoate (BB), propylene glycol, diethyl phthalate, tripropylene glycol, aborin ( Dimethyl phthalate), deltyl prime (isopropyl palmitate), dipropylene glycol (DPG), farnesene, dioctyl adipate Tributyrin (glyceryl tributanoate), hydrolite-5 (1,2-pentanediol), propylene glycol diacetate, cetyl acetate (hexadecyl acetate), ethyl abiate, avaline (methyl abieticate), citroflex A-2 (Acetyl triethyl citrate), citroflex A-4 (tributyl acetyl citrate), citroflex no. 2 (triethyl citrate), Citroflex No. 4 (tributyl citrate), Durafix (methyl dihydroabietate), MITD (isotridecyl myristate), polylimonene (limonene polymer), 1,3-butylene glycol and the like.
Although these solvents are mix | blended, for example in 0.1-30 mass% in a fragrance | flavor composition, Preferably 1-20 mass% is mix | blended.
In the present invention, the blending amount of the component (C) is not particularly limited, but when used for the fiber treatment agent 1, it is preferably 0.01 to 5% by mass, more preferably 0.1 to 5%, based on the total mass of the fiber treatment agent 1. It is 0.5 mass%, More preferably, it is 0.5-3 mass%. When using it for the fiber treatment agent 2, Preferably it is 0.001-1 mass% with respect to the total mass of the fiber treatment agent 2, More preferably, it is 0.005-1 mass%, More preferably, it is 0.01-0.5 mass%. When the blending amount of the component (C) is less than 0.001% by mass, the aroma is weak and it is difficult to understand the effect of improving the residual fragrance. When the blending amount of the component (C) is more than 5% by mass, the storage stability at high temperature may be lowered.

[Optional ingredients]
The fiber treatment agent 1 and the fiber treatment agent 2 of the present invention may contain components other than the above-described components (A) to (C) as necessary, as long as the effects of the present invention are not impaired.
As this other component, a well-known component can be suitably mix | blended in the liquid processing agent composition for textiles. For example, water; nonionic surfactant; amphoteric surfactant; semipolar surfactant; anionic surfactant; silicone; water-soluble solvent; dye and / or pigment; preservative; An acid or a salt thereof; a stabilizer such as calcium chloride can be contained.
The fiber treatment agent 1 and the fiber treatment agent 2 of the present invention are preferably aqueous compositions and preferably contain water.
As water, any of tap water, ion exchange water, pure water, distilled water, and the like can be used. Of these, ion-exchanged water is preferred.

The nonionic surfactant is preferably used mainly for the purpose of improving the emulsion dispersion stability of the oil-soluble component in the emulsion when the fiber treatment agent 1 and the fiber treatment agent 2 of the present invention are emulsions. obtain. In particular, when a nonionic surfactant is blended, a sufficient level of freeze / restoration stability is easily secured in terms of commercial value.
As the nonionic surfactant, for example, those derived from higher alcohols, higher amines or higher fatty acids can be used. More specifically, polyoxyethylene alkyl ethers and polyoxyethylene fatty acid alkyls having an alkyl group or alkenyl group having 10 to 22 carbon atoms and an average addition mole number of ethylene oxide of 8 to 100 mol (carbon of the alkyl) 1 to 3) ester; polyoxyethylene alkylamine having an average addition mole number of ethylene oxide of 10 to 100 mol, alkyl polyglucoside having an alkyl group or alkenyl group having 8 to 18 carbon atoms, and an average addition mole number of ethylene oxide. Examples include hydrogenated castor oil that is 10 to 100 mol. Among these, a polyoxyethylene alkyl ether having an alkyl group having 10 to 18 carbon atoms and an average added mole number of ethylene oxide of 8 to 80 mol is preferable.
The content of the nonionic surfactant in the fiber treatment agent 1 and the fiber treatment agent 2 of the present invention can be determined according to the desired function, for example, preferably 0.01 to 10% by mass, more preferably 0.8. 1-8 mass%, More preferably, it is 0.5-5 mass%. When the content of the nonionic surfactant is equal to or higher than the lower limit, the emulsion dispersion stability of the oil-soluble component in the emulsion and the freeze recovery stability of the emulsion are further improved. If it is below an upper limit, the raise of the viscosity of the fiber processing agent 1 and the fiber processing agent 2 can be suppressed, and it can be made favorable in terms of usability.
The amphoteric surfactant is an N-alkyl-N, N-dimethyl-N- (2-hydroxy-3-sulfopropyl) ammonium betaine having an alkyl group having 10 to 24 carbon atoms, an alkyl group having 10 to 24 carbon atoms. N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine, N-alkanoylaminopropyl-N, N-dimethyl-N- (2-hydroxy-3-sulfo having an alkanoyl group having 10 to 24 carbon atoms Propyl) ammonium betaine, N-alkanoylaminopropyl-N, N-dimethyl-N-carboxymethylammonium betaine having an alkanoyl group having 10 to 24 carbon atoms, and the like. The content of the amphoteric surfactant is preferably 0.01 to 10% by mass with respect to the total mass of the fiber treatment agent.
Examples of the semipolar surfactant include alkyldimethylamine oxide having an alkyl group having 10 to 24 carbon atoms, alkanoylamidopropyldimethylamine oxide having an alkanoyl group having 10 to 24 carbon atoms, and the like. The content of the amphoteric surfactant or the semipolar surfactant is preferably 0.01 to 10% by mass with respect to the total mass of the fiber treatment agent.
The anionic surfactant is an alkylbenzene sulfonate having an alkyl group having 10 to 15 carbon atoms, an alkyl sulfate ester salt having an alkyl group having 10 to 24 carbon atoms, an α-olefin sulfonate having 10 to 24 carbon atoms, Examples include α-sulfo fatty acid methyl ester salts having 10 to 24 carbon atoms of fatty acids, polyoxyethylene alkyl sulfate salts having an alkyl group having 10 to 24 carbon atoms and an oxyethylene group having 1 to 6 number average added moles. be able to. Among these, alkylbenzene sulfonates having an alkyl group having 10 to 15 carbon atoms are preferable. The content of the anionic surfactant is preferably 0.01 to 25% by mass with respect to the total mass of the fiber treatment agent.

There is no restriction | limiting in particular in the kind of a silicone compound, According to the objective, it can select suitably. The molecular structure of the silicone compound may be linear, branched, or cross-linked. The silicone compound may be a modified silicone compound, and the modified silicone compound may be modified with one organic functional group or modified with two or more organic functional groups. It may be.
The silicone compound can be used in the state of oil, and can also be used in the state of an emulsion dispersed by any emulsifier.
Specific examples of the silicone compound include, for example, dimethyl silicone, polyether modified silicone, methylphenyl silicone, alkyl modified silicone, higher fatty acid modified silicone, methyl hydrogen silicone, fluorine modified silicone, epoxy modified silicone, carboxy modified silicone, carbinol. Examples thereof include modified silicone and amino-modified silicone.
Among these, polyether-modified silicone, amino-modified silicone, dimethyl silicone and the like are preferable from the viewpoint of versatility and deodorizing and deodorizing effect, and polyether-modified silicone and amino are particularly preferable from the viewpoint of effect and handling during production. Modified silicone is preferred.
Specific examples of the polyether-modified silicone include, for example, a copolymer of alkylsiloxane and polyoxyalkylene. In addition, as carbon number of the alkyl group of the said alkylsiloxane, 1-3 are preferable, and as carbon number of the alkylene group of the said polyoxyalkylene, 2-5 are preferable. Among these, the polyether-modified silicone is preferably a copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, a random or block copolymer of ethylene oxide and propylene oxide, etc.). Specific examples of such a polyether-modified silicone include, for example, a compound represented by the following general formula (I), a compound represented by the following general formula (II), and the like.

In the general formula (I), M, N, a, and b represent the average degree of polymerization, and R represents hydrogen or an alkyl group. Here, M is preferably 10 to 10,000, and more preferably 100 to 300. N is preferably 1 to 1,000, and more preferably 1 to 100. Furthermore, it is preferable that M> N. a is preferably 2 to 100, and more preferably 2 to 50. b is preferably 0 to 50, and more preferably 0 to 10. R is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
The polyether-modified silicone represented by the general formula (I) generally has an organohydrogenpolysiloxane having a Si-H group and a carbon-carbon double bond such as polyoxyalkylene allyl ether at the terminal. It can be produced by addition reaction of polyoxyalkylene alkyl ether with a platinum catalyst. Therefore, the polyether-modified silicone may contain a slight amount of unreacted polyoxyalkylene alkyl ether or organohydrogenpolysiloxane having a Si—H group. Since the organohydrogenpolysiloxane having a Si—H group has high reactivity, the abundance in the polyether-modified silicone is preferably 30 ppm or less (as the amount of Si—H).

In the general formula (II), 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, and 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 linear polysiloxane-polyoxyalkylene block copolymer represented by the general formula (II) has a polyoxyalkylene compound having a reactive terminal group and a terminal group that reacts with the reactive terminal group of the compound. It can be produced by reacting with dihydrocarbylsiloxane. Such polyether-modified silicone has a longer side chain polyoxyalkylene chain, and the higher the degree of polymerization of the polysiloxane chain, the higher the viscosity. Therefore, it is easy to improve workability during production and blend into aqueous compositions. Therefore, it is preferable to use it in the form of a premix with a water-soluble organic solvent. Examples of the water-soluble organic solvent include ethanol, dipropylene glycol, butyl carbitol and the like.

More specifically, examples of the polyether-modified silicone include SH3772M, SH3775M, FZ-2166, FZ-2120, L-720, SH8700, L-7002, and L-, manufactured by Toray Dow Corning Co., Ltd. 7001, SF8410, FZ-2164, FZ-2203, FZ-2208, manufactured by Shin-Etsu Chemical Co., Ltd., KF352A, KF615A, X-22-6191, X-22-4515, KF-6012, KF-6004, etc. Examples include TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, and TSF4460 manufactured by Momentive Performance Materials Japan GK.
The amino-modified silicone is a silicone oil in which an amino group is introduced into the terminal or side chain of the dimethyl silicone skeleton, and a substituent such as a hydroxyl group, an alkyl group, or a phenyl group may be substituted in addition to the amino group. Moreover, the form of oil may be sufficient, and the form of the amino modified silicone emulsion which emulsified the nonionic surfactant or the cationic surfactant as an emulsifier may be sufficient. A preferred amino-modified silicone oil or base oil in the case of an emulsion is represented by the following general formula (III).

In formula (III), R ₁ and R ₆ may be the same as or different from each other and each represents a methyl group, a hydroxyl group, or hydrogen. R ₂ represents any _one of — (CH ₂ ) _n —A ₁ and — (CH ₂ ) _n —NHCO— (CH ₂ ) _m —A ₁ . A ₁ represents any _one of —N (R ₃ ) (R ₄ ) and —N ⁺ (R ₃ ) (R ₄ ) (R ₅ ) · X ⁻ . R _{3 to} R ₅ may be the same or different from each other, and are any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, and — (CH ₂ ) _n —NH ₂ . Represents. X ⁻ represents any one of fluorine ion, chlorine ion, bromine ion, iodine ion, methyl sulfate ion, and ethyl sulfate ion. The values of m and n may be the same as or different from each other, and represent an integer of 0 to 12. The values of p and q represent the degree of polymerization of the polysiloxane and may be the same or different from each other. p is 0 to 20000, preferably 10 to 10000, q is 1 to 500, preferably 1-100 are represented.
For amino-modified silicone oil used in the fiber treatment agent of the present invention preferably has a kinematic viscosity at 25 ° C. is 50~20000mm ² / s, more preferably 100~10000mm ² / s. When the kinematic viscosity is in this range, a high texture imparting effect is exhibited, manufacturability is good, and the composition is easy to handle, which is preferable.
Commercially available amino-modified silicones can be used. For example, amino-modified silicone oils sold by Toray Dow Corning Co., Ltd. as SF-8417, BY16-892, BY16-890. From Shin-Etsu Chemical Co., Ltd., KF-864, KF-860, KF-8004, KF-8002, KF-8005, KF-867, KF-861, KF-880, KF-867S and the like can be mentioned.

The amino-modified silicone emulsion type is sold by Toray Dow Corning Co., Ltd. as SM8904, BY22-079, FZ-4671, FZ-4672, and sold by Shin-Etsu Chemical Co., Ltd. in the Polon series. Polon MF-14, Polon MF-29, Polon MF-14D, Polon MF-44, Polon MF-14EC, Polon MF-52, sold by Asahi Kasei Wacker Silicone Co., Ltd., WACKER FC201, WACKER FC218 Can be given.
The kinematic viscosity of the dimethyl silicone is not particularly limited but is preferably 1~100,000,000mm ² / s, more preferably ^{10~10,000,000mm 2 / s, 100~1,000,000mm 2 /} s Is more preferable. Further, it may be an oil or an emulsion.

The fiber treatment agent of the present invention preferably contains a water-soluble solvent in addition to water.
The water-soluble solvent is preferably one or more selected from the group consisting of lower (1 to 4 carbon atoms) alcohols, glycol ether solvents, and polyhydric alcohols. Specifically, ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, dipropylene glycol monomethyl ether, and water represented by the following general formula (X) It is preferable to mix | blend the solvent component chosen from an ionic solvent.
^{_{R 11 -O- (C 2 H 4}} O) y - (C 3 H 6 O) z -H ··· (X)
In the formula, R ¹¹ is an alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms. y and z are average addition mole numbers, y is 1-10, Preferably it is 2-5, z shows the number of 0-5, Preferably it is 0-2.
Among the above-mentioned water-soluble solvents, ethanol, ethylene glycol, butyl carbitol, propylene glycol, diethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether are preferable.
The water-soluble solvent is preferably added to the fiber treatment agent of the present invention in an amount of 0 to 30% by mass, more preferably 0.01 to 25% by mass, and still more preferably 0.1 to 20% by mass.

The dye and / or pigment can be blended for the purpose of improving the appearance of the liquid treating agent composition for textiles of the present invention. Preferably, it is one or more of red, blue, yellow or purple water-soluble dyes selected from acid dyes, direct dyes, basic dyes, reactive dyes, and mordant / acid mordant dyes.
Specific examples of the dyes that can be added are described in the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, published on July 20, 1970, Maruzen Co., Ltd.).
From the viewpoint of the storage stability of the fiber composition treating agent composition of the present invention and the dyeing property to fibers, the composition has at least one functional group selected from a hydroxyl group, a sulfonic acid group, an amino group, and an amide group in the molecule. Acid dyes, direct dyes, and reactive dyes are preferable, and the blending amount thereof is preferably 1 to 50 ppm, more preferably 1 to 30 ppm, based on the entire composition.
Examples of the dye used in the liquid treatment composition for textile products of the present invention include JP-A-6-123081, JP-A-6-123082, JP-A-7-18573, JP-A-8-27669, It is also possible to use dyes described in JP-A-9-250085, JP-A-10-77576, JP-A-11-43865, JP-A-2001-181972, JP-A-2001-348784, etc. it can.

The preservative can be used mainly in the fiber treatment agent of the present invention in order to enhance the antiseptic and sterilizing power and maintain the antiseptic property during long-term storage.
Examples of the preservative include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, and the like.
Examples of isothiazolone organic sulfur compounds include 5-chloro-2-methyl-4-isothiazoline-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, or a mixture thereof. Among them, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferable, and 5-chloro-2-methyl-4-isothiazolin-3-one and 2- A mixture of methyl-4-isothiazolin-3-one is more preferred, and a mixture of about 77% by weight of the former and about 23% by weight of the latter is particularly preferred.
Examples of benzisothiazolone-based organic sulfur compounds include 1,2-benzisothiazoline-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and dithio-2,2-bis ( Benzmethylamide) or a mixture thereof. Among these, 1,2-benzisothiazolin-3-one is particularly preferable.
Examples of benzoic acids include benzoic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, benzyl paraoxybenzoate, and the like.
In the fiber treatment agent of the present invention, the blending amount of the preservative is preferably 0.0001 to 1% by mass with respect to the total amount of the fiber treatment agent. When the blending amount of the preservative is less than the lower limit, it is difficult to obtain the effect of adding the preservative, and when it exceeds the upper limit, the storage stability may be lowered.

An ultraviolet absorber is a chemical | medical agent with the effect which protects an ultraviolet-ray, it is a component which absorbs an ultraviolet-ray, converts into infrared rays, visible light, etc., and discharge | releases.
Examples of the ultraviolet absorber include aminobenzoic acid derivatives such as p-aminobenzoic acid, ethyl p-aminobenzoate, glyceryl p-aminobenzoate, and amyl p-dimethylaminobenzoate; ethylene glycol salicylate, dipropylene glycol salicylate , Salicylic acid derivatives such as octyl salicylate, myristyl salicylate; methyl diisopropylcinnamate, ethyl p-methoxycinnamate, isopropyl p-methoxycinnamate, p-methoxycinnamate-2-ethylhexyl, p-methoxycinnamic acid Cinnamic acid derivatives such as butyl; benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and 2,2′-dihydroxy-4-methoxybenzophenone; urocanic acid, Ouro Examples include azole compounds such as ethyl kanate; 4-t-butyl-4′-methoxybenzoylmethane.

The antibacterial agent is a component having an effect of suppressing the growth of bacteria on the fiber and further suppressing the generation of an unpleasant odor derived from the degradation product of the microorganism.
As the antibacterial agent, for example, in addition to the component (B), a cationic fungicide such as a quaternary ammonium salt (benzalkonium chloride), diclosan, triclosan, bis- (2-pyridylthio-1-oxide) zinc, poly Examples include hexamethylene biguanidine hydrochloride, 8-oxyquinoline, polylysine and the like.
An aminocarboxylic acid or a salt thereof is a compound containing at least one amino group and one carboxy group in one molecule.
Examples of aminocarboxylic acids or salts thereof include methylglycine diacetate (MGDA), aspartate diacetate (ASDA), isoserine diacetate (ISDA), β-alanine diacetate (ADAA), serine diacetate (SDA), and glutamate diacetate. (GLDA), iminodisuccinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA), triethylenetetra Amine hexaacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA-OH), hydroxyethyleneiminodiacetic acid (HIDA), dihydroxyethyl group Shin (DHEG), glycol ether diaminetetraacetic acid (GEDTA), dicarboxylate methyl glutamate (CMGA), (S, S) - ethylenediamine disuccinic acid (EDDS) and salts thereof, and the like.
In addition to the above-mentioned compounds, as a function improver, a shrinkage inhibitor, an anti-wrinkle agent, a shape retention agent, a drape retention agent, an iron property improvement agent, an oxygen bleaching inhibitor, a whitening agent, a whitening agent, and a fabric softening Clay, antistatic agent, dye transfer inhibitor such as polyvinylpyrrolidone, polymer dispersant, stain remover, scum dispersant, 4,4-bis (2-sulfostyryl) biphenyl disodium (Cino Pearl CBS manufactured by Ciba Specialty Chemicals) X) fluorescent whitening agents, dye fixing agents, anti-fading agents such as 1,4-bis (3-aminopropyl) piperazine, stain removers, fiber surface modifiers such as cellulase, amylase, protease, lipase, keratinase, etc. Silk protein powders and surface modified products that can give silk texture and functions such as There are emulsified dispersions, specifically K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (upper hair) Anti-contamination of SILKGEN G Solvel S (Ichimaru Falcos), alkylene terephthalate and / or nonionic polymer compound comprising alkylene isophthalate unit and polyoxyalkylene unit, such as FR627 manufactured by Kyoyo Chemical Industry, SRC-1 manufactured by Clariant Japan An agent or the like can be blended.

[PH of composition]
The pH of the fiber treatment agent of the present invention is not particularly limited, but the fiber treatment agent 1 has a pH of 1 to 6 at 25 ° C. from the viewpoint of suppressing hydrolysis of the component (B) accompanying storage aging. It is preferable to be within the range, and it is more preferable to be within the range of 2 to 4.
In the fiber treatment agent 2 of the present invention, the pH at 25 ° C is preferably 5 to 11 and more preferably 7 to 10 from the viewpoint of enhancing the stability of the aroma.
When adjusting pH, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, p-toluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethane diphosphonic acid, phytin PH adjusting agents such as acids, short-chain amine compounds such as ethylenediaminetetraacetic acid and dimethylamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates and alkali metal silicates can be used.

[Viscosity of composition]
The viscosity of the fiber treatment agent of the present invention is not particularly limited, but the fiber treatment agent 1 is preferably less than 1000 mPa · s (B-type viscometer, manufactured by TOKIMEC, 25 ° C., the same applies hereinafter). Considering the increase in viscosity due to storage aging, the viscosity immediately after production is more preferably less than 800 mPa · s, and further preferably less than 500 mPa · s. When it is in such a range, the usability such as handling property at the time of loading into the washing machine is good.
The fiber treatment agent 2 of the present invention has a viscosity at 25 ° C. of preferably 10 mPa · s or less, and more preferably 5 mPa · s or less, from the viewpoint of handling properties.

[Production method]
The method for preparing the fiber treatment agent 1 and the fiber treatment agent 2 of the present invention is not particularly limited.
When the fiber treatment agent 1 is a liquid softener composition, it can be produced by a known method, for example, a method similar to the conventional method for producing a liquid softener composition using a cationic surfactant as a main agent.
For example, an emulsion is prepared by mixing an oil phase containing the component (B) and a nonionic surfactant and an aqueous phase under temperature conditions equal to or higher than the melting point of the component (B), and then, if necessary. It can be produced by adding and mixing other components to the obtained emulsion. The oil phase can be prepared by mixing the component (B), the nonionic surfactant and, if necessary, an optional component at a temperature equal to or higher than the melting point of the component (B). The aqueous phase can be prepared by mixing water and optional components as necessary.
When the fiber treatment agent 2 is a spray-type fiber treatment agent, it is not particularly limited and can be prepared according to a conventional method. For example, it can prepare by mixing each said component with water as needed.

[Treatment methods and applications of textile products]
The fiber product treatment method of the present invention is a method of treating a fiber product with the fiber treatment agent 1 and then treating with the fiber treatment agent 2 through a dehydration step. Dehydration is a process of dehydrating the treatment liquid from the textile product. For example, it can be carried out by a dehydration step performed in ordinary laundry at home. The dehydration does not need to be performed completely, and may contain water up to about 120% by mass or less based on the dried clothes. A step of drying may be included between the step of dehydrating and the treatment of the fiber treatment agent 2. After the fiber product is treated with the fiber treatment agent 1, the fiber product is dehydrated and dried, and the dried fiber product is treated with the fiber treatment agent 2. After the fiber product is treated with the fiber treatment agent 1, it is dehydrated and wet. A method of treating the fiber product in a wet state with the fiber treatment agent 2 is preferable. More preferably, the fiber product is treated with the fiber treatment agent 1 and then dehydrated, and the wet fiber product is treated with the fiber treatment agent 2. The preferable moisture content of the wet textile product (the percentage of water contained in the dry total mass of the textile product expressed as a percentage) is 20 to 120% by mass, preferably 30 to 110% by mass. %, More preferably 40 to 100% by mass. The dry state of the fiber product is defined as a fiber product left for 24 hours under the condition of 20 ° C. and 45% RH, and the dry mass of the fiber product is 24 hours under the condition of 20 ° C. and 45% RH. It is defined as the mass of the left textile product.

The uses of the fiber treatment agent 1 and the fiber treatment agent 2 of the present invention are not particularly limited.
The fiber treatment agent 1 can be applied to a detergent composition, a bleaching agent composition, a liquid softener composition, a spray fiber treatment agent, and the fiber treatment agent 2 can be applied to a spray fiber treatment agent. Especially, it is preferable to apply the fiber treatment agent 1 as a liquid softening agent composition and the fiber treatment agent 2 as a spray type fiber treatment agent.
The method for treating textile products such as clothing with the fiber treatment agent 1 and the fiber treatment agent 2 of the present invention is not particularly limited, and conventionally known detergents, finishing agents (softeners, glues, etc.), spray type It can process similarly to a fiber processing agent etc.
In the case of a liquid softener composition, the fiber treatment agent 1 of the present invention is not particularly limited in the method of use. For example, in the rinsing stage of washing, the composition of the present invention is dissolved in water for treatment. Alternatively, there is a method in which the composition of the present invention is dissolved in water using a container such as a tub, and further garment is added to dip treatment. In that case, the solution is diluted to an appropriate concentration. In that case, the bath ratio (weight ratio of the treatment liquid to the textile product) is preferably 3 to 100 times, particularly preferably 5 to 50 times. Specifically, when performing the flexible treatment, it is preferably used in such an amount that the concentration of the component (C) is 0.01 ppm to 1000 ppm, more preferably 0.1 ppm to 300 ppm with respect to the total amount of water used. Is used in such an amount.
When the fiber treatment agent 2 of the present invention is used as a spray-type fiber treatment agent composition, the method of use is not particularly limited. For example, the treatment agent is accommodated in a trigger spray container or a dispenser type pump spray container, This can be done by spraying directly on the textile. After spraying, you may perform a drying process as needed. The fiber product is not particularly limited, and examples thereof include clothing, curtains, sofas, carpets, towels, handkerchiefs, sheets, and macula covers. The material may also be natural fibers such as cotton, silk, and wool, or chemical fibers such as polyester. The amount of the treatment composition applied to the fiber product is preferably 0.5 to 10 g, more preferably 1 to 5 g, per 100 g of the fiber product.
The spray type fiber treatment agent is preferably contained in a trigger type spray container (hereinafter referred to as trigger container). The trigger container is not particularly limited, and is generally the same as the trigger container used for the fiber treatment product used for imparting a scent or deodorizing effect to a textile product such as clothing. Can be used. As the trigger container used in the present invention, an accumulator type trigger container is preferable from the viewpoints of good spray properties and spray pattern and no occurrence of afterdraw. Further, the amount of spraying once is 0 from the viewpoint of preventing the fiber product sprayed with the treating agent composition from causing stains and giving a preferable effect without giving the hand excessive fatigue. It is preferable that it is 2-0.6g.

[(A) component]
A-1: Cluster dextrin (registered trademark, manufactured by Glico Nutrition Foods Co., Ltd.)
A-2 (comparative example): Hydroxypropyl-β-cyclodextrin (trade name Celdex HP-β-CD, manufactured by Nippon Food Chemical Co., Ltd.)

[Component (B)]
B-1: Cationic surfactant (cationic surfactant described in Example 4 of JP-A-2003-12471)
B-2: Cationic surfactant (cationic surfactant described in Example 1 of JP-A-2002-167366)
B-3: Didecyldimethylammonium salt (trade name: ARCARD 210, Lion Akzo)

[Other optional ingredients]
D-1:
・ Primary isotridecyl alcohol ethylene oxide 60 mol adduct: 2.5%
・ Calcium chloride (trade name: granular calcium chloride, Tokuyama Corporation): 0.5%
-Isothiazolone solution (trade name: Caisson CG-ICP, Dow Chemical): 100 ppm ^*
D-2:
Polyoxyethylene lauryl ether ethylene oxide 8 mol adduct (trade name: New Coal 1100, Japanese emulsifier): 0.2%
・ Isothiazolone solution (trade name: Caisson CG-ICP, Dow Chemical) 100 ppm <sup>*
* The</sup> amount of isothiazolone solution is shown as it is.
“%” Is mass% and is a value based on the total mass of each of the fiber treatment agent 1 and the fiber treatment agent 2.

[Method for Preparing Fiber Treatment Agent 1]
The amount of each component was adjusted as described in Table 2 below, and a fiber treating agent 1 was prepared by the following procedure. In addition, the numerical value in a table | surface is the mass%, and is based on the total mass of the fiber processing agent 1. FIG.
The fiber treatment agent 1 was prepared by the following procedure using a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation). First, the component (B) and the optional primary isotridecyl alcohol ethylene oxide 60 mol adduct, and the fiber treating agent 1-6 were mixed and stirred together with the component (C) to obtain an oil phase mixture. On the other hand, the component (A) and the isothiazolone liquid which is an optional component were dissolved in purified water for balance to obtain an aqueous phase mixture. Here, the mass of the ion-exchange water for balance is equivalent to the balance obtained by subtracting the total mass of the oil phase mixture and (A) from 980 g. Next, the oil phase mixture heated above the melting point of the component (B) is placed in a glass container and stirred, and the aqueous phase mixture heated above the melting point of the component (B) is added in two portions. And stirred. Here, the division ratio of the aqueous phase mixture was 30:70 (mass ratio), and the stirring was performed at a rotational speed of 1,000 rpm for 3 minutes after the first aqueous phase mixture addition and for 2 minutes after the second aqueous phase mixture addition. It was. Thereafter, calcium chloride as an optional component is added, and if necessary, hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) is added in an appropriate amount to adjust the pH to 2.5. Then, ion-exchanged water was added so that the total mass became 1,000 g, and the target fiber treating agent 1 was obtained. It was 20 mPa * s when the viscosity at 25 degrees C of the fiber processing agent 1 was measured using the B-type viscosity meter (TOKIMEC company).

[Method for Preparing Fiber Treatment Agent 2]
The amount of each component was adjusted as shown in Table 3 below, and a fiber treating agent 2 was prepared according to the following procedure. In addition, the numerical value in a table | surface is the mass%, and is based on the total mass of the fiber processing agent 2. FIG.
Using a 500 ml beaker, a solution in which component (C) was dissolved in ethanol as an optional component, and ion-exchanged water in which the optional component was dissolved therein were added under stirring conditions. Thereafter, if necessary, hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) is added in an appropriate amount to adjust to pH 5.0, and the total mass is further adjusted to 400 g. Ion exchange water was added so that the desired fiber treating agent 2 was obtained. It was 5 mPa * s when the viscosity at 25 degrees C of the fiber processing agent 2 was measured using the B-type viscosity meter (TOKIMEC company).

[Evaluation of residual fragrance]
1. Pretreatment of cotton knitted fabric for evaluation As a pretreatment, two pieces of commercial cotton knitted fabric (100% cotton, Tanigami Shoten) cut into 10cm x 10cm with the commercial detergent "Top Platinum Clear" (manufactured by Lion) The following pretreatment was performed three times using a type washing machine (VH-30S manufactured by Toshiba).
Pretreatment: Standard detergent usage, 30 times the bath ratio, washing with tap water at 45 ° C. for 10 minutes, followed by two cycles of 10 minutes of water rinsing.

2. Processing method It processed using the fiber processing agent 1 prepared as mentioned above, dehydrated for 1 minute, and was dried. The dried cotton knitted fabric was filled with the fiber treatment agent 2 prepared as described above in a trigger container, sprayed, and dried.
After drying, the fragrance strength of the treated fabric (cotton knitted fabric) after being stored for 30 days under the conditions of 20 ° C. and 60 RH was subjected to sensory evaluation in accordance with the following 6-step odor intensity display method. Based on the average score of 10 professional panelists (calculated to the first decimal place), fragrance persistence was determined according to the following criteria. In terms of product value, ○ or more was considered acceptable.
The treatment with Textile Treatment Agent 1 was carried out using a two-tank washing machine (VH-30S manufactured by Toshiba) (compared to 1.5 kg of cotton knitted fabric, 10 mL of composition, 15 times the bath ratio, using tap water at 25 ° C) ).
The treatment with Textile Treatment Agent 2 is a trigger container, and the contents of a commercial clothing care product (trade name “Style Guard wrinkles and odors are refreshing spray”, manufactured by Lion Co., Ltd.) are taken out, washed thoroughly, and firmly Prepared the dried water. Fill the trigger container with the spray-type fiber treatment agent composition and equalize the amount of 2% owf (= weight of the treatment agent composition (g) / weight of the treatment cloth (g) × 100) with respect to the evaluation cloth. Sprayed.

<6-level odor intensity display method>
0: Odorless 1: A scent that can be finally detected 2: A scent that understands what scent 3: A scent that can be easily detected 4: A strong scent 5: A strong scent

<Criteria>
◎◎◎: 3.0 points or more ◎◎: 2.9 to 2.5 points ◎: 2.4 to 2.0 points ○: 1.9 to 1.5 points △: 1.4 to 1.0 points ×: 0.9 point or less

Claims (5)

Step 1: After treating a fiber product with a fiber treatment agent 1 containing (A) a highly branched cyclic dextrin and (B) a cationic surfactant or an amine compound,
Step 2: dehydrate,
Step 3: A method for treating a textile product, comprising the step of treating the dehydrated textile product with (C) a fiber treatment agent 2 containing a fragrance composition ,
The component (A) used for the fiber treatment agent 1 is a glucan having an inner branched ring structure portion and an outer branch structure portion, and having a polymerization degree in the range of 50 to 10,000, wherein the inner branch ring structure portion Is a cyclic structure portion formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond, and the outer branched structure portion is an acyclic structure portion bonded to the inner branched cyclic structure portion. Said method.   The method for treating a textile product according to claim 1, wherein the component (A) used in the fiber treatment agent 1 is contained in an amount of 0.01 to 10% by mass based on the total mass of the fiber treatment agent 1. The method for treating a textile product according to claim 1 or 2 , wherein the component (C) used for the fiber treatment agent 2 contains a fragrance component having a CLogP value of 5.0 or less or a fragrance component having a cyclic structure in the structure. The (B) component used for the fiber treating agent 1 is an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms, which may be separated by an ester group or an amide group, a salt thereof or 4 The method for treating a textile product according to any one of claims 1 to 3 , which is a cationic surfactant selected from a graded product. A fiber treatment agent 1 containing (A) a highly branched cyclic dextrin and (B) a cationic surfactant or an amine compound;
(C) a fiber product treatment agent kit comprising at least a fiber treatment agent 2 containing a fragrance composition, each of which is contained in a separate container ,
The component (A) used for the fiber treatment agent 1 is a glucan having an inner branched ring structure portion and an outer branch structure portion, and having a polymerization degree in the range of 50 to 10,000, wherein the inner branch ring structure portion Is a cyclic structure portion formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond, and the outer branched structure portion is an acyclic structure portion bonded to the inner branched cyclic structure portion. The kit .