JP2013133552A - Deodorant for fiber and deodorant fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant for a fiber, which has superior product stability and also has superior compatibility with various functional processing agents, and to provide a deodorant fiber product obtained by using the same.SOLUTION: The deodorant for the fiber contains (A) particulates of silicon dioxide or particulates of a complex substance of silicon dioxide and zinc oxide, and (B) a compound that is represented by the following general formula (1) and the general formula (2) and is at least one compound selected from the group consisting of compounds that have an average molecular weight of 400 to 50,000 and contain 40 mass% or more of an ethyleneoxy group with respect to a molecular weight of the compound. The deodorant fiber product obtained by using the same is also disclosed.

Description

  The present invention relates to a fiber deodorant and a deodorant fiber product. The present invention particularly relates to a fiber deodorant having excellent product stability and compatibility with various functional processing agents, and a deodorant fiber product obtained by treatment with the deodorant.

  Conventionally, as a component having deodorizing performance, a composite of a metal oxide and silicon dioxide as described in Patent Document 1 is known. Among them, from the viewpoint of deodorizing performance, price, and safety, a composite of zinc oxide and silicon dioxide is widely used, and a fiber deodorant containing this composite is on the market.

  However, since this composite has poor dispersibility in an aqueous solution, the fiber deodorant containing this composite has a problem in product stability, and such a fiber deodorant with poor product stability is used as a fiber. When processed into a product, there is also a problem that whitening or processing spots occur in the fiber product. In addition, with the globalization of economic activities, the frequency of textile deodorants exported overseas and long-distance transportation is increasing, and the stability of products over an extended period is required.

  Patent Document 2 proposes a fiber deodorant using an anionic dispersant such as polycarboxylic acid or a salt thereof in order to improve the dispersibility of a composite of zinc oxide and silicon dioxide.

  In recent years, there has been an increase in cases in which various fiber functional processing agents are used in combination during fiber processing due to the increasing needs for high functionality for fiber products. However, fiber deodorization using the anionic dispersant of Patent Document 2 is increasing. When a cationic functional processing agent is used in combination with the agent, there is a problem in that the compatibility is poor, and there is a problem that processing spots are generated in the fiber product, and there is a problem that the types of the functional processing agent that can be used in combination are limited. In order to solve this problem, when a composite of zinc oxide and silicon dioxide is dispersed with a nonionic surfactant, compatibility with various functional processing agents is good, but product stability is poor, There is a problem that it becomes difficult to store the fiber deodorant for a long period of time.

Japanese Patent Publication No. 7-51486 JP 2006-336176 A

  The present invention has been made in view of the above-described problems of the prior art, and has excellent product stability and compatibility with various functional processing agents, and a deodorant obtained using the same. The object is to provide odorous fiber products.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention achieved product stability by dispersing fine particles of silicon dioxide or a composite of silicon dioxide and zinc oxide using a specific compound. It has been found that a fiber deodorant having excellent properties and compatibility with various functional finishing agents can be obtained, and the present invention has been completed.

  That is, the present invention comprises (A) fine particles of silicon dioxide or a composite of silicon dioxide and zinc oxide, and (B) a compound represented by the following general formulas (1) and (2), Provided is a fiber deodorant comprising: at least one selected from the group consisting of compounds having a molecular weight of 400 to 50,000 and containing 40% by mass or more of ethyleneoxy groups with respect to the molecular weight of the compound. To do.

(In the above formula, R ¹ , R ² and R ³ may be the same or different, and each represents hydrogen, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or- (A ¹ O) _n H, R ⁴ represents an alkylene group having 2 to 10 carbon atoms, m represents 0, 1 or 2, and when m is 2, a plurality of R ³ may be the same or a phase The plurality of R ⁴ may be the same or different, A ¹ represents an alkylene group having 2 to 4 carbon atoms, and n represents an alkylene represented by (A ¹ O). The average number of moles added of the oxy group is 2 to 550, and the plurality of A ¹ may be the same or different)

(In the above formula, R ⁵ represents an alkyl group having 1 to 21 carbon atoms or an alkenyl group having 2 to 21 carbon atoms, and R ⁶ represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or — (A ² O) _p H R ⁷ represents hydrogen, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or — (A ² O) _p H, and R ⁸ represents an alkylene group having 2 to 10 carbon atoms. , O represents 0, 1 or 2, and when o is 2, a plurality of R ⁷ may be the same or different, and a plurality of R ⁸ may be the same or different. , A ² represents an alkylene group having 2 to 4 carbon atoms, p is an average addition mole number of an alkyleneoxy group represented by (A ² O), and represents ² to 550, and a plurality of A ² are the same Or it may be different)

In the present invention, among the compounds represented by the general formula (1), at least one of R ¹ and R ² is — (A ¹ O) _n H, and R ³ is — (A ¹ O) _n H or A compound in which R ⁴ is an alkylene group having 2 to ⁴ carbon atoms and m is 0 or 1 is preferable, and among the compounds represented by the general formula (2), R ⁷ is — (A ² O ) and _p H, ^{R 8} is an alkylene group having 2 to 4 carbon atoms, o compound is 0 or 1 is preferred.

  The present invention also provides a deodorant fiber product obtained by treatment with a treatment liquid containing the fiber deodorant.

  ADVANTAGE OF THE INVENTION According to this invention, the deodorizer for textiles with the favorable deodorizing performance which is excellent in product stability and compatibility with various functional processing agents is obtained. Since this fiber deodorant can be stored for a long period of time, it can also be exported to overseas.

  In addition, according to the treatment liquid containing the fiber deodorant of the present invention, it is possible to perform treatment with them regardless of the ionicity of the functional processing agent to be used, and a highly functional fiber product is obtained by one bath treatment. be able to.

  Hereinafter, preferred embodiments of the present invention will be described.

  As a composite of silicon dioxide and zinc oxide in the component (A) used in the present invention, the mass ratio of silicon dioxide and zinc oxide as described in paragraph 0016 of Patent Document 2 is silicon dioxide: oxide. Zinc = 1: 10 to 10: 1, which is an amorphous compound (composite). For example, by mixing and reacting an aqueous solution of sodium silicate and an aqueous solution of zinc water-soluble salt The obtained gel can be obtained by drying. Alternatively, for example, according to the production method described in Patent Document 1, an aqueous solution of sodium silicate and an aqueous solution of zinc water-soluble salt are mixed and reacted so that the water content in the reaction system is 85% or more. Then, an amorphous composite slurry of gel-like silicon dioxide and zinc oxide was prepared, and this slurry was used as a mother liquor while maintaining the pH at 6.5 to 8.0, and a new aqueous solution of sodium silicate and zinc It can be obtained by adding the aqueous solution of the salt salt gradually and separately at the same time and drying the resulting gel.

  Examples of sodium silicate include sodium orthosilicate, sodium metasilicate, and water glass. Alternatively, it can be obtained by heating and melting silicon dioxide with sodium carbonate or sodium hydroxide.

  Examples of the water-soluble salt of zinc include zinc sulfate, zinc nitrate, and zinc chloride.

  Moreover, a commercial item can be used as a composite of a silicon dioxide and a zinc oxide, for example, a shoe clean series (made by Rasa Industrial Co., Ltd.) etc. can be mentioned.

  Such a composite of silicon dioxide and zinc oxide in component (A) may be used alone or in combination of two or more.

  In the present invention, the amount of component (A) is not particularly limited, but is preferably 0.5 to 60% by mass in the fiber deodorant. When the component (A) is less than 0.5% by mass, the efficiency as a fiber deodorant is low, and the deodorant performance of the resulting deodorant fiber product tends to be insufficient. On the other hand, when it exceeds 60 mass%, the product stability of the fiber deodorant tends to be lowered.

  (B) component used for this invention is a compound represented by General formula (1) and General formula (2), Comprising: An average molecular weight is 400-50,000, and 40 mass% with respect to the molecular weight of a compound It consists of at least one of the above-mentioned compounds containing an ethyleneoxy group.

In the compound represented by the general formula (1), the alkyl group having 1 to 22 carbon atoms and the alkenyl group having 2 to 22 carbon atoms represented by R ¹ , R ² and R ³ may be linear or branched. It may be.

Examples of the alkylene group having 2 to 10 carbon atoms represented by R ⁴ include an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, and an octamethylene group. Among these, from the viewpoint of product stability of the fiber deodorant, an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group are preferable.

Examples of the alkylene group having 2 to 4 carbon atoms represented by A ¹ include ethylene group, propylene group, and butylene group. Among these, from the viewpoint of product stability of the fiber deodorant, an ethylene group and a pyropyrene group are preferable, and an ethylene group is more preferable.

  m is 0, 1 or 2, but m is preferably 0 or 1 from the viewpoint of easy availability of raw materials.

In the compound represented by the general formula (1), when m is 0, at least one of R ¹ and R ² is — (A ¹ O) _n H from the viewpoint of product stability of the fiber deodorant. It is preferable that ^one of R ¹ and R ² is — (A ¹ O) _n H, and the other is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. More preferred. In-(A ¹ O) _n H, n is preferably 8 to 220, more preferably 8 to 110. When R ¹ and R ² are an alkyl group having 1 to 22 carbon atoms or an alkenyl group having ² to 22 carbon atoms, the carbon number is 12 to 18 from the viewpoint of product stability of the fiber deodorant. preferable.

In the compound represented by the general formula (1), when m is 1 or 2, from the viewpoint of product stability of the fiber deodorant, at least one of R ¹ and R ² is-(A ¹ O) _n H. It is preferable that R ³ is — (A ¹ O) _n H or hydrogen, and it is more preferable that all of R ¹ , R ² , and R ³ are — (A ¹ O) _n H. In-(A ¹ O) _n H, n is preferably 5 to 110, and more preferably 5 to 55. When R ¹ and R ² are an alkyl group having 1 to 22 carbon atoms or an alkenyl group having ² to 22 carbon atoms, the carbon number is 12 to 18 from the viewpoint of product stability of the fiber deodorant. preferable.

  The compound represented by the general formula (1) can be prepared by, for example, reacting an aliphatic amine represented by the following general formula (3) with an alkylene oxide containing ethylene oxide or a polyoxy group containing an ethyleneoxy group according to a conventional method. It can be obtained by reacting alkylene glycol.

(In the above formula, R ⁹ , R ¹⁰ and R ¹¹ may be the same or different and each represents hydrogen, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. R ¹² represents hydrogen, and R ⁴ and m represent the same as defined in the general formula (1))

  Commercially available products can also be used as the compound represented by the general formula (1), for example, the Esomin series, the Esododumin series (manufactured by Lion Co., Ltd.)); ADEKA); Amito series (Kao Co., Ltd.) and the like can be used.

In the compound represented by the general formula (2), the alkyl group having 1 to 21 carbon atoms and the alkenyl group having 2 to 21 carbon atoms represented by R ⁵ may be linear or branched. Among these, it is preferable that carbon number is 11-17 from a viewpoint of the product stability of the deodorizer for fibers.

R ⁶ is hydrogen, an alkyl group having 1 to 3 carbon atoms, or — (A ² O) _p H, and is hydrogen or — (A ² O) _p H from the viewpoint of product stability of the fiber deodorant. It is preferable.

R ⁷ is hydrogen, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms - is a ^(A 2 _{O) p} H, alkyl group having 1 to 22 carbon atoms, 2 to 22 carbon atoms The alkenyl group may be linear or branched.

Examples of the alkylene group having 2 to 10 carbon atoms represented by R ⁸ include an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, and an octamethylene group. Among these, an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group are preferable from the viewpoint of product stability of the fiber deodorant.

Examples of the alkylene group having 2 to 4 carbon atoms represented by A ² include an ethylene group, a propylene group, and a butylene group. Among these, from the viewpoint of product stability of the fiber deodorant, an ethylene group and a pyropyrene group are preferable, and an ethylene group is more preferable.

  Although o is 0, 1 or 2, o is preferably 0 or 1 from the viewpoint of easy availability of raw materials.

In the compound represented by the general formula (2), from the viewpoint of the product stability of fiber deodorant, R ⁷ is - is preferably a (A 2 ^O) p _H. When o is 0, p is preferably 8 to 220, more preferably 8 to 110. When o is 1 or 2, p is preferably 5 to 220, more preferably 5 to 110. When R ⁷ is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, the carbon number is preferably 12 to 18 from the viewpoint of product stability of the fiber deodorant.

  The compound represented by the general formula (2) reacts, for example, a fatty acid represented by the following general formula (4) with an amine represented by the following general formula (5) or the general formula (6) according to a conventional method. Or an amide compound obtained by reacting a fatty acid represented by the following general formula (4) and an amine represented by the following general formula (7) or (8) with an alkylene oxide containing ethylene oxide It can be obtained by reacting or reacting a polyoxyalkylene glycol containing an ethyleneoxy group.

R ¹³ COOH (4)

(In the above formula, R ¹³ represents an alkyl group having 1 to 21 carbon atoms or an alkenyl group having 2 to 21 carbon atoms)

(In the above formula, R ¹⁴ represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or — (A ² O) _p H, and A ² and p represent the same as those defined in the general formula (2). )

(In the above formula, R ¹⁵ represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or — (A ² O) _p H, and R ¹⁶ represents hydrogen, an alkyl group having 1 to 22 carbon atoms, or 2 to 22 carbon atoms. Represents an alkenyl group or — (A ² O) _p H, R ¹⁷ represents — (A ² O) _p H, and R ⁸ , A ² , o, and p are the same as those defined in the general formula (2). Represents a thing)

(In the above formula, R ¹⁸ represents hydrogen or an alkyl group having 1 to 3 carbon atoms)

(In the above formula, R ¹⁹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms, R ²⁰ represents hydrogen, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, and R ⁸ , o Represents the same as defined in the general formula (2)

  As the compound represented by the general formula (2), a commercially available product can be used, and for example, the Esomeide series (manufactured by Lion Corporation)) and the like can be used.

  The average molecular weight of the component (B) used in the present invention is 400 to 50,000, preferably 1,000 to 20,000, and more preferably 1,000 to 10,000. When the molecular weight is less than 400, the product stability of the fiber deodorant is poor. When the molecular weight is greater than 50,000, the product stability of the fiber deodorant is poor, and the fiber deodorant is not stable. The viscosity of the odorant becomes high, making it difficult to use. This average molecular weight can be measured by gel permeation chromatography.

  Moreover, although (B) component used for this invention contains 40 mass% or more of ethyleneoxy groups with respect to the molecular weight of a compound, it is preferable to contain 70 mass% or more, and it is more preferable to contain 80 mass% or more. preferable. When the content of the ethyleneoxy group is outside the above range, the product stability of the fiber deodorant becomes poor.

   Such (B) component may use 1 type and may be used in combination of 2 or more type.

  In the present invention, the amount of component (B) is not particularly limited, but it is preferably 0.05 to 10% by mass in the fiber deodorant. When the component (B) is less than 0.05% by mass, the product stability of the fiber deodorant tends to be insufficient. On the other hand, if it exceeds 10% by mass, the washing durability of the textile product tends to be insufficient.

  The fiber deodorant of the present invention may be used in combination with an anionic surfactant or a cationic surfactant for the purpose of improving the product stability of the fiber deodorant.

  The anionic surfactant that can be used in combination is not particularly limited. For example, a linear or branched alcohol having 8 to 24 carbon atoms or an anion of an alkenol, or a linear or branched carbon having 8 to 24 carbon atoms. Anionized products of alkylene oxide adducts of alcohols or alkenols, anionized products of alkylene oxide adducts of polycyclic phenols, anionized products of alkylene oxide adducts of linear or branched aliphatic amines having 8 to 44 carbon atoms, Anionized products of alkylene oxide adducts of linear or branched fatty acid amides having 8 to 44 carbon atoms, linear or branched fatty acid alkylene oxide adducts, sulfonated products of fats and oils, etc. Is mentioned. These anionic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

  The cationic surfactant that can be used in combination is not particularly limited, and examples thereof include monoalkyltrimethylammonium salts having 8 to 24 carbon atoms, dialkyldimethylammonium salts having 8 to 24 carbon atoms, and monoalkyls having 8 to 24 carbon atoms. Examples thereof include amine acetates, dialkylamine acetates having 8 to 24 carbon atoms, and alkyl imidazoline quaternary salts having 8 to 24 carbon atoms. These cationic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

  The blending ratio (mass basis) of the component (B) and the anionic surfactant should be in the range of component (B): anionic surfactant = 75: 25 to 100: 0, more preferably 100: 0. It is. When an anionic surfactant exceeds 25 mass%, there exists a tendency for compatibility with a cationic functional processing agent to fall.

  The blending ratio (mass basis) of the component (B) and the cationic surfactant should be in the range of component (B): cationic surfactant = 75: 25 to 100: 0, more preferably 100: 0. It is. When a cationic surfactant exceeds 25 mass%, there exists a tendency for compatibility with an anionic functional processing agent to fall.

  The fiber deodorant of the present invention can be prepared, for example, by dispersing the component (A) in an aqueous medium using the component (B) or by continuously mixing the component (A), the component (B), and the aqueous medium. It can be obtained by performing distributed processing.

  The aqueous medium is preferably water or a mixed solvent of water and a hydrophilic solvent miscible with water. Examples of the hydrophilic solvent include methanol, ethanol, isopropyl alcohol, ethylene glycol, hexylene glycol, glycerin, butyl glycol, and sol-fit.

  In order to disperse the component (A) in an aqueous medium, a conventionally known disperser may be used. Conventionally known dispersers are not particularly limited. A disperser can be mentioned. One type of these dispersers may be used, or two or more types may be used in combination.

  The average particle size of the resulting fiber deodorant particles is preferably 0.05 to 10 μm, more preferably 0.1 to 3 μm, and even more preferably 0.1 to 2 μm. When the average particle size exceeds 10 μm, the product stability of the fiber deodorant tends to decrease. On the other hand, when the average particle size is smaller than 0.05 μm, the product stability of the fiber deodorant tends to decrease, and the deodorizing performance tends to decrease. This average particle diameter can be measured by a laser diffraction / scattering method.

  In addition, the fiber deodorant of the present invention includes a conventionally known deodorant other than the component (A), a nonionic surfactant other than the component (B), an antibacterial agent, a softener, and a water absorption as necessary. Agent, water / oil repellent, smoothing agent, penetrating agent, dispersion leveling agent, antistatic agent, chelating agent, antioxidant, antifoaming agent, solvent, synthetic resin (acrylic resin, silicone resin, urethane resin, polyester resin, Glyoxal resin, melamine resin, etc.), cross-linking agent, flame retardant, anti-freezing agent, freezing stabilizer, matting agent, pigment, dye, fixing agent, wetting agent, light stabilizer, UV absorber, thickener (PEG, poly Acrylamide, xanthan gum, polyacrylic acid soda, CMC, PVA, etc.), film-forming aids, rust preventives, antiseptics, antifungal agents, anti-yellowing agents, etc., as long as the effects of the present invention are not impaired. Also good. Moreover, you may process with these chemical | medical agents before and after processing the fiber deodorant of this invention into a textile product.

  According to the present invention, a deodorant fiber product can be obtained by applying a treatment liquid containing a fiber deodorant containing the component (A) and the component (B) to a fiber product. The method for applying the treatment liquid containing the fiber deodorant of the present invention to the fiber product is not particularly limited, and known methods such as a dipping method, a padding method, a coating method, and a spray method can be appropriately used.

  In the case of applying by immersion treatment, the concentration of the component (A) in the treatment liquid is, for example, 0.01 to 10% o.d. w. f. It is preferable to be in the range. In the case of padding treatment, the concentration of the component (A) in the treatment liquid is preferably in the range of 0.01 to 10% by mass, for example.

  When the fiber product is applied by the dipping method or padding method, the supported amount of the component (A) is 0.01 to 10% o. w. f. It can be given and used. (A) Component loading is 0.01% o. w. f. Is less than 10%, the deodorizing performance of the resulting deodorant fiber product tends to be insufficient. w. f. If it exceeds 1, deodorant performance is not improved, and the resulting deodorant fiber product tends to be whitened and the appearance is impaired.

  In the case of the dipping method, it is dehydrated after being processed at a predetermined temperature for a predetermined time using a dyeing machine generally used, that is, wins, liquid dyeing machine, zicker, cheese dyeing machine, skein dyeing machine, etc. The deodorant fiber product can be obtained by drying. In the case of the padding method, a deodorant fiber product can be obtained by immersing the fiber product in a treatment liquid, adjusting the amount to a predetermined pick-up amount using a mangle or the like, and then drying.

  In the case of coating, for example, a mixture obtained by mixing a treatment liquid containing the components (A) and (B) of the present invention with a binder can be used. In this case, it is preferable that (A) component is the range of 0.1-10 mass% with respect to a binder, for example. In the case of spraying, it is preferable to perform the spray treatment using a solution having a component (A) concentration in the range of 10 to 90% by mass, for example.

When apply | coating to a textile product by coating and spray, it can provide and use so that (A) component may be 0.1-20 g / m < ² >, for example. If it is less than 0.1 g / m ² , sufficient deodorizing performance tends to be hardly exhibited, and even if it is used in excess of 20 g / m ² , the effect of improving the deodorizing performance is small, and there is a tendency that it is not economical.

  In the case of coating, a deodorant fiber product can be obtained by painting by brush coating, roller coating, flow coater coating, electrodeposition coating, etc. and drying.

  There is no restriction | limiting in particular in drying conditions, For example, what is necessary is just to dry for about 5 second-several days at 0-300 degreeC. If necessary, heat treatment (curing) may be performed at a temperature of 100 ° C. or higher for about 10 seconds to 10 minutes after drying.

  The material of the fiber product to which the treatment liquid containing the fiber deodorant of the present invention can be applied is not particularly limited. For example, natural fibers such as cotton, silk, and wool, polyamide fibers, polyurethane fibers, Mention fiber products made of synthetic fibers such as polyester fibers, polyethylene fibers, polypropylene fibers, acrylic fibers, semi-synthetic fibers such as acetate fibers, regenerated fibers such as rayon, composite fibers, blended fibers, etc. Can do.

  Moreover, there is no restriction | limiting in particular in the form of a textile product, For example, a short fiber, a long fiber, a thread | yarn, a textile fabric, a knitted fabric, a cotton, a sliver, a top, a nonwoven fabric etc. can be mentioned.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Preparation Example 1 Preparation of Component (A) (Silicon Dioxide / Zinc Oxide Composite) First, 19.8 g (0.069 mol) of zinc sulfate heptahydrate was dissolved in 50 ml of water. On the other hand, No. 3 sodium silicate (molar ratio: Na ₂ O / SiO ₂ = 1/3, Na ₂ O content: 7.0 mass%, SiO ₂ content: 21.0 mass%) 50 g (Na ₂ O: 0.056 mol, SiO ₂ : 0.175 mol) was dissolved in 170 ml of water. These solutions were mixed and reacted at 20-30 ° C. for 90 minutes to obtain a gel slurry. The pH of the resulting gel slurry was 6.8.

200 ml of the resulting gel slurry was placed in a 3 L container, and stirred at 40 ° C., 1 L of zinc sulfate aqueous solution (0.67 mol / L) and No. 3 sodium silicate aqueous solution (Na ₂ O: 0.7 mol / L, SiO 2 ₂ : 2.1 mol / L) 1 L was simultaneously added dropwise at a rate of 5.5 ml / min, and then reacted at 40 ° C. for 60 minutes. The pH of the slurry during the reaction was 7.5. Thereafter, 200 ml of this slurry was suction filtered with a Buchner funnel, washed 5 times with 100 ml of water, dried at 110 ° C. and pulverized to obtain a white powdery component (A). As a result of measuring the obtained component (A) with a fluorescent X-ray analyzer, silicon dioxide was 63% by mass, zinc oxide was 22% by mass, and the water content was 15% by mass.

Synthesis example 1
269 parts by mass (1.0 mol) of stearylamine was charged into an autoclave, and 88 parts by mass (2.0 mol) of ethylene oxide was added under a nitrogen gas atmosphere at a temperature of 150 to 160 ° C. and a pressure of 0.39 MPa or less. Diethanolamine was obtained.

  The obtained stearyldiethanolamine (357 parts by mass (1.0 mol)) and sodium hydroxide (0.5 parts by mass) were charged in an autoclave and heated to 120 ° C. in a nitrogen gas atmosphere. Next, 92.4 parts by mass (2.1 mol) of ethylene oxide was reacted at a temperature of 150 to 160 ° C. and a pressure of 0.39 MPa or less. After completion of the reaction, the reaction mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain 4.1 mol of stearylamine ethylene oxide adduct.

  Gel permeation chromatography (High-speed GPC “HLC-8220 type” manufactured by Tosoh Corporation), standard substance: polyethylene glycol, solvent: THF, flow rate: 0.25 ml / min, column: TSK-GEL SuperHZ (manufactured by Tosoh Corporation) ), Injection amount: 5 μl, column temperature: 40 ° C., detector: RI, UV (254 nm)), the weight average molecular weight was measured to be 450. The proportion of ethyleneoxy groups was 40% by mass.

Synthesis example 2
Stearylamine was operated in the same manner as in Synthesis Example 1 except that sodium hydroxide was 0.9 part by mass and ethylene oxide 572 parts by mass (13.0 mol) with respect to 357 parts by mass (1.0 mol) of stearyldiethanolamine. Of 15 moles of ethylene oxide was obtained.
The weight average molecular weight of this adduct was 928, and the proportion of ethyleneoxy groups was 71% by mass.

Synthesis example 3
Stearylamine was operated in the same manner as in Synthesis Example 1 except that sodium hydroxide was 2.5 parts by mass and ethylene oxide was 2112 parts by mass (48.0 mol) with respect to 357 parts by mass (1.0 mol) of stearyldiethanolamine. Of ethylene oxide was obtained.
The weight average molecular weight of this adduct was 2,468, and the proportion of ethyleneoxy groups was 89% by mass.

Synthesis example 4
It was set as the mixture of sodium hydroxide 2.6 mass part, ethylene oxide 1980 mass part (45.0 mol), and propylene oxide 232 mass part (4.0 mol) with respect to 357 mass parts (1.0 mol) of stearyl diethanolamine. Except for the above, the same operation as in Synthesis Example 1 was carried out to obtain a 47 mol propylene oxide 4 mol adduct of ethylene oxide of stearylamine.
The weight average molecular weight of this adduct was 2,500, and the proportion of ethyleneoxy groups was 80% by mass.

Synthesis example 5
It was set as the mixture of sodium hydroxide 2.5 mass part, ethylene oxide 1672 mass part (38.0 mol), and propylene oxide 464 mass part (8.0 mol) with respect to 357 mass parts (1.0 mol) of stearyl diethanolamine. Except for the above, the same operation as in Synthesis Example 1 was carried out to obtain a stearylamine ethylene oxide 40 mol propylene oxide 8 mol adduct.
The weight average molecular weight of this adduct was 2,450, and the proportion of ethyleneoxy groups was 70% by mass.

Synthesis Example 6
A mixture of 2.6 parts by weight of sodium hydroxide, 924 parts by weight of ethylene oxide (21.0 moles) and 1242.9 parts by weight (21.4 moles) of propylene oxide with respect to 357 parts by weight (1.0 moles) of stearyl diethanolamine A stearylamine ethylene oxide 25 mol propylene oxide 21.4 mol adduct was obtained in the same manner as in Synthesis Example 1 except that.
The weight average molecular weight of this adduct was 2,520, and the proportion of ethyleneoxy groups was 40% by mass.

Synthesis example 7
Except for 357 parts by mass (1.0 mol) of stearyl diethanolamine, 10.0 parts by mass of sodium hydroxide and 9531.1 parts by mass (216.6 mol) of ethylene oxide were operated in the same manner as in Synthesis Example 1, 218.6 mol adduct of stearylamine with ethylene oxide was obtained.
The weight average molecular weight of this adduct was 9,800, and the proportion of ethyleneoxy groups was 97% by mass.

Synthesis Example 8
Stearylamine was operated in the same manner as in Synthesis Example 1 except that sodium hydroxide was 19.3 parts by mass and ethylene oxide 18931 parts by mass (430.3 mol) with respect to 357 parts by mass (1.0 mol) of stearyldiethanolamine. Of ethylene oxide was obtained.
The weight average molecular weight of this adduct was 19,200, and the proportion of ethyleneoxy groups was 99% by mass.

Synthesis Example 9
Instead of stearylamine, 185 parts by mass (1.0 mol) of dodecylamine was used to synthesize dodecyldiethanolamine, 2.4 parts by mass of sodium hydroxide with respect to 273 parts by mass (1.0 mol) of dodecyldiethanolamine, ethylene The procedure was the same as in Synthesis Example 1 except that 2112 parts by mass (48.0 mol) of oxide was used to obtain a 50 mol adduct of dodecylamine with ethylene oxide.
The weight average molecular weight of this adduct was 2,385, and the proportion of ethyleneoxy groups was 92% by mass.

Synthesis Example 10
Decyldiethanolamine was synthesized using 157 parts by mass (1.0 mol) of decylamine instead of stearylamine. 2.6 parts by mass of sodium hydroxide and ethylene oxide with respect to 245 parts by mass of decyldiethanolamine (1.0 mol) Except having been 2323.1 mass parts (52.8 mol), it operated similarly to the synthesis example 1, and obtained the ethylene oxide 54.8 mol adduct of decylamine.
The weight average molecular weight of this adduct was 2,568, and the proportion of ethyleneoxy groups was 94% by mass.

Synthesis Example 11
Tetraethanolethylenediamine was synthesized using 104 parts by mass (1.0 mol) of aminoethylethanolamine instead of stearylamine, and 3 parts by mass of sodium hydroxide with respect to 236 parts by mass (1.0 mol) of tetraethanolethylenediamine. , Ethylenediamine ethylene oxide 48 mol propylene oxide, operating in the same manner as in Synthesis Example 1 except that a mixture of ethylene oxide 1936.0 parts by mass (44.0 mol) and propylene oxide 841 parts by mass (14.5 mol) was used. 14.5 mol adduct was obtained.
The weight average molecular weight of this adduct was 3,000, and the proportion of ethyleneoxy groups was 70% by mass.

Synthesis Example 12
A mixture of sodium hydroxide 3 parts by mass, ethylene oxide 2224.0 parts by mass (50.5 mol) and propylene oxide 540 parts by mass (9.3 mol) with respect to 236 parts by mass (1.0 mol) of tetraethanolethylenediamine In the same manner as in Synthesis Example 11 except for the above, an ethylene oxide 54.5 mol propylene oxide 9.3 mol adduct was obtained.
The weight average molecular weight of this adduct was 3,000, and the proportion of ethyleneoxy groups was 70% by mass.

Synthesis Example 13
Tetraethanolethylenediamine was synthesized using 104 parts by mass (1.0 mol) of aminoethylethanolamine instead of stearylamine, and 9 parts by mass of sodium hydroxide with respect to 236 parts by mass (1.0 mol) of tetraethanolethylenediamine. The ethylene diamine ethylene oxide 185 mol propylene oxide was operated in the same manner as in Synthesis Example 1 except that a mixture of 9764.0 parts by mass (181.0 mol) of ethylene oxide and 870 parts by mass (15.0 mol) of propylene oxide was used. A 15 molar adduct was obtained.
The weight average molecular weight of this adduct was 9000, and the proportion of ethyleneoxy groups was 90% by mass.

Synthesis Example 14
Sodium hydroxide 48.1 parts by mass, ethylene oxide 43023.2 parts by mass (977.8 mol) and propylene oxide 4802.4 parts by mass (82.8 mol) with respect to 236 parts by mass (1.0 mol) of tetraethanol ethylenediamine ), Except that the mixture was used in the same manner as in Synthesis Example 11 to obtain an ethylene oxide 981.8 mol propylene oxide 82.8 mol adduct of ethylenediamine.
The weight average molecular weight of this adduct was 48,000, and the proportion of ethyleneoxy groups was 90% by mass.

Synthesis Example 15
A reaction vessel was charged with 200 parts by mass (1.0 mol) of lauric acid and 118 parts by mass (1.0 mol) of 3- (2-hydroxyethylamino) propylamine, and reacted at 160 to 170 ° C. for 5 hours in a nitrogen stream. To give 3-laurylamide-N- (2-hydroxyethyl) propylamine.

With respect to 300 parts by mass (1.0 mol) of 3-laurylamide-N- (2-hydroxyethyl) propylamine, 3.0 parts by mass of sodium hydroxide, 2699.8 parts by mass of ethylene oxide (61.4 mol) and The procedure was the same as in Synthesis Example 1 except that 62.4 mol adduct of 3- (laurylamido) propylamine with ethylene oxide was obtained.
The weight average molecular weight of this adduct was 3,000, and the proportion of ethyleneoxy groups was 91% by mass.

Comparative Synthesis Example 1
By operating in the same manner as in Synthesis Example 1, 269 parts by mass (1.0 mol) of stearylamine (2.0 mol) of ethylene oxide was obtained.
The weight average molecular weight of this adduct was 357, and the proportion of ethyleneoxy groups was 25% by mass.

Comparative Synthesis Example 2
The same as Synthesis Example 1 except that 119 parts by mass (1.0 mol) of N-methyldiethanolamine, 0.4 parts by mass of sodium hydroxide, and 231.1 parts by mass (5.3 mol) of ethylene oxide were used instead of stearyl diethanolamine. To give a 7.3 molar adduct of N-methylamine.
The weight average molecular weight of this adduct was 350, and the proportion of ethyleneoxy groups was 91% by mass.

Comparative Synthesis Example 3
Stearylamine was operated in the same manner as in Synthesis Example 1 except that sodium hydroxide was 55.0 parts by mass and ethylene oxide 54670 parts by mass (1242.5 mol) with respect to 357 parts by mass (1.0 mol) of stearyldiethanolamine. Of ethylene oxide was obtained.
The weight average molecular weight of this adduct was 55,000, and the ratio of ethyleneoxy groups was 99.5% by mass.

Comparative Synthesis Example 4
Sodium hydride 2.2 parts by mass, ethylene oxide 792.0 parts by mass (18.0 mol) and propylene oxide 1363.0 parts by mass (23.5 mol) with respect to 357 parts by mass (1.0 mol) of stearyl diethanolamine Except that the mixture was used, the same operation as in Synthesis Example 1 was carried out to obtain a stearylamine ethylene oxide 20 mol propylene oxide 23.5 mol adduct.
The weight average molecular weight of this adduct was 2,500, and the proportion of ethyleneoxy groups was 35% by mass.

Comparative Synthesis Example 5
Ethylenediamine ethylene was prepared in the same manner as in Synthesis Example 11 except that sodium hydroxide was 0.4 parts by mass and ethylene oxide was 114 g (2.6 mol) with respect to 236 parts by mass (1.0 mol) of tetraethanolethylenediamine. An oxide 6.6 mol adduct was obtained.
The weight average molecular weight of this adduct was 350, and the proportion of ethyleneoxy groups was 83% by mass.

Comparative Synthesis Example 6
Sodium hydroxide 2.5 parts by mass, ethylene oxide 699.2 parts by mass (15.9 mol) and propylene oxide 1564.8 parts by mass (27.0 mol) with respect to 236 parts by mass (1.0 mol) of tetraethanol ethylenediamine ), Except that the mixture was made in the same manner as in Synthesis Example 11 to obtain an ethylene oxide 19.9 mol propylene oxide 27 mol adduct of ethylenediamine.
The weight average molecular weight of this adduct was 2500, and the proportion of ethyleneoxy groups was 35% by mass.

Comparative Synthesis Example 7
A mixture of sodium hydroxide 55.2 parts by mass, ethylene oxide 44000 parts by mass (1000 mol) and propylene oxide 10938.8 parts by mass (188.6 mol) with respect to 236 parts by mass (1.0 mol) of tetraethanol ethylenediamine. Except for the above, the same operation as in Synthesis Example 11 was carried out to obtain an ethylene oxide 1004 mol propylene oxide 188.6 mol adduct of ethylenediamine.
The weight average molecular weight of this adduct was 55,000, and the proportion of ethyleneoxy groups was 80% by mass.

Comparative Synthesis Example 8
A reaction vessel was charged with 94 parts by mass (1.0 mol) of phenol and 0.1 part by mass of sulfuric acid, heated with heating in a nitrogen gas stream while stirring, and 312 parts by mass of styrene monomer (3. 0 mol) was added dropwise, and an addition reaction was carried out at 125 to 135 ° C. for about 3 hours, followed by cooling to obtain a brown transparent viscous liquid tristyrenated phenol.

The same procedure as in Synthesis Example 11 was repeated, except that sodium hydroxide was 4.5 parts by mass and ethylene oxide was 880 parts by mass (20 mol) with respect to 403 parts by mass (1 mol) of the obtained tristyrenated phenol. A 20 mol adduct of styrenated phenol with ethylene oxide was obtained.
The weight average molecular weight of this adduct was 1,280, and the proportion of ethyleneoxy groups was 69% by mass.

Example 1
200 parts by mass of the compound of Preparation Example 1 as the component (A), 30 parts by mass of the compound of Synthesis Example 1 as the component (B), and 670 parts by mass of water are mixed, and the mixture is microparticulated until the average particle size becomes 0.5 μm with a pearl mill. did. The average particle size is determined by measuring the cumulative volume particle size distribution of the fiber deodorant using a laser diffraction / scattering particle size distribution analyzer ("LA-920" manufactured by HORIBA), and the particle size at which the integrated volume is 50%. The (median particle size) was defined as the average particle size (μm). To this micronized product, 100 parts by mass of a 3% by mass aqueous solution of hydroxyethyl cellulose (trade name HEC SE-850, manufactured by Daicel Chemical Industries, Ltd.) was mixed and stirred to obtain a fiber deodorant.

  The obtained fiber deodorant was evaluated for product stability test, drug compatibility test, deodorization test, and whitening test. Moreover, the deodorant test and the whitening test were evaluated about the fiber deodorant after a 60 degreeC x 20 day product stability test. About the fiber deodorizer after a 60 degreeC x 20 day product stability test, about what thickening and isolation | separation were recognized, it evaluated using what was made uniform. The results are shown in Table 1.

Examples 2-30 and Comparative Examples 1-14
For the fibers of Examples 2 to 30 and Comparative Examples 1 to 14, except that the components (A) and (B) of Example 1 were replaced with those described in Tables 1 to 5 in the same manner as in Example 1. A deodorant was obtained. In Example 8, Example 9, and Example 29, an Aspec mill was used in place of the pearl mill as the micronizing device.

  The obtained fiber deodorant was evaluated for product stability test, drug compatibility test, deodorization test, and whitening test. Moreover, the deodorant test and the whitening test were evaluated about the fiber deodorizer after a 60 degreeC x 20 day product stability test. About the fiber deodorizer after a 60 degreeC x 20 day product stability test, about what thickening and isolation | separation were recognized, it evaluated using what was made uniform. The results are shown in Tables 1-5.

  In Examples and Comparative Examples, product stability tests, drug compatibility tests, deodorization tests, and whitening tests of fiber deodorants were performed and evaluated according to the following methods.

Product stability test Fiber deodorant was put in a glass bottle and sealed, and the appearance after 5 and 20 days at 60 ° C and after 2 weeks and 3 months at 20 ° C was visually observed and evaluated according to the following criteria. did.
7: No increase in viscosity or separation, the same as before the product stability test 6: There is very little separation, but it easily returns to the state before the product stability test with weak agitation 5: Some increase in viscosity or separation Yes, if it is stirred, it will easily return to the state before the product stability test. 4: There will be thickening and separation, but if it is stirred, it will return to the state before the product stability test. 2: Some coarse particles are observed 2: Thickening and separation are large, and coarse particles are observed even when stirred 1: Solidification and large separation are observed, and a large amount of coarse particles are observed even when stirred

Drug compatibility test Mix 5 parts by weight of fiber deodorant (2 parts by weight only in Example 17), 2 parts by weight of functional processing agent, and 93 parts by weight of water (96 parts by weight only in Example 17) until uniform. A treatment solution was prepared. The appearance after 1 hour of preparation of the treatment liquid was visually observed and evaluated in the following three stages.
A: No separation or sedimentation is observed B: Some separation or sedimentation is observed C: Separation or sedimentation is observed immediately after preparation

In addition, as a functional processing agent, the following 2 types from which ionicity differs were used.
Cationic functional processing agent: Neofix R-800 (Nikka Chemical Co., Ltd., cationic polymer compound)
Anionic functional finishing agent: Nicepol PR-99 (Nikka Chemical Co., Ltd., anionic polyester resin)

Deodorization test (ammonia deodorization rate)
Preparation of deodorant fiber product 5 parts by mass of fiber deodorant (2 parts by mass only in Example 17), 2 parts by mass of silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KM-2002-L-1”) Part of the water and 93 parts by weight of water (96 parts by weight only in Example 17) were mixed to prepare a treatment liquid. Using this treatment solution, 100% polyester knitted fabric or 100% cotton knitted fabric was padded. The pickup was 70% by mass. Subsequently, after drying at 120 degreeC for 3 minute (s), it heat-processed at 160 degreeC for 1 minute (s), and obtained the deodorizing fiber product before washing.

  The deodorant fiber product before washing was washed 10 times to obtain a deodorant fiber product after 10 washings. The washing method was in accordance with JIS L 0217-1995 (Method 103). That is, 40 ml of JAFET standard detergent was used, and the bath ratio was 1:30. After washing at 40 ° C. for 5 minutes, dehydration was performed, and overflow rinse for 2 minutes was repeated twice. This process was carried out once, and overflow rinsing was carried out for another 5 minutes after 10 washings.

  Next, the deodorant fiber product before washing and after 10 washings was dried at 105 ° C. for 2 hours and then allowed to stand for 24 hours under conditions of 20 ° C. and 65% RH to adjust the humidity.

Measurement of Ammonia Deodorization Rate One dehumidified fiber product (10 cm × 10 cm) having been conditioned was put into a 5 L tedlar bag, the inside of the bag was deaerated, and then 3 L of air containing 100 ppm of ammonia was injected and sealed. After leaving at 20 ° C. for 2 hours, the residual concentration of ammonia was measured with a detector tube (No. 3L, manufactured by GASTEC). Moreover, as a blank test, the test was performed in the same manner without adding the deodorant fiber product, and the residual concentration was measured. The ammonia deodorization rate (%) was calculated by the following formula.

  Ammonia deodorization rate (%) = {1− (residual concentration) / (residual concentration in blank test)} × 100

Whitening test The appearance of the deodorant fiber product obtained by the preparation of the above-mentioned deodorant fiber product was visually observed and evaluated in the following three stages.
A: No whitening B: Some whitening C: Whitening

  From Examples 1 to 30, the deodorant for fibers of the present invention obtained by dispersing fine particles of silicon dioxide or a composite of silicon dioxide and zinc oxide as component (A) using a specific component (B) It can be seen that the agent is excellent in product stability and drug compatibility. Moreover, the deodorant fiber product obtained by processing with the fiber deodorant of the present invention can exhibit excellent deodorizing performance.

  From Comparative Examples 1 to 10, it is understood that the product stability is inferior when a nonionic surfactant other than the component (B) of the present invention is used.

  From Comparative Examples 11-13, product stability is good when surfactants with ionicity are used, but drug compatibility is poor when used in combination with drugs with the opposite ionicity. I understand.

  When the treatment is performed using the fiber deodorant after the product stability test at 60 ° C. × 20 days, the fiber deodorant of Examples 1 to 30 hardly shows whitening after the treatment. However, in the deodorizer for fibers using the nonionic surfactant other than the component (B) of the present invention in Comparative Examples 1 to 10, whitening was observed after the treatment. In the fiber deodorizers using the surfactants having ionic properties of Comparative Examples 12 to 13, whitening was observed after the treatment. In the case of fiber deodorants other than the present invention of Comparative Examples 1 to 10, 12, and 13, when a fiber product dyed using a product after long-term storage is processed, the hue changes, and the quality of the fiber product It is considered that there is a great possibility of causing a decrease.

  In the case of fiber deodorants other than the present invention of Comparative Examples 1 to 10, 12, and 13, after the product stability test of 60 ° C. × 20 days and 20 ° C. × 3 months, solidification and separation are uniformly stirred. After that, coarse particles were observed, and the phenomenon of separation was observed on the next day.

  When using the fiber deodorants of Comparative Examples 1 to 10, 12, and 13 other than the present invention after long-term storage, separation occurs immediately despite the need for uniform stirring before use. There is a tendency, and even in the same product, handling is not easy, such as a difference in deodorizing performance depending on the sampling location, and processing efficiency may be deteriorated.

  INDUSTRIAL APPLICATION Since this invention can provide the deodorizer for fibers excellent in product stability and excellent in compatibility with various functional processing chemicals, it is industrially useful.

Claims (3)

(A) Fine particles of silicon dioxide or a composite of silicon dioxide and zinc oxide, and (B) a compound represented by the following general formula (1) and general formula (2), having an average molecular weight of 400 to 50, And at least one selected from the group consisting of compounds having an ethyleneoxy group of 40% by mass or more with respect to the molecular weight of the compound.

(In the above formula, R ¹ , R ² and R ³ may be the same or different, and each represents hydrogen, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or- (A ¹ O) _n H, R ⁴ represents an alkylene group having 2 to 10 carbon atoms, m represents 0, 1 or 2, and when m is 2, a plurality of R ³ may be the same or a phase The plurality of R ⁴ may be the same or different, A ¹ represents an alkylene group having 2 to 4 carbon atoms, and n represents an alkylene represented by (A ¹ O). The average number of moles added of the oxy group is 2 to 550, and the plurality of A ¹ may be the same or different)

(In the above formula, R ⁵ represents an alkyl group having 1 to 21 carbon atoms or an alkenyl group having 2 to 21 carbon atoms, and R ⁶ represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or — (A ² O) _p H R ⁷ represents hydrogen, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or — (A ² O) _p H, and R ⁸ represents an alkylene group having 2 to 10 carbon atoms. , O represents 0, 1 or 2, and when o is 2, a plurality of R ⁷ may be the same or different, and a plurality of R ⁸ may be the same or different. , A ² represents an alkylene group having 2 to 4 carbon atoms, p is an average addition mole number of an alkyleneoxy group represented by (A ² O), and represents ² to 550, and a plurality of A ² are the same Or it may be different) In the compound represented by the general formula (1), at least one of R ¹ and R ² is — (A ¹ O) _n H, R ³ is — (A ¹ O) _n H or hydrogen, and R ⁴ is An alkylene group having 2 to 4 carbon atoms, m is 0 or 1, R ⁷ is — (A ² O) _p H in the compound represented by the general formula (2), and R ⁸ is 2 carbon atoms. The fiber deodorant according to claim 1, which is an alkylene group of ˜4 and o is 0 or 1.   A deodorant fiber product obtained by treatment with a treatment liquid containing the fiber deodorant according to claim 1.