JP2014159660A - Method of manufacturing functional fiber product and ultraviolet absorber for fiber using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a functional fiber product having no hue change by coloring specific to an ultraviolet absorber, and good ultraviolet absorption property with washing resistance, water absorption property and flexibility, and to provide the ultraviolet absorber for a fiber for obtaining the functional fiber product.SOLUTION: A fiber product is treated with (A) an acrylate compound having 2 phenyl groups and (B) a compound which is a copolymer of a polymerizable vinyl monomer having a triazole ring and a phenol group, or a copolymer of the polymerizable vinyl monomer and the other vinyl monomer polymerizable with the same. Further in addition to (A) and (B), (C) at least one kind of compound selected from a group consisting of amino modified silicone and an alkylene oxy-containing compound is treated on the fiber product.

Description

The present invention relates to a fiber for UV absorbers used in the production method and the method for producing a functional fiber products.

  For the purpose of preventing deterioration and hue change of textiles due to ultraviolet rays, treatment of the textiles with ultraviolet absorbers is performed. In recent years, there are concerns about adverse effects on the skin due to an increase in the amount of ultraviolet rays due to the destruction of the ozone layer, and there is an increasing demand for treatment of ultraviolet absorbents on textiles for the purpose of reducing the amount of UV exposure to the human body. UV absorbers are used (Patent Documents 1 to 3).

  However, the compound as in Patent Document 1 is a high-melting ultraviolet absorber, and when an aqueous dispersion of this compound is processed into a fiber product, the flexibility is lowered (expression of roughness), the water absorption is lowered, and the drying is performed. There is a problem that solid UV absorbers powder later on the surface of the textile. In order to prevent these problems, the ultraviolet absorber can be used only at an extremely low concentration, and in this case, a sufficient ultraviolet absorbing effect cannot be obtained. Furthermore, some solid ultraviolet absorbers have a specific coloration, and there is a problem that the hue of the functional fiber product may change.

Although the polymer type ultraviolet absorber as in Patent Document 2 can impart a good ultraviolet absorption effect with washing resistance to the textile, it reduces the flexibility and water absorption of the functional textile. There's a problem.
Moreover, in the liquid ultraviolet absorber as in Patent Document 3, the change in the hue of the functional fiber product is small and the flexibility and water absorption are not lowered, but the washing resistance is not sufficient.

Japanese Patent Laid-Open No. 2-17583 JP-A-4-316679 JP 2012-167382 A

The present invention has been made in view of the above circumstances, and there is no hue change due to coloring characteristic of an ultraviolet absorber, and a functional fiber having good ultraviolet absorption, water absorption and flexibility that is wash-resistant. It aims at providing the manufacturing method of a product.
Another object of the present invention is to provide an ultraviolet absorbent for fibers for obtaining the functional fiber product described above.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have demonstrated that the two kinds of compounds having a specific structure are processed into a textile product, each of which has not been able to be exerted alone, and has laundry resistance. It was found that a functional fiber product having good UV absorption, water absorption and flexibility, and having no change in hue of the fiber product due to coloring characteristic of the UV absorber can be obtained, and the present invention was completed based on this finding. It was.

  Therefore, the present invention provides a compound (A) represented by the following general formula (1) and a polymer of a polymerizable vinyl monomer represented by the following general formula (2), or a copolymer thereof with this polymerizable vinyl monomer. Provided is a method for producing a functional fiber product, which comprises treating a compound (B), which is a copolymer with other possible vinyl monomers, into a fiber product.

(In the above formula, R ¹ and R ² are each independently in the para-position or meta-position, and each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ³ is a carbon atom having 1 to 22 carbon atoms. Represents a hydrogen group, and R ⁴ represents a hydrogen atom or a -CN group)

(In the above formula, R ⁵ represents hydrogen, halogen or methyl group, R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ⁷ represents an alkylene group having 1 to 6 carbon atoms, R ⁸ represents a hydrogen atom or a methyl group)

  In the production method of the present invention, in addition to the compound (A) and the compound (B), at least one compound (C) selected from the group consisting of an amino-modified silicone and an alkyleneoxy group-containing compound is used as a fiber product. It is preferable to process.

  The amino-modified silicone is preferably a compound represented by the following general formula (3), and the alkyleneoxy group-containing compound is a compound represented by the following general formula (4), (a) an organic polyisocyanate and (b A) an aqueous polyurethane resin obtained by reacting at least one compound selected from the group consisting of mono- and / or polyalkylene glycols and polyether polyols with (c) a chain extender; and a polyether group-containing modified silicone. It is preferably at least one selected from the group.

(In the above formula, a plurality of R ⁹ may be the same as or different from each other, each independently represents a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ¹⁰ has 1 to 8 carbon atoms. A plurality of R ¹¹ may be the same as or different from each other, and each independently represents a monovalent hydrocarbon group having 1 to 5 carbon atoms, a hydroxyl group, 1 to carbon atoms. 5 an alkoxy group or a group represented by the formula —R ¹⁰ — (NHCH ₂ CH ₂ ) cNHR ¹² (wherein R ¹⁰ is the same as defined above, and c is 0 or an integer of 1 to 10). R ¹² represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, a is an integer of 5 to 10,000, and b is 0 or an integer of 1 to 1,000)

(In the above formula, R ¹³ represents an —OH group or — (R ¹⁴ O) dOH group, R ¹⁴ represents an alkylene group having 2 to 4 carbon atoms, d is an integer of 1 to 200, and d is 2) In the above case, a plurality of (R ¹⁴ O) may be the same as or different from each other, and when two or more (R ¹⁴ O) are present, they may be randomly added. It may be a block addition, e is an integer of 2 to 100, and a plurality of R ¹⁶ existing in one molecule may be the same as or different from each other, and each independently represents a hydrogen atom or — SO ₃ X group (X represents a hydrogen atom, an alkali metal atom or an amine group), a plurality of d's present in one molecule may be the same as or different from each other, and R ¹⁵ is a hydrogen atom. Atom or following formula (5):

(R ¹⁶ in the above formula represents the same as defined above)
Represents a group represented by

  The compounding ratio (mass basis) of the compound (A) and the compound (B) is preferably (A) :( B) = 95: 5 to 5:95, and the compound (A) and the compound (B) And the compounding ratio (mass basis) of the compound (C) is preferably (A + B) :( C) = 100: 5 to 100: 200.

  The present invention also provides a compound (A) represented by the general formula (1) and a polymer of the polymerizable vinyl monomer represented by the general formula (2), or a copolymer thereof and the polymerizable vinyl monomer. Provided is an ultraviolet absorbent for fibers, which is used in the method for producing a functional fiber product, comprising a compound (B) which is a copolymer with other possible vinyl monomers.

  The ultraviolet absorbent for fibers of the present invention preferably contains at least one compound (C) selected from the group consisting of an amino-modified silicone and an alkyleneoxy group-containing compound together with the compound (A) and the compound (B). .

  In the ultraviolet absorbent for fibers of the present invention, the amino-modified silicone is preferably a compound represented by the general formula (3), and the alkyleneoxy group-containing compound is a compound represented by the general formula (4), An aqueous polyurethane resin obtained by reacting (a) an organic polyisocyanate, (b) at least one compound selected from the group consisting of mono- and / or polyalkylene glycols and polyether polyols, and (c) a chain extender. And at least one selected from the group consisting of polyether group-containing modified silicones.

  Moreover, it is preferable that the compounding ratio (mass standard) of the said compound (A) and a compound (B) is (A) :( B) = 95: 5-5: 95, The said compound (A) and a compound ( The blending ratio (mass basis) of the sum of (B) and the compound (C) is preferably (A + B) :( C) = 100: 5 to 100: 200.

  According to the present invention, two kinds of compounds (A) and (B) having a specific structure are processed into a textile product, thereby having good UV absorption, water absorption and flexibility with washing resistance. A functional fiber product can be obtained. Moreover, the said effect can be improved by using a specific compound (C) together.

A preferred embodiment of the present invention will be described below.
Compound (A)
The compound (A) used in the present invention, when combined with the compound (B), can synergistically impart UV-absorbing, water-absorbing and softness to a textile product with laundry resistance. It is represented by the general formula (1).

In the general formula (1), the hydrocarbon group having 1 to 8 carbon atoms represented by R ¹ and R ² may be saturated or unsaturated, and may be linear or branched. There may be. The hydrocarbon group having 1 to 22 carbon atoms represented by R ³ may be saturated or unsaturated, and may be linear or branched.

From the viewpoint of ultraviolet absorption, flexibility and water absorption of the functional fiber product, in the compound represented by the general formula (1), R ¹ and R ² are hydrogen atoms, and R ³ has 4 to 4 carbon atoms. 22 branched alkyl groups, R ⁴ is preferably a —CN group, and R ³ is more preferably a 2-ethylhexyl group.

  In the present invention, the compound represented by the general formula (1) is preferably hydrophobic. Here, hydrophobic refers to not being emulsified, dispersed or dissolved when 1 g of compound is added to 100 g of ion exchange water at 20 ° C. and mixed. When it is not hydrophobic, the washing resistance of the functional fiber product tends to be inferior. In the following, unless otherwise specified, “emulsification dispersion or dissolution” is described as “emulsion dispersion”, “emulsification dispersion or solubility” is described as “emulsification dispersion”, and “water emulsion dispersion or “Aqueous solution” is referred to as “water-emulsified dispersion”.

Moreover, it is preferable that the compound represented by General formula (1) is liquid at 20 degreeC. Here, the liquid state means that the viscosity measured at 20 ° C. using a BH viscometer (manufactured by Tokimec) is 50,000 mPa · s or less. In the present invention, those having a viscosity of 50,000 to 100 mPa · s can be used, and among them, those having a viscosity of 20,000 to 100 mPa · s are preferable, and 10,000 to 1,000 mPa · s are more preferable. . When the viscosity exceeds 50,000 mPa · s, handling tends to be difficult, and when it is less than 100 mPa · s, the washing resistance tends to be inferior.
As for the compound represented by the general formula (1), one type may be used alone, or two or more types may be used in combination.

  Commercially available products can be used as the compound represented by the general formula (1), and examples include Seesorb 502 (manufactured by Sipro Kasei Co., Ltd.), Chisorb 336 (manufactured by DOUBLE BOND CHEMICAL IND. CO., LTD), and the like.

Compound (B)
The compound (B) used in the present invention, when combined with the compound (A), can synergistically impart UV-absorbing, water-absorbing, and softness with washing resistance to textiles. It is a polymer of a polymerizable vinyl monomer represented by the formula (2) or a copolymer of this polymerizable vinyl monomer and another vinyl monomer copolymerizable therewith.

  In the compound (B), specific examples of the polymerizable vinyl monomer represented by the general formula (2) include 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] benzotriazole, 2- [ 2′-hydroxy-5 ′-(acryloyloxyethyl) phenyl] benzotriazole, 2- [2′-hydroxy-3′-t-butyl-5 ′-(methacryloyloxyethyl) phenyl] benzotriazole, 2- [2 '-Hydroxy-3'-methyl-5'-(acryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -5-chlorobenzotritriazole, 2- [2′-Hydroxy-5 ′-(acryloyloxybutyl) phenyl] -5-methylbenzene Zotoriazoru and the like.

  One type of the polymerizable vinyl monomer represented by the general formula (2) may be used alone, or two or more types may be used in combination. Among these, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotriazole is preferable from the viewpoint of ultraviolet absorption and washing resistance.

  Other vinyl monomers copolymerizable with the polymerizable vinyl monomer represented by the general formula (2) include carboxyl group-containing monomers, (meth) acrylic acid ester monomers, vinyl ether monomers, vinyl ester monomers, styrenic monomers, hydroxyl groups Examples thereof include group-containing monomers, amide group-containing monomers, and cyano group-containing monomers.

  Examples of the carboxyl group-containing monomer include monocarboxylic acid monomers such as (meth) acrylic acid, crotonic acid, cinnamic acid, and atropic acid; dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid. Monomers and acid anhydrides thereof; and dicarboxylic acid monoalkyl ester monomers. Among these, acrylic acid and methacrylic acid are preferable from the viewpoint of ultraviolet absorption and washing resistance.

  Examples of the (meth) acrylate monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) Examples thereof include alkyl esters of 1 to 8 carbon atoms of (meth) acrylic acid such as 2-ethylhexyl acrylate. Among these, alkyl esters having 1 to 4 carbon atoms are preferable from the viewpoints of ultraviolet absorption and washing resistance.

  Examples of the vinyl ether monomer include alkyl vinyl ethers having 1 to 8 carbon atoms such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and 2-ethylhexyl vinyl ether. Among these, alkyl vinyl ethers having 1 to 4 carbon atoms are preferable from the viewpoints of ultraviolet absorption and washing resistance.

  Examples of vinyl ester monomers include vinyl esters having 1 to 8 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate, vinyl caproate, vinyl acrylate, vinyl butyrate, vinyl crotonic acid, vinyl monochloroacetate, etc. Is mentioned. Among these, vinyl esters having a hydrocarbon group having 1 to 4 carbon atoms are preferable from the viewpoints of ultraviolet absorption and washing resistance.

  Styrene monomers include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, o-isopropyl styrene, m- Examples thereof include isopropyl styrene and p-isopropyl styrene. Among these, styrene is preferable from the viewpoints of ultraviolet absorption and washing resistance.

  Hydroxyl group-containing monomers include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxyethylene polyoxypropylene mono (meth) acrylate Glycerol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, (meth) allyl alcohol, glycerol mono (meth) allyl ether, and the like.

As amide group-containing monomers, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-methylol (meth) acrylamide, N-ethylol (meth) Examples include acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, maleic acid amide, and maleic acid imide.
Examples of the cyano group-containing monomer include (meth) acrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like.

  Such other vinyl monomers copolymerizable with the polymerizable vinyl monomer represented by the general formula (2) may be used alone or in combination of two or more. Among these, a styrene monomer is preferable from the viewpoint of ultraviolet absorption and washing resistance. In this specification, (meth) acryl means acryl or methacryl, (meth) acrylate means acrylate or methacrylate, (meth) acrylonitrile means acrylonitrile or methacrylonitrile, (Meth) allyl means allyl or methallyl.

The compound (B) used in the present invention is a copolymer of a polymerizable vinyl monomer represented by the general formula (2) and another vinyl monomer copolymerizable therewith from the viewpoint of ultraviolet absorption and washing resistance. It is preferable that the blending ratio (mass basis) of the polymerizable vinyl monomer represented by the general formula (2): other vinyl monomers copolymerizable = 20: 80 to 60:40, and 30: More preferably, it is 70-50: 50.
When the monomer represented by the general formula (2) is less than 20% by mass, the ultraviolet absorbability of the functional fiber product tends to decrease. When it exceeds 60% by mass, the washing resistance tends to decrease.

  The compound (B) used in the present invention preferably has a weight average molecular weight of 5,000 to 1,000,000, more preferably 10,000 to 800,000. When the weight average molecular weight is less than 5,000, the washing resistance tends to decrease, and when it exceeds 1,000,000, handling tends to be difficult.

The compound (B) used in the present invention uses an aqueous medium from the viewpoint that a polymer having the above molecular weight range can be obtained relatively easily and can be obtained as an aqueous emulsion dispersion having good product stability. Thus, it is preferably obtained by emulsion polymerization in the presence of a polymerization initiator, an emulsifier and, if necessary, a chain transfer agent or a crosslinking agent.

  In this case, the polymerization temperature is preferably 5 to 100 ° C. (more preferably 50 to 80 ° C.), and other conditions and methods may be carried out according to general polymerization conditions and methods, for example, polymerization of monomers and the like. Examples of the addition method to the system include a batch addition method, a continuous addition method, and a divided addition method, and these may be adopted.

  As an aqueous medium, the thing similar to what is described in the water (E) mentioned later can be used. Furthermore, the organic solvent similar to the organic solvent which can be used together with water (E) can be used.

  The polymerization initiator is not particularly limited, and a polymerization initiator generally used in radical polymerization can be used.For example, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide, redox initiator ( Hydrogen peroxide-ferrous chloride, ammonium persulfate-sodium acid sulfite, ascorbic acid (salt), Rongalite, etc.), 1,1-di-t-butylperoxy-2-methylcyclohexane, 2,2-bis (4 4-di-t-butylperoxycyclohexyl) propane, water-soluble azo initiators and the like. Further, radicals may be generated by photopolymerization with ultraviolet rays, electron beams, radiation, or the like. In this case, a photosensitizer or the like may be used.

  As an emulsifier, the thing similar to the thing as described in surfactant (D) mentioned later can be used. In the present invention, in addition to these normal surfactants, a reactive group called a polymerizable group such as a vinyl group or an allyl group, and a hydrophilic group such as a sulfonate group or a polyoxyethylene group Can also be used effectively. In addition, these emulsifiers can be used individually or in mixture of 2 or more types. The added amount of the emulsifier is preferably 0.1 to 10% by mass based on the total monomer amount. If the addition amount is less than 0.1% by mass, the polymerization reaction tends to be poor and the desired polymer cannot be obtained, and if it exceeds 10% by mass, there is no further improvement in performance and this tends to be industrially disadvantageous. There is.

  As chain transfer agents, mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan, tetraethylthiuran sulfide, pentaphenylethane, terpinolene, α- What can be used by normal emulsion polymerization, such as methylstyrene dimer, can be used individually or in combination of 2 or more types. Further, as a method of use, any method of batch addition, divided addition or continuous addition may be used. In addition, it is preferable that the usage-amount of a chain transfer agent shall be 2 mass% or less with respect to the total amount of monomers, More preferably, it is 0.5 mass% or less. When the addition amount exceeds 2% by mass, the durability tends to decrease.

  The crosslinking agent is not particularly limited as long as it is a compound having two or more radically polymerizable double bonds. For example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerin di (meth) Acrylate, glycerin tri (meth) acrylate, diethylene glycol di (meth) acrylate, diallyl phthalate, diallyl malate, diallyl fumarate, allyl (meth) acrylate, N, N'-methylenebis (meth) acrylamide, divinylbenzene, etc. Can be used as needed.

  In addition, pH buffering agents, chelating agents, etc. may be used during polymerization. Examples of pH buffering agents include sodium bicarbonate, sodium carbonate, sodium dihydrogen phosphate, sodium phosphate, sodium acetate, potassium acetate, etc. Examples of the chelating agent include sodium ethylenediaminetetraacetate and sodium nitrilotriacetate.

The compound (B) obtained by such emulsion polymerization may be used as an emulsified dispersion, or the compound (B) may be isolated and used once.
Such a compound (B) used for this invention may be used individually by 1 type, and may be used in combination of 2 or more type.

Compound (C)
The compound (C) used in the present invention is an effect exhibited by the combined use of the compound (A) and the compound (B) (each of which has not been able to be exhibited alone, has good UV absorption with washing resistance, Water absorption and flexibility), which is at least one selected from the group consisting of amino-modified silicones and alkyleneoxy group-containing compounds.

In the amino-modified silicone used in the present invention, part or all of the amino group and / or imino group is preferably blocked, and more preferably 30% or more of the amino group and / or imino group is blocked. .
The amino-modified silicone in which part or all of the amino group and / or imino group is blocked is an amino-modified silicone and two or more compounds selected from compounds capable of reacting with the amino group and / or imino group Doo was reaction is obtained. In the following description, unless otherwise specified, “amino-modified silicone in which part or all of amino group and / or imino group is blocked” is referred to as “blocked amino-modified silicone”, and “amino group and / or “A compound capable of reacting with an imino group” is referred to as an “amino group-blocking compound”.

  The amino-modified silicone used in the present invention contains an amino group and / or an imino group at at least one position selected from the group consisting of a side chain, a terminal and a main chain of dimethylpolysiloxane. The amino-modified silicone used in the present invention may contain a functional group such as an aryl group, an amide group, an alkyl group, an aralkyl group, an alkyloxy group, and a hydroxy group in addition to the amino group and / or imino group. Good.

The amino-modified silicone used in the present invention operates at 25 ° C. from the viewpoint of the mechanical stability of the blocked amino-modified silicone, the good UV-absorbing property with water resistance and flexibility imparted to the functional fiber product. viscosity 10~100,000mm ² / s, more preferably 100~10,000mm ² / s, preferably further preferably in the range of 100~4,000mm ² / s.

Moreover, it is preferable that the refractive index in 25 degreeC is 1.35-1.55, and it is preferable that it is 1.40-1.50.
Moreover, it is preferable that functional group (amino group, imino group) equivalent is 500-5,000 g / mol, and it is more preferable that it is 1000-3,000 g / mol.

Among such amino-modified silicones, those containing an amino group and / or imino group at the side chain and / or terminal are preferable, and compounds represented by the general formula (3) are more preferable. .

In the compound represented by the general formula (3), R ⁹ is a monovalent hydrocarbon group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Although all of R ^{9 in them} may be the same or different, 80% or more of R ⁹ is preferably a methyl group, and more preferably all are methyl groups.

R ¹⁰ is a divalent hydrocarbon group having 1 to 8 carbon atoms, _{e.g., -CH 2 -, - CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH ₃ ) alkylene groups such as —CH ₂ — and — (CH ₂ ) ₄ — and alkylene arylene groups such as — (CH ₂ ) ₂ C ₆ H ₄ —. Among these, —CH ₂ —CH ₂ —CH ₂ — is preferable.

R ¹¹ is a monovalent hydrocarbon group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, or —R ¹⁰ — (NHCH ₂ CH ₂ ) cNHR ¹² , and at least one of R ¹¹ is —R ¹⁰ - _{(NHCH 2} CH ₂₎ in the case of CNHR ¹² is b may also be zero.

R ¹² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and examples of the monovalent hydrocarbon group having 1 to 5 carbon atoms include a methyl group, an ethyl group, and a propyl group. From the viewpoint of the reactivity of the compound represented by the general formula (3) and availability, R ¹² is preferably a hydrogen atom.

  a is preferably 10 to 5,000, and more preferably 100 to 2,000. When a is less than 5, the effect of imparting good washing resistance, UV absorption, water absorption and flexibility tends to be poor, and when it exceeds 10,000, the blocked amino-modified silicone is emulsified and dispersed. There is a tendency to become difficult.

  b is preferably 1 to 500, and more preferably 2 to 100. When b exceeds 1,000, the blocked amino-modified silicone tends to be difficult to emulsify and disperse, and the functional fiber product tends to yellow.

  Examples of the amino group blocking compound include a monocarboxylic acid compound, a dicarboxylic acid compound, an alkylene carbonate compound, and an epoxy compound.

  Examples of the monocarboxylic acid compound include monocarboxylic acids having 1 to 20 carbon atoms, monocarboxylic acid anhydrides or chlorides having a linear alkyl group having 1 to 8 carbon atoms, and preferably 1 to 1 carbon atoms. It is an anhydride or chloride of a fatty acid having 5 linear alkyl groups.

  The dicarboxylic acid compound is a dicarboxylic acid having 2 to 8 carbon atoms which may have a hydroxy group or a cyclic acid anhydride thereof. For example, oxalic acid, malonic acid, maleic acid, maleic anhydride, glutaric acid Adipic acid, fumaric acid, malic acid, succinic acid, succinic anhydride, tartaric acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride and the like.

  Examples of the alkylene carbonate compound include ethylene carbonate, propylene carbonate, isobutylene carbonate, 1,2-butylene carbonate, pentylene carbonate, hexylene carbonate, and the like.

  As an epoxy compound, the glycidyl ether which has a C1-C20 alkyl group or an alkenyl group is mentioned.

  The capped amino-modified silicone used in the present invention can be obtained by reacting the amino-modified silicone and two or more compounds selected from the amino group-capped compounds by an ordinary method. For example, in the reaction between the amino-modified silicone and the monocarboxylic acid compound, it is desirable to react in a temperature range of 50 to 120 ° C. under a nitrogen gas stream. Similarly, in the reaction with the dicarboxylic acid compound, it is desirable to react in the temperature range of 100 to 150 ° C., in the reaction with the alkylene carbonate compound, it is desirable to react in the temperature range of 70 to 140 ° C. In this reaction, it is desirable to react in the temperature range of 70 to 110 ° C.

  In these reactions, within the range of the reaction temperature, the amino-modified silicone and two or more compounds selected from amino group-blocked compounds may be reacted simultaneously, and the amino group and / or You may make it react sequentially, confirming the reaction rate (blocking rate of an amino group and / or imino group) with an imino group and each compound.

  By combining two or more kinds of compounds selected from amino group-blocking compounds and adjusting the reaction rate, good UV-absorbing property, water absorption and flexibility and blocking that are imparted to functional fiber products It is possible to control the performance of the amino-modified silicone such as anti-discoloration, compatibility with concomitant drugs, and mechanical stability. When the blocking ratio of the amino group and / or imino group of the amino-modified silicone is less than 30%, the functional fiber product obtained tends to be easily discolored by heat or light. In particular, in order to increase the compatibility with concomitant drugs such as anionic drugs and the stability of the treatment bath, a combination with a monocarboxylic acid compound, an alkylene carbonate compound or an epoxy compound in the form of a dicarboxylic acid compound as an essential component. It is preferable to select. In addition, in order to improve the compatibility of the blocked amino-modified silicone with the concomitant drug, improve the stability of the treatment bath, or improve the water absorption, the alkylene before and / or after the reaction between the amino-modified silicone and the amino group blocking compound. Oxide (preferably ethylene oxide) may be reacted.

  The ratio of each of the two or more compounds selected from the amino group-blocking compounds varies depending on the type of the compound selected and the degree of reaction with the amino group or imino group. It is preferable to use 10 to 90% by mass of each selected component, and in the case of 3 or more, it is preferable to use 2 to 80% by mass of each selected component. In the present invention, it is not particularly necessary to use a reaction solvent or a catalyst during the reaction.

  The alkyleneoxy group-containing compound used in the present invention is a compound containing an alkyleneoxy group in the compound. The alkyleneoxy group has 2 to 2 carbon atoms from the viewpoint of combined use with concomitant drugs, mechanical stability, good UV absorption with washing resistance imparted to functional fiber products, water absorption and flexibility. 4 alkyleneoxy groups are preferable, and alkyleneoxy groups having 2 to 3 carbon atoms are more preferable.

  Further, the alkyleneoxy group-containing compound preferably contains 10% by mass to 95% by mass of alkyleneoxy groups with respect to the molecular weight of the compound. When the amount is less than 10% by mass, there is a tendency that the effect of improving good UV absorption, water absorption and flexibility with washing resistance is reduced. When the amount exceeds 95% by mass, the viscosity of the alkyleneoxy group-containing compound becomes too high. Tend to be difficult to handle. Such alkyleneoxy group may be used individually by 1 type, and may be used in combination of 2 or more type.

  Such an alkyleneoxy group-containing compound is, for example, selected from the group consisting of a compound represented by the general formula (4), (a) an organic polyisocyanate, and (b) a mono and / or polyalkylene glycol and a polyether polyol. Examples thereof include an aqueous polyurethane resin and a polyether group-containing modified silicone obtained by reacting at least one compound with (c) a chain extender.

  The compound represented by the general formula (4) used in the present invention is an aqueous polyester resin. In the present invention, the aqueous polyester resin refers to a polyester resin in which separation or sedimentation is not observed even when an aqueous emulsified dispersion having an aqueous polyester resin concentration in water of 40% by mass is left at 20 ° C. for 12 hours.

In the general formula (4), R ¹³ represents a HO— group or a HO (R ¹⁴ O) d— group, and R ¹⁴ represents an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include ethylene, trimethylene, propylene, tetramethylene, and butylene, and an ethylene group is particularly preferable from the viewpoint of emulsifying dispersibility in water.

d is an integer of 1-200, and 1-150 is more preferable. When d exceeds the above upper limit, the viscosity of the compound represented by the general formula (4) tends to be too high and handling tends to be difficult. When d is 2 or more, (R ¹⁴ O) may be the same or different, and when (R ¹⁴ O) is 2 or more, it may be random addition or block addition. Good.

e is an integer of 2 to 100, and an integer of 2 to 30 is preferable. When e is less than the lower limit, it becomes difficult to obtain a stable flame-retardant effect. On the other hand, when the above upper limit is exceeded, the viscosity of the compound represented by the general formula (4) tends to be too high and handling tends to be difficult. Another aspect is d a plurality present in the molecule may be the same or different and represent each R ¹⁶ there are a plurality of independently hydrogen or -SO 3 _X groups per molecule, X is hydrogen, an alkali Represents a metal or an amine. Examples of the alkali metal include sodium and potassium. Examples of amines include primary amines such as ammonia, methylamine, ethylamine, propylamine, butylamine, and allylamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, and diallylamine; trimethylamine, triethylamine, Tertiary amines such as tripropylamine and tributylamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.

The compound represented by the general formula (4) includes an aromatic dicarboxylic acid or a derivative thereof, and the following formula (6): HO— (R ¹⁴ O) d—H (wherein R ¹⁴ and d are Can be produced by a known method.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, and alkali metal salts or amine salts of aromatic dicarboxylic acids having a sulfonic acid group such as sulfoterephthalic acid, sulfoisophthalic acid, and sulfophthalic acid. Examples of the derivatives thereof include, for example, dimethyl esters, diethyl esters, dipropyl esters, and dibutyl esters of these aromatic dicarboxylic acids, alkyl esters having 1 to 4 carbon atoms, chlorides of these aromatic dicarboxylic acids, anhydrous anhydrides, and the like. Examples include phthalic acid. These aromatic dicarboxylic acids or derivatives thereof can be used singly or in combination of two or more.

  Examples of the compound represented by the formula (6) include ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, both at both ends. Examples thereof include a random copolymer or block copolymer of ethylene oxide and propylene oxide having a hydroxyl group. These compounds can be used individually by 1 type, and can also be used in combination of 2 or more type.

For example, when R ¹⁴ is ethylene, a polyester resin in which a plurality of d values present in the formula (4) are all the same has a transesterification reaction involving dehydration of the aromatic dicarboxylic acid and polyethylene glycol having a certain molecular weight. Or a transesterification reaction involving removal of methanol between the dimethyl ester of the aromatic dicarboxylic acid and polyethylene glycol having a certain molecular weight. The polyester resin having a repeating unit in which d is 1 in the formula (4) and a repeating unit in which d is 2 or more includes a dihydroxyethyl ester of the aromatic dicarboxylic acid, a polyalkylene glycol having a certain molecular weight, and It can manufacture by performing transesterification reaction with deethylene glycol of.
In the compound represented by the general formula (4), it is preferable that an alkyleneoxy group is contained in an amount of 50% by mass to 90% by mass with respect to the molecular weight of the compound.

The weight average molecular weight of the polyester resin used in the present invention is preferably 5,000 to 200,000, and more preferably 10,000 to 50,000.
When the weight average molecular weight of the polyester resin is less than the lower limit, there is a tendency that the effect of improving the good UV absorption, flexibility and water absorption with washing resistance is reduced. On the other hand, when the upper limit is exceeded, the viscosity of the polyester resin tends to be too high and handling tends to be difficult. The weight average molecular weight of the polyester resin can be determined by gel permeation chromatography using monodispersed polyethylene glycol having a known molecular weight as a measurement standard substance.

The emulsifying dispersibility of the polyester resin is obtained by the hydrophilic group in the polyester resin. A plurality of such polyester resins exist in the formula (4), a method of synthesizing the polyester resin so that at least a part of R ¹⁶ present in the formula (4) is a —SO ₃ X group. It can be obtained by adjusting the proportion of ethyleneoxy groups in (R ¹⁴ O), the polymerization degree d and e, and synthesizing a polyester resin having appropriate hydrophilicity.

  The compound represented by the general formula (4) used in the present invention is not particularly limited, but is a soap-free self-emulsifying / dispersing polyester resin containing no emulsifying dispersant from the viewpoint of fastness of the functional fiber product. Preferably there is.

From the viewpoint of further improving the emulsion dispersion stability of this compound, the emulsion dispersion stability of the ultraviolet absorber for fibers, and the emulsion dispersion stability of the treatment liquid, the compound represented by the general formula (4) used in the present invention. A polyester resin having a sulfonic acid group in addition to an alkyleneoxy group in the compound is preferable. Such a polyester resin contains 4% by mole or more (more preferably 15% by mole or more, particularly preferably 50% by mole or more) of the aromatic dicarboxylic acid used for synthesizing the polyester resin. A polyester resin in which at least part of R ¹⁶ present in the formula (4) prepared by using an aromatic dicarboxylic acid having a sulfonic acid group such as isophthalic acid or sulfophthalic acid is a —SO ₃ X group . The counter cation X of the —SO ₃ X group is not particularly limited, but an alkali metal is preferable from the viewpoint of improving the stability of the emulsified dispersion state.

The aqueous polyurethane resin used in the present invention comprises (a) an organic polyisocyanate, (b) at least one compound selected from the group consisting of mono- and / or polyalkylene glycols and polyether polyols, and (c) a chain extender. It is an aqueous polyurethane resin obtained by reacting.
In the present invention, the aqueous polyurethane resin refers to a polyurethane resin in which separation or sedimentation is not observed even when an aqueous emulsified dispersion having an aqueous polyurethane resin concentration of 40 mass% in water is left at 20 ° C. for 12 hours.

(A) Organic polyisocyanate (a) Organic polyisocyanate used in producing the aqueous polyurethane resin used in the present invention is not particularly limited, and examples thereof include diisocyanate compounds, triisocyanate compounds, tetraisocyanate compounds, and diisocyanate compounds. Modified polyisocyanate compounds such as dimers or trimers can be used.

  Examples of the diisocyanate compound include aliphatic diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3- Alicyclic diisocyanate compounds such as bis (isocyanatomethyl) cyclohexane and 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate; phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 3,3′-dimethyl-4, 4'-biphenylene diisocyanate, 3,3'-dichloro-4,4 - biphenylene diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, aromatic diisocyanate compounds such as tetramethyl xylylene diisocyanate.

  Examples of the triisocyanate compound and the tetraisocyanate compound include triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, and tris (isocyanatophenyl) -thiophosphate.

The modified polyisocyanate compound derived from the diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups. For example, biuret structure, isocyanurate structure, urethane structure, uretdione structure, allophanate structure, trimer Examples thereof include polyisocyanates having a body structure, etc., adducts of aliphatic isocyanates of trimethylolpropane, and polymeric MDI (MDI = diphenylmethane diisocyanate).
These polyisocyanate compounds may be used alone or in combination of two or more.

Among these polyisocyanate compounds, aliphatic polyisocyanates and alicyclic polyisocyanates can be suitably used because the resulting functional fiber products tend to be non-yellowing.
In particular, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and norborane diisocyanate can be suitably used.

(B) At least one compound selected from the group consisting of mono and / or polyalkylene glycol mono and polyether polyols As mono and / or polyalkylene glycol used in producing the aqueous polyurethane resin used in the present invention, The same compounds as those represented by the formula (6) can be used.

  Examples of the polyether polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, bisphenol A, bisphenol S, hydrogenated bisphenol A, aconitic acid, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, Triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2,3-propanetrithiol, monoethanolamine, diethano To compounds having at least two active hydrogens such as amine and triethanolamine, monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, trimethylene oxide, tetramethylene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, etc. Examples thereof include polymers obtained by addition polymerization of one kind or two or more kinds by a conventional method. In this case, the addition polymerization method may be any of homopolymerization, block copolymerization, and random copolymerization.

  At least one compound selected from the group consisting of these mono- and / or polyalkylene glycols and polyether polyols may be used alone or in combination of two or more. Further, the weight average molecular weight of at least one compound selected from the group consisting of such mono- and / or polyalkylene glycols and polyether polyols is preferably 500 to 5,000, and preferably 1,000 to 3 Is more preferable.

(B-1) Other polyols When producing the aqueous polyurethane resin used in the present invention, one of at least one compound selected from the group consisting of (b) mono- and / or polyalkylene glycols and polyether polyols. (B-1) Other polyols can be used as part. Such (b-1) other polyols are not particularly limited as long as they have two or more hydroxyl groups, and polyester polyols, polycarbonate polyols, dimer diols, alcohol-modified silicone oils and the like can be used. it can.

  Examples of the polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, and polybutylene sebacate. Diol, poly-ω-capololactone diol, poly (3-methyl-1,5-pentylene) adipate diol, polycondensate of 1,6-hexanediol and dimer acid, 1,6-hexanediol and adipic acid Examples thereof include a copolycondensate of dimer acid, a polycondensate of nonanediol and dimer acid, a copolycondensate of ethylene glycol, adipic acid and dimer acid, and the like.

  Examples of the polycarbonate polyol include polycarbonate polyols obtained by reacting glycols such as 1,4-butanediol, 1,6-hexanediol, and diethylene glycol with diphenyl carbonate, phosgene, and the like. Examples of such a polycarbonate polyol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, 3-methyl-1,5-pentanediol carbonate diol, poly-1,4-cyclohexanedimethylene carbonate diol, 1,6 -Hexanediol polycarbonate polyol etc. are mentioned.

  Examples of the dimer diol include those mainly composed of a diol obtained by reducing a polymerized fatty acid. Examples of such polymerized fatty acids include Diels-Alder type bimolecular polymerization of unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, dry oil fatty acids, semi-dry oil fatty acids, and lower monoalcohol esters of these fatty acids. What reacted is mentioned.

  The alcohol-modified silicone oil is one in which two or more organic groups having a hydroxy group and / or a hydroxy group are introduced into the terminal and / or side chain of dimethylpolysiloxane. Examples of such alcohol-modified silicone oil include BY16-848, BX16-848B, BX16-001, BX16-002, BX16-003, BX16-004, BX16-005, BX16-006, BX16-007, BX16- 008, BX16-009, BX16-010, BX16-011, BX16-012, SF8427, SF8428, SH3771, SH3746, BY16-036, BY16-027, BY16-038, BY16-018 (above, Toray Dow) Manufactured).

  These other polyols may be used alone or in combination of two or more. Moreover, as a weight average molecular weight of such a polyol, it is preferable that it is 500-5,000, and it is more preferable that it is 1,000-3,000.

  Among these (b) and (b-1), it is at least one selected from the group consisting of mono- and / or polyalkylene glycol, polycarbonate polyol and polyether polyol from the viewpoint of low hydrolysis. From the viewpoint of flexibility of the functional fiber product, alcohol-modified silicone oil is preferable.

(C) Chain extender As the chain extender, various low molecular polyols and low molecular polyamines can be used. Examples of the low molecular polyol include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1 , 6-hexanediol, 3-methyl 1,5-pentanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol and the like. Low molecular weight polyamines include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, hydrazine, piperazine, 2-methylpiperazine, isophoronediamine, norboranediamine, diaminocyclohexylmethane, diaminodiphenylmethane, tolylenediamine, xylylenediamine, Examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and iminobispropylamine. These may be used alone or in combination of two or more.

  The aqueous polyurethane resin used in the present invention has the above-mentioned (a) to (a) to improve the emulsion dispersion stability of the aqueous polyurethane resin, the emulsion dispersion stability of the ultraviolet absorbent for fibers, and the emulsion dispersion stability of the treatment liquid. In addition to the component c), (d) a compound having an anionic group and two or more active hydrogens or (e) a compound having a cationic group and two or more active hydrogens can be used in combination.

  Examples of such a compound (d) having an anionic group and two or more active hydrogens include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2-sulfo-1,3. -Propanediol, 2-sulfo-1,4-butanediol and their ammonium salts, trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, N, N-dimethyldiethanolamine, N, N-diethyl Examples include organic amine salts such as ethanolamine, and alkali metal salts such as sodium and potassium. These may be used alone or in combination of two or more.

  Among these, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and a salt thereof are preferably a compound having a carboxy group and two or more active hydrogens. The total content of the carboxyl group and the carboxylate group is preferably 0.1 to 5.0% by mass, more preferably 0.2 to 4.0% by mass, and 0.5 to 2. Even more preferably, it is 5% by weight.

  When the total content of the carboxy group and the carboxylate group is less than the lower limit, the effect of improving the emulsion dispersion stability of the aqueous polyurethane resin, the ultraviolet absorbent for fibers and the treatment liquid tends to be small, and the upper limit is set. When exceeding, the softness | flexibility of a functional fiber product falls, and there exists a tendency for stability when a cationic compound is used together to become bad.

(E) As the compound having a cationic group and two or more active hydrogens, alkanolamines are preferable, and examples thereof include N-methyldiethanolamine and triethanolamine. Moreover, these may be used independently and may be used in combination of 2 or more type. These can be used by neutralization with various organic acids such as hydrochloric acid, nitric acid, formic acid, acetic acid, etc., or quaternization with dimethyl sulfate, diethyl sulfate, benzyl chloride, epichlorohydrin, and the like. From the viewpoint of light fastness, it is preferable that (d) a compound having an anionic group and two or more active hydrogens is used in combination for the purpose of improving emulsion dispersion stability.
In the aqueous polyurethane resin used in the present invention, it is preferred that the alkylene group in the compound is contained 50 wt% to 95 wt%, and more preferably contained 50 wt% to 90 wt%.

  When (a) an organic polyisocyanate and (b) at least one compound selected from the group consisting of mono- and / or polyalkylene glycols and polyether polyols and (c) a chain extender are reacted, as necessary A reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, or N-methylmorpholine can be added. Moreover, the organic solvent which does not react with an isocyanate group can be added during reaction or after completion | finish of reaction. As such an organic solvent, for example, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, methyl isobutyl ketone and the like can be used.

  The aqueous polyurethane resin used in the present invention can be obtained by using various methods such as a one-shot method and a prepolymer method which are usually used for the synthesis of urethane. That is, at least one compound selected from the group consisting of (I) (a) organic polyisocyanate, (b) mono- and / or polyalkylene glycol and polyether polyol, if necessary, in the organic solvent, (c) chain (II) (a) an organic polyisocyanate and (b) at least one compound selected from the group consisting of mono- and / or polyalkylene glycols and polyether polyols. Thereafter, (c) a method of polymerizing by adding a chain extender and reacting, (III) selected from the group consisting of (a) a part of an organic polyisocyanate and (b) a mono and / or polyalkylene glycol and a polyether polyol After reacting at least one compound, the remaining (a) organic polyisocyanate and Technique such as a method of polymerizing by charged reacting c) a chain extender and the like. At this time, the component (d) or the component (e) can be used as all or part of the chain extender.

  The aqueous polyurethane resin used in the present invention can be made into an aqueous emulsified dispersion of an aqueous polyurethane resin by adding water and emulsifying and dispersing it after synthesizing polyurethane by such a method. Here, the timing of adding water may be after polymerization, or water may be charged at the prepolymer stage of terminal isocyanate, and after emulsification and dispersion, a chain extender may be charged and polymerized. As the chain extender in this case, the above low molecular polyamines are preferable. Further, neutralization of the ionic group may be performed before or after charging water. The solvent used can be removed by increasing the temperature under reduced pressure after emulsification and dispersion. Furthermore, a crosslinking component can be used in combination with the aqueous emulsion dispersion of the aqueous polyurethane resin, if necessary.

The polyether group-containing modified silicone used in the present invention has a polyether group (-(R ¹⁴ O)-) (wherein at least one position selected from the group consisting of side chain, terminal and main chain of dimethylpolysiloxane, R ¹⁴ represents the same as defined above). In this case, the polyether group may be reactive or non-reactive. In addition, the polyether group may be one in which one alkyleneoxy group is addition-polymerized, or two or more alkyleneoxy groups in which block addition polymerization is performed, or one in which random addition polymerization is performed. It does not matter.

  In the polyether group-containing modified silicone used in the present invention, the compound preferably contains 50% by mass to 95% by mass of alkyleneoxy groups.

  In addition to the polyether group, the polyether group-containing modified silicone used in the present invention contains a functional group such as an amino group, an amide group, an epoxy group, an alkyl group, an aralkyl group, an alkyloxy group, or a hydroxy group. It may be. Examples of the polyether group-containing modified silicone used in the present invention include, for example, polyether-modified silicone, amino / polyether-modified silicone, amide / polyether-modified silicone, epoxy / polyether-modified silicone, and alkyl / aralkyl / polyether. Examples thereof include modified silicone, alkyl / polyether-modified silicone, and alkyloxy / polyether-modified silicone.

The polyether-modified silicone contains only a polyether group as a functional group at at least one position selected from the group consisting of a side chain, a terminal, and a main chain of dimethylpolysiloxane.
The kinematic viscosity at 25 ° C. is 10 to 100,000 mm from the viewpoints of compatibility with the concomitant drugs, mechanical stability, good UV absorption with washing resistance imparted to functional fiber products, water absorption and flexibility. ² / s, more preferably 100 to 10,000 mm ² / s, and still more preferably 1,000 to 3,000 mm ² / s.
Moreover, it is preferable that the refractive index in 25 degreeC is 1.35-1.55, and it is preferable that it is 1.40-1.50.
Moreover, it is preferable that HLB value is 5-10, and it is more preferable that it is 6-8.

The HLB value of the silicone compound was determined from the cloudiness number A measured by the following method described on page 324 of “Surfactant Handbook” (edited by Nishiichiro et al., Published by Sangyo Tosho Co., Ltd., 1960). It is calculated by the formula.
HLB value = 0.89 × A + 1.1

  The cloud number A was measured as follows. Dissolve 0.5 g of an evaluation sample (silicone compound) in 5 ml of 98% ethyl alcohol, and titrate with 2% aqueous phenol solution while stirring at 25 ° C., and the end point is when the liquid becomes turbid. The number of ml of 2% aqueous phenol required for the titration is defined as the cloud number A.

  A commercial item can be used as such a polyether modified silicone, for example, X-22-4952, X-22-4727, X-22-6266, KF-351A, KF-352A, KF-353. KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-6191, X-22-4515, KF-6011, KF -6012, KF-6015, KF-6017, KF-6004 (manufactured by Shin-Etsu Chemical Co., Ltd.), FZ-2110, FZ-2191, FZ-2166, FZ-2154, FZ-2120, L-720, SH8700 , L-7002, L-7001, SF8410, FZ-2123, SH8400, FZ-2164, FZ-77, Z-2105, L-7604, FZ-2104, FZ-2162, FZ-2203, FZ-2207, FZ-2208, SH3749, BX16-033, SH3748, BX16-034, BX16-035 (above, Toray Dow Corning Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (above, Momentive Performance Materials Japan GK), L03, L033, L051, L066 (above, made by Asahi Kasei Wacker Co., Ltd.) It is done.

The amino / polyether-modified silicone contains an amino group and / or imino group and a polyether group as functional groups in at least two positions selected from the group consisting of side chain, terminal and main chain of dimethylpolysiloxane. is there.
The kinematic viscosity at 25 ° C. is 10 to 100,000 mm from the viewpoints of compatibility with the concomitant drugs, mechanical stability, good UV absorption with washing resistance imparted to functional fiber products, water absorption and flexibility. ² / s, more preferably 100 to 10,000 mm ² / s, and even more preferably 100 to 4000 mm ² / s.
Moreover, it is preferable that the refractive index in 25 degreeC is 1.35-1.55, and it is preferable that it is 1.40-1.50.
The functional group (amino group, imino group) equivalent is preferably 500 to 5,000 g / mol.

  As such amino / polyether-modified silicone, commercially available products can be used. For example, X-22-3939A (manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-893, FZ-3789 (above, Toray Dow) Corning Inc.), Magnasoft JSS, Magnasoft DermaNT, Magnasoft SRS (Momentive Performance Materials Japan GK).

The amide / polyether-modified silicone contains an amide group and / or imino group and a polyether group as functional groups in at least two positions selected from the group consisting of side chain, terminal and main chain of dimethylpolysiloxane. is there.
The kinematic viscosity at 25 ° C. is 10 to 100,000 mm from the viewpoints of compatibility with the concomitant drugs, mechanical stability, good UV absorption with washing resistance imparted to functional fiber products, water absorption and flexibility. ² / s, more preferably 100~10,000mm ² / s, preferably further preferably in the range of 100~4,000mm ² / s.
Further, the functional group (amino group, imino group) equivalent is preferably 1,000 to 5,000 g / mol.
As such an amide / polyether-modified silicone, a commercially available product can be used, and examples thereof include BY16-891 (manufactured by Dow Corning Toray).

The epoxy / polyether-modified silicone is one in which an epoxy group and a polyether group are introduced as functional groups in at least two positions selected from the group consisting of side chain, terminal and main chain of dimethylpolysiloxane.
The kinematic viscosity at 25 ° C. is 10 to 100,000 mm from the viewpoints of compatibility with the concomitant drugs, mechanical stability, good UV absorption with washing resistance imparted to functional fiber products, water absorption and flexibility. ² / s, more preferably 100~10,000mm ² / s, preferably further preferably in the range of 100~7,000mm ² / s.
Moreover, it is preferable that the refractive index in 25 degreeC is 1.35-1.55, and it is preferable that it is 1.40-1.50.
The functional group (epoxy group) equivalent is preferably 1,000 to 15,000 g / mol.

  As such an epoxy-polyether-modified silicone, commercially available products can be used. For example, X-22-4741, KF-1002 (manufactured by Shin-Etsu Chemical Co., Ltd.), FZ-3736, BY16-876. SF-8421, BY16-845, BY16-863, BY16-865, BY16-866 (above, manufactured by Toray Dow Corning Co., Ltd.), Magnasoft HWS (above, Momentive Performance Materials Japan GK) Can be mentioned.

The alkyl / aralkyl / polyether-modified silicone contains an alkyl group, an aralkyl group, and a polyether group as functional groups in at least three positions selected from the group consisting of side chain, terminal and main chain of dimethylpolysiloxane. is there.
The kinematic viscosity at 25 ° C. is 10 to 10,000 mm from the viewpoints of the compatibility with the concomitant drugs, mechanical stability, good UV absorption with washing resistance imparted to functional fiber products, water absorption and flexibility. ² / s, more preferably 10~5,000mm ² / s, preferably further preferably in the range of 10~1,000mm ² / s.
Moreover, it is preferable that the refractive index in 25 degreeC is 1.35-1.55, and it is preferable that it is 1.40-1.50.
As such alkyl-aralkyl-polyether-modified silicone, commercially available products can be used, for example, X-22-2516 (manufactured by Shin-Etsu Chemical Co., Ltd.), SF8419 (manufactured by Toray Dow Corning Co., Ltd.), etc. Is mentioned.

The alkyl / polyether-modified silicone contains an alkyl group and a polyether group as functional groups at at least two positions selected from the group consisting of side chain, terminal and main chain of dimethylpolysiloxane.
The kinematic viscosity at 25 ° C. is 10 to 100,000 mm from the viewpoints of compatibility with the concomitant drugs, mechanical stability, good UV absorption with washing resistance imparted to functional fiber products, water absorption and flexibility. ² / s, more preferably 100 to 10,000 mm ² / s, and still more preferably 1,000 to 3,000 mm ² / s.
Moreover, it is preferable that the refractive index in 25 degreeC is 1.35-1.55, and it is preferable that it is 1.40-1.50.
A commercial item can be used as such an alkyl polyether modified silicone, for example, TSF4450 (above, Momentive Performance Materials Japan LLC) can be mentioned.

The alkyloxy / polyether-modified silicone contains an alkyloxy group and a polyether group as functional groups at at least two positions selected from the group consisting of side chain, terminal and main chain of dimethylpolysiloxane.
The kinematic viscosity at 25 ° C. is 10 to 100,000 mm from the viewpoints of compatibility with the concomitant drugs, mechanical stability, good UV absorption with washing resistance imparted to functional fiber products, water absorption and flexibility. ² / s, more preferably 100 to 10,000 mm ² / s, and even more preferably 100 to 3,000 mm ² / s.
Moreover, it is preferable that the refractive index in 25 degreeC is 1.35-1.55, and it is preferable that it is 1.40-1.50.
A commercial item can be used as such alkyloxy polyether modified silicone, for example, KF-889 (above, Shin-Etsu Chemical Co., Ltd. product) can be mentioned.
Such a compound (C) used for this invention may be used individually by 1 type, and may be used in combination of 2 or more type.

  In this invention, it is preferable that the compounding ratio (mass standard) of the said compound (A) and the said compound (B) is (A) :( B) = 95: 5-5: 95, 35: 65- More preferably, it is 15:85. When the compound (A) exceeds 95% by mass, the washing resistance of the functional fiber product tends to decrease. When the compound (A) is less than 5% by mass, in addition to the decrease in flexibility and water absorption, a fluorescent dye is used. In this case, the effect of the fluorescent dye tends to be hindered.

  In the present invention, the blending ratio (mass basis) of the total of the compound (A) and the compound (B) and the compound (C) is (A + B) :( C) = 100: 5 to 100: 200. It is preferable that the ratio is 100: 30 to 100: 100. When the compound (C) is less than the lower limit, the effect of improving good UV absorption, water absorption and flexibility with washing resistance tends to be small. When the upper limit is exceeded, there is little improvement in performance and it is not economical.

The functional fiber product of the present invention can be obtained by treating the compound (A) and the compound (B) into a fiber product.
As a method of treating the compound (A) and the compound (B) into a textile product, a method of treating the compound (A) and the compound (B) simultaneously in one step (AB1 step), or any one of the compounds The method in 2 processes (AB2 process) which processes the other compound after processing can be mentioned.

  When the compound (C) is used in combination, a method in which the compound (A), the compound (B) and the compound (C) are simultaneously treated in one step (ABC1 step), a method in which the compound (C) is treated in two steps (ABC2 step), 3 The method of processing at a process (ABC3 process) can be mentioned.

  The compound (A), the compound (B), and the compound (C) are preferably used in a state where they are emulsified and dispersed in an aqueous medium from the viewpoint of easy treatment of the fiber product. In this case, the water emulsified dispersion may be used as it is as the treatment liquid, or may be diluted with an aqueous medium or added to the treatment bath to obtain a treatment liquid.

  The aqueous medium is preferably water or a mixed solvent of water and a hydrophilic solvent miscible with water. As the water, ion-exchanged water or distilled water can be suitably used. Examples of the hydrophilic solvent include methanol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, hexylene glycol, glycerin, butyl glycol, butyl diglycol, solfit, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, and the like. It is done.

  In order to emulsify and disperse the compound (A), the compound (B) and the compound (C) used in the present invention in an aqueous medium, a conventionally known emulsifying disperser may be used. Conventionally known emulsifiers and dispersers are not particularly limited, and emulsifiers such as milders, homogenizers, ultrasonic homogenizers, homomixers, bead mills, pearl mills, dyno mills, Aspec mills, basket mills, ball mills, nanomizers, optimizers, starbursts, etc. A disperser can be mentioned. One type of these emulsifying and dispersing machines may be used, or two or more types may be used in combination.

  The compound (A), the compound (B), the compound (C) or the treatment liquid containing them preferably has a 50% cumulative particle size of 0.05 to 10 μm from the viewpoint of emulsion dispersion stability and its improving effect. 0.1 to 3 μm is more preferable, and 0.1 to 2 μm is even more preferable.

The treatment liquid used in the AB1 step can be prepared using the ultraviolet absorbent for fibers of the present invention containing the compound (A) and the compound (B), and the compound (A), the compound (B), and Can also be used to prepare.
In the AB2 step, either (A) or (B) may be processed first.

The treatment liquid used in the ABC1 step can be prepared using the ultraviolet absorbent for fibers of the present invention containing the compound (A), the compound (B), and the compound (C). Moreover, it can also prepare using any 2 types of compounds chosen from the group of a compound (A), a compound (B), and a compound (C), and the remaining 1 type of compound. In this case, since the ultraviolet absorber for fibers of the present invention containing the compound (A) and the compound (B) can be used, the treatment is not complicated, and further, the compound (A) and the compound (B) From the viewpoint that it is easy to change the amount of the compound (C) used with respect to the total, the ultraviolet absorber for fibers of the present invention containing the compound (A) and the compound (B), and the compound (C) It is preferable to prepare using
Moreover, it can also prepare using a compound (A), a compound (B), and a compound (C).

  As a method of treating in the ABC2 step, any one compound in the group of the compound (A), the compound (B) and the compound (C) is treated in the first step, and then the remaining two compounds are treated in the first step. Examples thereof include a method of simultaneously treating in two steps, or a method of treating any two kinds of compounds simultaneously in the first step and then treating the remaining one compound in the second step. Among these, since the ultraviolet absorber for fibers of the present invention containing the compound (A) and the compound (B) can be used, the total treatment of the compound (A) and the compound (B) from the viewpoint that the treatment is not complicated. On the other hand, from the viewpoint that the amount of the compound (C) used can be changed as appropriate, and from the viewpoint of good ultraviolet absorption, water absorption and flexibility with washing resistance, the compound (C) is first. A method of treating the compound (A) and the compound (B) simultaneously in the second step after treating in the step is preferred. In this case, the treatment liquid used in the second step can be the same as the treatment liquid used in the AB1 step.

The method of treating in the ABC3 step is a method of treating the compound (A), the compound (B) and the compound (C) separately. The order of treatment in this case may be any order, but from the viewpoint of good UV absorption, water absorption and flexibility with washing resistance, a method of treating compound (C) in the first step It is preferable that
In any treatment, a heat treatment step such as drying or curing may be inserted after each step.

  The water emulsified dispersion and / or treatment liquid may further contain a surfactant as the component (D) from the viewpoint of emulsion dispersion stability. The component (D) is not particularly limited as long as it can improve the emulsion dispersion stability, and at least one of known nonionic surfactants and anionic surfactants can be used.

Nonionic surfactants include alcohols, polycyclic phenols, aliphatic amines having 8 to 44 carbon atoms, fatty acid amides having 8 to 44 carbon atoms, fatty acids having 8 to 24 carbon atoms, polyhydric alcohol fatty acid esters, fats and oils And an alkylene oxide adduct of polypropylene glycol.
Among these, from the viewpoint of treatment bath stability, an alkylene oxide adduct of alcohols and an alkylene oxide adduct of polycyclic phenols are preferable.

Examples of alcohols include alcohols having 8 to 24 carbon atoms or alkenols.
As polycyclic phenols, monovalent phenols such as phenol and naphthol which may have a hydrocarbon group having 1 to 12 carbon atoms or styrenes thereof (styrene, α-methylstyrene, vinyltoluene) addition Or their benzyl chloride reactants.

Examples of monovalent phenols include phenol, 4-cumylphenol, 4-phenylphenol, 2-naphthol, and the like.
The molar ratio of monovalent phenols to styrenes or benzyl chloride is preferably 1: 1 to 10, and more preferably 1: 3 to 8.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin and the like. Among these, ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable from the viewpoint of treatment bath stability. preferable.
Examples of the addition method of alkylene oxide include single addition, block addition, random addition, and the like, but a method of adding ethylene oxide alone is preferable.
The number of moles of alkylene oxide added is preferably 1 to 200, more preferably 10 to 100, and even more preferably 10 to 50. When the added mole number of alkylene oxide is less than 1 mole, the treatment bath stability tends to deteriorate, and when it exceeds 200 mole, the washing resistance of the functional fiber product tends to deteriorate.

  Examples of the anionic surfactant include an anionized product of the nonionic surfactant, a linear or branched C8-24 alcohol or alkenol anionized product, a sulfonated product of oils and fats, an alkylbenzene sulfonic acid, and an alkylnaphthalene sulfonic acid. And a formalin condensate of naphthalenesulfonic acid or a salt thereof.

There is no restriction | limiting in particular in the process to the textiles of the said processing liquid, For example, it can implement by well-known methods, such as a pad method, an immersion method, and a spray method.
In the case of the pad method, the fiber product may be immersed in the treatment liquid and adjusted to a predetermined pickup amount using a mangle or the like. In the case of the immersion method, it is dehydrated after being treated at a predetermined temperature for a predetermined time using a dyeing machine generally used, that is, a winch, a liquid dyeing machine, a zicker, a cheese dyeing machine, a skein dyeing machine, etc. That's fine.

  You may dry after processes, such as a pad, immersion, and spraying. There are no particular limitations on the drying conditions. For example, the drying may be performed at 0 to 200 ° C. for 10 seconds to several days. If necessary, a heat treatment (curing) may be performed after drying at a temperature of 100 ° C. or higher, preferably about 110 to 180 ° C. for 10 seconds to 10 minutes, preferably about 30 seconds to 3 minutes.

  As a provision amount, it is preferable that the sum total of a compound (A), a compound (B), and the compound (C) depending on the case is 0.1-10 mass% with respect to fiber mass. If it is less than 0.1% by mass, it is difficult to exhibit good UV absorption, water absorption and flexibility with washing resistance, and even if it is used in excess of 10% by mass, there is little improvement in performance and it is not economical. .

  The treatment of the treatment liquid into the fiber product can be processed alone into the fiber product, but can also be used in steps such as dyeing and finishing. In this case, dyes or inorganic or organic chemicals usually used in dyeing baths or finishing baths can be used without any problem.

  There are no particular limitations on the material of the textile product that can be treated with the treatment liquid according to the present invention, and various examples can be given. For example, natural fibers such as cotton, kapok, flax, hemp, cannabis, jute, manila hemp, sisal hemp, wool, cashmere, mohair, alpaca, camel hair, silk, feathers, etc., regenerated fibers such as rayon, polynosic, cupra, tencel, Cellulose acetate fiber, semi-synthetic fiber such as Promix, polyamide fiber, polyester fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyurethane fiber, polyoxymethylene fiber, polytetrafluoroethylene fiber, benzoate fiber, Synthetic fibers such as polyparaphenylenebenzbisthiazole fiber, polyparaphenylenebenzbisoxazole fiber, polyimide fiber, asbestos, glass fiber, carbon fiber, alumina fiber, silicon carbide fiber, boron fiber, Tyranno fiber, inorganic fiber Scar, rock fibers, inorganic fibers such as slag fibers, mention may be made of these composite fibers, the fiber products made of mixed fibers.

  Among these, cellulose fibers including cellulose fibers such as cotton, hemp, rayon, polynosic, cupra, and Tencel (trademark) are preferable. The cellulose fiber preferably contains 30% or more of the above cellulose fiber, more preferably 50% or more, and even more preferably 65% or more.

In this way, by using cellulosic fiber products in particular as fiber products, functional fibers with UV-absorbing effect that are wash-resistant without hindering the water absorption and flexibility inherent in cellulosic fiber products You can get a product.
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 woven fabric, a knitted fabric, a cotton, a sliver, a top, a nonwoven fabric, a synthetic paper etc. can be mentioned.

  The ultraviolet absorber for fibers of the present invention is used in the method for producing a functional fiber product, and includes the compound (A) and the compound (B). It is preferable that the ultraviolet absorbent for fibers of the present invention further contains the compound (C). As such a compound (A), a compound (B), and a compound (C), the same thing as what is used in the manufacturing method of the said functional fiber product can be used, and those compounding quantities are the said, Is the same.

  In the ultraviolet absorber for fibers of the present invention, the surfactant (D) is contained in an amount of 0.1 to 30% by mass with respect to the total of the component (A), the component (B), and optionally the component (C). Is preferable, and it is more preferable to contain 0.5-10 mass%. When the amount of the surfactant (D) used is less than the lower limit, the emulsifying dispersibility of the ultraviolet absorbent for fibers of the present invention tends to be poor. When the upper limit is exceeded, the ultraviolet absorbing effect, the softening effect, and Various fastnesses of functional fiber products tend to decrease.

The 50% cumulative particle size of the ultraviolet absorbent for fibers of the present invention 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 50% cumulative particle diameter exceeds 10 μm, the product stability of the ultraviolet absorbent for fibers tends to be lowered. On the other hand, when the average particle size is smaller than 0.05 μm, the effect of further improving the product stability of the ultraviolet absorbent for fibers is small, and it takes time to make fine particles, which is economically disadvantageous.
The 50% cumulative particle size is measured by using a laser diffraction type / scattering type particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.), and the percentage integrated value of the particle size of the ultraviolet absorber for fibers is 50% from the small particle size side. Can be measured by setting the particle size of the particles to 50% cumulative particle size.

  The ultraviolet absorbent for fibers of the present invention includes conventionally known ultraviolet absorbents, antioxidants, penetrants, softeners, water and oil repellents, flame retardants, fixing agents, antibacterial agents, antifouling agents, antistatic agents, and water absorbing agents. An agent or the like may not be blended to such an extent that the effects of the present invention are not hindered, and these agents may be treated before or after processing the ultraviolet absorbent for fibers of the present invention into a fiber product.

  In the ultraviolet absorbent for fibers of the present invention, the total of the compound (A), the compound (B) and, in some cases, the compound (C) is preferably 5 to 50% by mass. More preferably, it is 15-35 mass%. If it is less than 5% by mass, the product stability tends to decrease or a functional fiber product with good performance tends not to be obtained. If it exceeds 50% by mass, the viscosity tends to be high and the handling tends to be difficult. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not restrict | limited at all by these Examples.

Preparation Example 1
As a compound represented by the general formula (1), 20 parts by mass of 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate (trade name Seesorb 502, manufactured by Cypro Kasei Co., Ltd., 20 ° C. viscosity = 4600 mPa · s), poly 5 parts by mass of oxyethylene polycyclic phenyl ether (trade name: New Coal 610, manufactured by Nippon Emulsifier Co., Ltd., HLB = 13.8) is charged into an emulsification container and heated to 80 ° C. while stirring and mixing. 80 ° C. hot water (75 parts by mass) was gradually added to the mixture while stirring and mixing, followed by homogenizer treatment at the same temperature. Thereafter, the mixture was cooled to 20 ° C. to obtain a water-emulsified dispersion of compound (A) (concentration of compound (A) 20.0 mass%, average particle size 0.1 μm).
In the present invention, the average particle size is measured with a laser diffraction type / scattering type particle size distribution measuring device LA-920 (manufactured by Horiba, Ltd.), and the particle size (median particle size) having a percentage integrated value of 50%. Was the average particle size (μm).

Preparation Example 2
In a reaction vessel, 67 parts by mass of water, 2 parts by mass of polyoxyethylene polycyclic phenyl ether (trade name New Coal 610, manufactured by Nippon Emulsifier Co., Ltd., HLB = 13.8), 12 parts by mass of styrene, General Formula (2) As a compound to be represented, 8 parts by mass of 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] benzotriazole (trade name RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) was charged, and 95 ° C. under a nitrogen stream. × Emulsification was performed for 30 minutes.
Next, an aqueous solution of 0.2 parts by mass of ammonium persulfate and 10.8 parts by mass of water was added to the reaction vessel, and reacted at 90 ° C. for 90 minutes to obtain an aqueous emulsion dispersion of compound (B) (compound (B) Concentration of 20.0% by mass, an average particle size of 0.3 μm, and a mass average molecular weight (Mw) of 350,000).

In the present invention, the molecular weight was measured from a polystyrene equivalent calibration curve using gel permeation chromatography. The measurement conditions are as follows.
Apparatus: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSK-gel Super HZ2000 × 30 cm 2 lines, Super HZ4000 × 15 cm 1 flow rate: 0.70 mL / min
Sample concentration: 0.1 g / L
Filtration: 0.45 μm-Millex-LH (Millipore)
Injection volume: 0.200 mL
Temperature: 23 ° C
Detector: differential refractive index detector (RI-8020 manufactured by Tosoh Corporation)

Preparation Example 3
In the general formula (3), R ⁹ and R ¹¹ are methyl groups, R ¹⁰ is — (CH ₂ ) ₃ —, R ¹² is a hydrogen atom, a = 400, b = 8, c = 1, and 1200 mm ² / 150 parts by weight of amino-modified silicone having a viscosity of s and 4 parts by weight of acetic anhydride are charged into a reaction vessel, heated and heated in a nitrogen gas stream, and reacted at a temperature of 100 to 110 ° C. for about 1 hour. 4 parts by weight of an acid was added, and the temperature was further increased by heating. After completion of the reaction, the reaction mixture was cooled, 17 parts by weight of Softanol 50 (manufactured by Nippon Shokubai Co., Ltd.), 28 parts by weight of Softanol 90 (manufactured by Nippon Shokubai Co., Ltd.), 40 parts by weight of Softanol 120 (manufactured by Nippon Shokubai Co., Ltd.), 757 water Mass parts were added and emulsified to obtain a water-emulsified dispersion of blocked amino-modified silicone (concentration of blocked amino-modified silicone of 15.6% by mass, average particle size of 0.1 μm or less).

Preparation Example 4
In a reaction vessel equipped with a stirrer, a thermometer, a methanol outflow tube, and a rectification tube, 87.3 parts by mass (0.45 mol) of dimethyl terephthalate and 14.8 parts by mass of sodium dimethyl 5-sulfoisophthalate (0. 05 mol), 310 parts by mass (0.1 mol) of polyethylene glycol (average molecular weight: 3100), 68.2 parts by mass (1.1 mol) of monoethylene glycol and 0.1 part by mass of antimony trioxide, 0. 1 part by mass was charged and N ₂ gas was introduced. Next, after heating this mixture to 130 degreeC, it heated up from 130 degreeC to 180 degreeC in 2 hours, and transesterification was performed. Further, the temperature was raised from 180 ° C. to 250 ° C. over 2 hours, and then the N ₂ gas flow was stopped. Thereafter, the pressure was reduced and the reaction was carried out at a pressure of 0.7 KPa at 255 ± 5 ° C. for 2 hours, and further the pressure was reduced and the reaction was carried out at a pressure of 0.3 KPa at 260 ° C. for 30 minutes to conduct a transesterification reaction. 425 parts by mass were obtained. The weight average molecular weight of this polyester resin was 15,000. Next, 100 parts by mass of this polyester resin was dissolved in 50 parts by mass of N, N-dimethylformamide, 850 parts by mass of hot water was added and emulsified, and a homogenizer treatment was performed at 80 ° C. Thereafter, the mixture is cooled to 20 ° C. to obtain a water-emulsified dispersion of the compound represented by the general formula (4) (the concentration of the compound represented by the general formula (4) is 10.0% by mass, the average particle size is 2.0 μm). It was.

Preparation Example 5
20 parts by mass of polyether-modified silicone (trade name SH8700, manufactured by Toray Dow Corning Co., Ltd.) and 80 parts by mass of water were charged into a container to obtain a uniform mixture, and an aqueous polyether-modified silicone solution (concentration of polyether-modified silicone 20.0) Mass%).

Preparation Example 6
20 parts by mass of epoxy / polyether-modified silicone (trade name Magnassoft HWS, manufactured by Momentive), 10 parts by mass of SOFTANOL 90, 0.3 part by mass of sodium laurylbenzenesulfonate are charged in a container, and 94.7 parts by mass of water is added. The mixture was emulsified to obtain a water-emulsified dispersion of epoxy / polyether-modified silicone (epoxy / polyether-modified silicone concentration 16.0% by mass, average particle size 0.1 μm or less).

Preparation Example 7
Polypropylene glycol (average molecular weight: 2000, bifunctional) 145.5 parts by mass in reaction kettle, polypropylene glycol (average molecular weight: 1500, trifunctional) 9.9 parts by mass, both-end alcohol-modified silicone oil (average molecular weight 1700, OH equivalent) 1200) 22.5 parts by mass and 10 parts by mass of dimethylformamide were charged and mixed uniformly. 17.8 parts by weight of hexamethylene diisocyanate was charged at 40 ° C. under a nitrogen stream, and reacted at 120 to 130 ° C. until the NCO% became 1.3 to 1.5%. At 80 ° C., 74.4 parts by mass of polyethylene glycol (average molecular weight: 1500, bifunctional) was added and reacted at 130-135 ° C. for 1 hour. 0.002 part by mass of dibutyltin dilaurate was added, and the mixture was further reacted for 1 hour. Add 20 parts by mass of Solfit at 100 ° C. to make the mixture uniform, and add 700 parts by mass of water at 60 ° C. to emulsify, and then water-emulsified dispersion of aqueous polyurethane resin (concentration of aqueous polyurethane resin 27.0% by mass, average particle size) 0.1 μm or less) was obtained.

Preparation Example 8
(2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole) (trade name Seesorb 703, manufactured by Cypro Kasei Co., Ltd.) 30 parts by mass, ethylene of tristyrenated phenol After predispersing 5 parts by mass of sodium sulfate ester salt of an adduct of 20 mol of oxide and 65 parts by mass of water with a stirrer, the mixture was dispersed and stirred with a sand grinder manufactured by Igarashi Machine Manufacturing Co., Ltd. An absorbent concentration of 30.0% by mass and an average particle size of 0.4 μm was obtained.

Preparation Example 9
Except for changing the UV absorber 2- (2'-hydroxy-4'-benzyloxyphenyl) -5-chloro benzotriazole Le performs the same operation as in Preparation Example 8, an ultraviolet absorber water emulsion dispersion A liquid (a concentration of an ultraviolet absorber of 30.0% by mass, an average particle size of 0.4 μm) was obtained.

Preparation Example 10
Preparation Example 8 except that the ultraviolet absorber was changed to [1,4-butanediylbis [oxy (2-hydroxy-4,1-phenylene)] bis (phenylmethanone) (Seees151, manufactured by Cypro Kasei Co., Ltd.) The same operation was carried out to obtain an ultraviolet absorbent aqueous emulsion dispersion (the concentration of the ultraviolet absorbent was 30.0% by mass, the average particle size was 0.3 μm).

Example 1
275 parts by weight of the water-emulsified dispersion of the compound (A) obtained in Preparation Example 1 (55 parts by weight as the compound (A)) and 25 parts by weight of the water-emulsified dispersion of the compound (B) obtained in Preparation Example 2 (5 parts by mass as the compound (B)) was added to obtain the ultraviolet absorbent 1 for fibers of the present invention. The average particle diameter of the ultraviolet absorbent 1 for fibers was 0.3 μm.
The ultraviolet absorbent 1 for fibers was diluted with water to prepare a treatment liquid containing 0.55% by mass of the compound (A) and 0.05% by mass of the compound (B).

A cotton knit bleached cloth (100% knit bleached cotton, 165 g / m ² , purchased from Dyeing Co., Ltd.) is immersed in this treatment solution, squeezed with a roll at a pickup rate of 70%, and dried at 130 ° C. for 2 minutes. The functional fiber product of Example 1 was obtained. Table 1 shows the concentrations of the compound (A) and the compound (B) in the treatment liquid, and the compounding ratio of the compound (A) and the compound (B).
This functional fiber product was evaluated for the UPF value, UV cut rate, water absorption, flexibility, whiteness, and powdering of laundry (JIS L 0217 (1995)) around 10 times. The results are shown in Table 1.

Examples 2-7
Functional fiber products of Examples 2 to 7 were obtained in the same manner as in Example 1 except that the compounds (A) and (B) were changed to the compositions shown in Table 1. Table 1 shows the concentrations of the compound (A) and the compound (B) in the treatment liquid, and the compounding ratio of the compound (A) and the compound (B).
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 1.

Example 8
The aqueous emulsion dispersion of the compound (A) obtained in Preparation Example 1 and the aqueous emulsion dispersion of the compound (B) obtained in Preparation Example 2 are added to a treatment bath, and the compound (A) is added in an amount of 0.15. A functional fiber product of Example 8 was obtained in the same manner as in Example 1 except that a treatment liquid containing 0.5% by mass and 0.45% by mass of compound (B) was prepared. Table 1 shows the concentrations of the compound (A) and the compound (B) in the treatment liquid, and the compounding ratio of the compound (A) and the compound (B).
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 1.

Example 9
The aqueous emulsified dispersion of the compound (A) obtained in Preparation Example 1 was diluted with water to prepare a treatment liquid 1 containing 0.15% by mass of the compound (A). The aqueous emulsion dispersion of the compound (B) obtained in Preparation Example 2 was diluted with water to prepare a treatment liquid 2 containing 0.45% by mass of the compound (B).
A cotton knit-exposed fabric is dipped in treatment liquid 1, squeezed with a roll at a pickup rate of 70%, then dipped in treatment liquid 2, squeezed with a roll at a pickup rate of 70%, and dried at 130 ° C. for 2 minutes. Nine functional fiber products were obtained. Table 1 shows the concentrations of the compound (A) and the compound (B) in the treatment liquid, and the compounding ratio of the compound (A) and the compound (B).
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 1.

Example 10
75 parts by mass of the water-emulsified dispersion of the compound (A) obtained in Preparation Example 1 (15 parts by mass as the compound (A)) and 225 parts by mass of the water-emulsified dispersion of the compound (B) obtained in Preparation Example 2 (45 parts by mass as the compound (B)) was added to obtain an ultraviolet absorbent 2 for fibers of the present invention (average particle size 0.3 μm). This fiber UV absorbent 2 and the blocked amino-modified silicone water emulsified dispersion obtained in Preparation Example 3 were added to a treatment bath, 0.15% by mass of compound (A) and 0.1% of compound (B) were added. A functional fiber product of Example 10 was obtained in the same manner as in Example 1 except that a treatment liquid containing 45% by mass and 0.1% by mass of compound (C) was prepared. Table 2 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 2.

Examples 11-22
Except having changed the compound (A), the compound (B), and the compound (C) to the compositions shown in Table 2, the same operation as in Example 10 was performed to obtain functional fiber products of Examples 11-22. . Table 2 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 2.

Example 23
A water-emulsified dispersion of the compound (A) obtained in Preparation Example 1, a water-emulsified dispersion of the compound (B) obtained in Preparation Example 2, and a water-emulsified dispersion of the compound (C) obtained in Preparation Example 3. And a treatment solution containing 0.15% by mass of compound (A), 0.45% by mass of compound (B), and 0.2% by mass of compound (C). Were operated in the same manner as in Example 10 to obtain a functional fiber product of Example 23. Table 3 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 3.

Examples 24-25
Except having changed compound (A), compound (B), and compound (C) into the composition shown in Table 3, it operated similarly to Example 23 and obtained the functional fiber product of Examples 24-25. . Table 3 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 3.

Example 26
The aqueous emulsified dispersion of the compound (C) obtained in Preparation Example 3 was diluted with water to prepare a treatment liquid 3 containing 0.2% by mass of the compound (C). The ultraviolet absorbent 2 for fibers obtained in Example 10 was diluted with water to prepare a treatment liquid 4 containing 0.15% by mass of the compound (A) and 0.45% by mass of the compound (B). . Table 3 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
A cotton knit-exposed fabric is dipped in the treatment liquid 3, squeezed with a roll at a pickup rate of 70%, then dipped in a treatment liquid 4, squeezed with a roll at a pickup rate of 70%, and dried at 130 ° C. for 2 minutes. 26 functional fiber products were obtained.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 3.

Example 27
The ultraviolet absorbent 2 for fibers obtained in Example 10 was diluted with water to prepare a treatment liquid containing 0.15 g / l of the compound (A) and 0.45 g / l of the compound (B).
Using this treatment solution, a cotton knit-exposed cloth is immersed at 80 ° C. for 30 minutes in a mini-color dyeing machine (manufactured by Teksam Giken Co., Ltd.) at a bath ratio of 1:10, washed with water (once), and dried. (60 ° C. × 30 minutes) to obtain a functional fiber product. Table 4 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), and the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 4.

Example 28
The ultraviolet absorbent 2 for fibers obtained in Example 10 and the water-emulsified dispersion of the blocked amino-modified silicone obtained in Preparation Example 3 were added to the treatment bath, so that the compound (A) was 0.15 g / l. The functional fiber product of Example 28 was prepared in the same manner as in Example 27 except that a treatment liquid containing 0.45 g / l of compound (B) and 0.2 g / l of compound (C) was prepared. Got. Table 4 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), and the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 4.

Examples 29-30
Except having changed the compound (A), the compound (B), and the compound (C) to the compositions shown in Table 4, the same operation as in Example 28 was performed to obtain functional fiber products of Examples 29-30. . Table 4 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), and the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 4.

Example 31
The aqueous emulsified dispersion of the compound (C) obtained in Preparation Example 3 was diluted with water to prepare a treatment liquid 5 containing 0.2 g / l of the compound (C).
Using treatment liquid 5, a cotton knit-exposed cloth was immersed in a mini-color dyeing machine at a bath ratio of 1:10 at 80 ° C. for 30 minutes. Subsequently, it was immersed in the processing liquid 4 obtained in Example 26, squeezed with a roll at a pickup rate of 70%, and dried at 130 ° C. for 2 minutes to obtain a functional fiber product of Example 31. Table 4 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), and the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 4.

Example 32
The ultraviolet absorbent 2 for fibers obtained in Example 10 was diluted with water to prepare a treatment liquid 6 containing 0.15 g / l of the compound (A) and 0.45 g / l of the compound (B). .
Using the treatment liquid 5 obtained in Example 31, a cotton knit-exposed fabric was immersed in a minicolor dyeing machine at a bath ratio of 1:10 at 80 ° C. for 30 minutes. Next, using treatment liquid 6, using a mini color dyeing machine, bathing ratio = 1: 10, soaking at 80 ° C. for 30 minutes, washing with water (once), drying (60 ° C. × 30 minutes), and functionality. A textile product was obtained. Table 4 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), and the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 4.

Example 33
The fiber ultraviolet absorbent 2 obtained in Example 10 was diluted with water to prepare a treatment liquid containing 0.15% by mass of the compound (A) and 0.45% by mass of the compound (B).
The function of Example 33 was carried out in the same manner as in Example 1 except that this treatment liquid was treated with T / C Broad (purchased from Tanigami Shoten Co., Ltd.) instead of the cotton knit bleached cloth. Fiber products were obtained. Table 5 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), and the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 5.

Example 34
The ultraviolet absorbent 2 for fibers obtained in Example 10 and the water-emulsified dispersion of the blocked amino-modified silicone obtained in Preparation Example 3 were added to a treatment bath, and 0.15% by mass of the compound (A) was obtained. The functional fiber product of Example 34 was prepared in the same manner as in Example 33 except that a treatment liquid containing 0.45% by mass of compound (B) and 0.2% by mass of compound (C) was prepared. Got. Table 5 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), and the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 5.

Examples 35-36
Except having changed the compound (A), the compound (B), and the compound (C) to the compositions shown in Table 5, the same operation as in Example 34 was performed to obtain functional fiber products of Examples 35 to 36. . Table 5 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), and the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 5.

Example 37
A functional fiber product of Example 37 was obtained in the same manner as in Example 28 except that T / C broad was used in place of the cotton knit bleached cloth and the minicolor processing temperature was changed to 130 ° C. Table 5 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), and the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 5.

Example 38
A functional fiber product of Example 38 was obtained in the same manner as in Example 31 except that T / C broad was used in place of the cotton knit bleached cloth and the minicolor treatment temperature was 130 ° C. Table 5 shows the concentrations of the compound (A), the compound (B) and the compound (C) in the treatment liquid, the compounding ratio of the compound (A) and the compound (B), and the compound (A) and the compound (B). The usage-amount (mass part) of the compound (C) with respect to a total of 100 mass parts is shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 5.

Comparative Example 1
The operation was performed in the same manner as in Example 1 except that the aqueous emulsion dispersion of the compound (A) obtained in Preparation Example 1 was diluted with water to prepare a treatment liquid containing 0.6% by mass of the compound (A). The functional fiber product of Comparative Example 1 was obtained. In Table 6, the density | concentration of each compound in a process liquid and the compounding ratio of a compound (A) and a compound (B) are shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 6.

Comparative Examples 2-6
The functional fiber products of Comparative Examples 2 to 6 were obtained in the same manner as in Comparative Example 1 except that the ultraviolet absorber shown in Table 6 was used instead of the compound (A). In Table 6, the density | concentration of each compound in a process liquid and the compounding ratio of a compound (A) and a compound (B) are shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 6.

Comparative Example 7
A functional fiber product of Comparative Example 7 was obtained in the same manner as in Comparative Example 1 except that T / C broad was used instead of the cotton knit bleached cloth. In Table 6, the density | concentration of each compound in a process liquid and the compounding ratio of a compound (A) and a compound (B) are shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 6.

Comparative Examples 8-9
The functional fiber products of Comparative Examples 8 to 9 were obtained in the same manner as in Comparative Example 7, except that the ultraviolet absorber shown in Table 6 was used instead of the compound (A). In Table 6, the density | concentration of each compound in a process liquid and the compounding ratio of a compound (A) and a compound (B) are shown.
The functional fiber product was evaluated for UPF value, UV cut rate, water absorption, flexibility, whiteness and powdering after 10 washings. The results are shown in Table 6.

Evaluation test (1) Evaluation of UV absorption effect (UPF value)
According to AS / NZS4399: 1996, Sun protective crossing-Evaluation and classification, UPF value (Ultraviolet Protection Factor) was measured. It is determined that the larger the value, the greater the ultraviolet shielding effect (ultraviolet absorption effect).

(2) Evaluation of UV absorption effect (UV cut rate)
Using a U-3000 spectrophotometer manufactured by Hitachi High-Technologies, the light blocking rate of the functional fiber product was measured in the wavelength range of 280 to 390 nm (every 5 nm), and the average value was taken as the UV cut rate. It is determined that the larger the value, the greater the ultraviolet shielding effect (ultraviolet absorption effect).

(3) Evaluation of Water Absorption According to JIS L 1907 (drop method), one drop of water was dropped on the functional fiber product, and the time (seconds) until the water drop completely disappeared was measured. The shorter the time until the water droplet disappeared, the better the water absorption.

(4) Evaluation of flexibility The flexibility was evaluated by tactile sensation. The evaluation of flexibility was determined based on the following criteria.
S: Very flexible A: Flexible B: Slightly flexible C: Coarse and hard The intermediate position between A and B is denoted as AB, and the intermediate position between B and C is denoted as BC.

(5) Measurement of whiteness Whiteness was measured using Minolta's integrating sphere photometer CM-3700d. The higher the value, the better the whiteness.

(6) Evaluation of powdering The presence or absence of powdering was visually evaluated.
A: No powdering is observed C: Powdering is observed

  The functional fiber product obtained by the method for producing a functional fiber product of the present invention exhibits good UV absorption, water absorption, flexibility, and whiteness with wash resistance. In addition, no powdering was observed, which was good.

The functional fiber product obtained by the present invention has a good UV-absorbing effect with washing resistance, and can reduce fiber deterioration, hue change, and influence of UV rays on the human body.
Furthermore, since the functional fiber product of the present invention expresses a good texture and water absorbency with washing resistance, it can be suitably applied to sportswear and clothing that is in direct contact with the skin (especially clothing made of cellulosic fibers). It is useful because it can.

Claims (10)

A compound (A) represented by the following general formula (1) and a polymerized polymerizable vinyl monomer represented by the following general formula (2) or other vinyl monomers copolymerizable with the polymerizable vinyl monomer A process for producing a functional fiber product, which comprises treating the compound (B), which is a copolymer of the above, with a fiber product.

(In the above formula, R ¹ and R ² are each independently in the para-position or meta-position, and each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ³ is a carbon atom having 1 to 22 carbon atoms. Represents a hydrogen group, and R ⁴ represents a hydrogen atom or a -CN group)

(In the above formula, R ⁵ represents hydrogen, halogen or methyl group, R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ⁷ represents an alkylene group having 1 to 6 carbon atoms, R ⁸ represents a hydrogen atom or a methyl group)   In addition to the compound (A) and the compound (B), at least one compound (C) selected from the group consisting of an amino-modified silicone and an alkyleneoxy group-containing compound is processed into a textile product, The manufacturing method of the functional fiber product of Claim 1. The amino-modified silicone is a compound represented by the following general formula (3), the alkyleneoxy group-containing compound is a compound represented by the following general formula (4), (a) an organic polyisocyanate, (b) mono and And / or selected from the group consisting of an aqueous polyurethane resin obtained by reacting at least one compound selected from the group consisting of polyalkylene glycols and polyether polyols and (c) a chain extender and a polyether group-containing modified silicone. The method for producing a functional fiber product according to claim 2, wherein the functional fiber product is at least one kind.

(In the above formula, a plurality of R ⁹ may be the same as or different from each other, each independently represents a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ¹⁰ has 1 to 8 carbon atoms. A plurality of R ¹¹ may be the same as or different from each other, and each independently represents a monovalent hydrocarbon group having 1 to 5 carbon atoms, a hydroxyl group, 1 to carbon atoms. 5 an alkoxy group or a group represented by the formula —R ¹⁰ — (NHCH ₂ CH ₂ ) cNHR ¹² (wherein R ¹⁰ is the same as defined above, and c is 0 or an integer of 1 to 10). R ¹² represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, a is an integer of 5 to 10,000, and b is 0 or an integer of 1 to 1,000)

(In the above formula, R ¹³ represents an —OH group or — (R ¹⁴ O) dOH group, R ¹⁴ represents an alkylene group having 2 to 4 carbon atoms, d is an integer of 1 to 200, and d is 2) In the above case, a plurality of (R ¹⁴ O) may be the same as or different from each other, and when two or more (R ¹⁴ O) are present, they may be randomly added. may be a block addition, e is an integer of 2 to 100, R ¹⁶ is more present in one molecule may be different or mutually the same other and from each other, each independently represent a hydrogen atom or a - SO ₃ X group (X represents a hydrogen atom, an alkali metal atom or an amine group), a plurality of d's present in one molecule may be the same as or different from each other, and R ¹⁵ is a hydrogen atom. Atom or following formula (5):

(R ¹⁶ in the above formula represents the same as defined above)
Represents a group represented by   The compounding ratio (mass basis) of the compound (A) and the compound (B) is (A) :( B) = 95: 5 to 5:95, according to any one of claims 1 to 3. A method for producing functional fiber products.   The compounding ratio (mass basis) of the sum of the compound (A) and the compound (B) and the compound (C) is (A + B) :( C) = 100: 5 to 100: 200. The manufacturing method of the functional fiber product of any one of -4.   The compound (A) represented by the general formula (1) and a polymer of the polymerizable vinyl monomer represented by the general formula (2) or another vinyl monomer copolymerizable with the polymerizable vinyl monomer. The ultraviolet absorber for fibers used for the manufacturing method of the functional fiber product of Claim 1 containing the compound (B) which is a copolymer with this.   The ultraviolet absorption for fibers according to claim 6, comprising at least one compound (C) selected from the group consisting of an amino-modified silicone and an alkyleneoxy group-containing compound in addition to the compound (A) and the compound (B). Agent.   The amino-modified silicone is a compound represented by the general formula (3), the alkyleneoxy group-containing compound is a compound represented by the general formula (4), (a) an organic polyisocyanate and (b) mono and / or poly At least one selected from the group consisting of an aqueous polyurethane resin obtained by reacting at least one compound selected from the group consisting of alkylene glycol and polyether polyol and (c) a chain extender and polyether group-containing modified silicone. The ultraviolet absorber for fibers according to claim 7, which is a seed.   The compounding ratio (mass basis) of the compound (A) and the compound (B) is (A) :( B) = 95: 5 to 5:95, according to any one of claims 6 to 8. UV absorber for textiles.   The blending ratio (mass basis) of the total of the compound (A) and the compound (B) and the compound (C) is (A + B) :( C) = 100: 5 to 100: 200. The ultraviolet absorber for fibers according to any one of? 9.