KR20080105992A - UV Absorbent Textile Treatment Composition - Google Patents

Abstract

The present invention provides a composition which enables the ultraviolet absorber to be uniformly adsorbed on a garment and suppresses discoloration with time.

(A) A composition containing cationic compounds, such as a polymer of dimethyldiallyl ammonium chloride, (B) ultraviolet absorbers, (C) antioxidants, such as dibutylhydroxytoluene, and (D) water-soluble solvents, such as ethanol.

Description

UV absorbing textile treatment composition {ULTRAVIOLET ABSORPTIVE FINISHING AGENT COMPOSITION FOR TEXTILE PRODUCT}

The present invention relates to an ultraviolet absorbent fiber treatment agent composition.

In recent years, ultraviolet rays are more likely to reach the surface due to the destruction of the ozone layer, and ultraviolet rays having strong energy are increasing. The skin becomes reddish and becomes blistered by such ultraviolet exposure, and it causes wrinkles and blemishes if it is continuously exposed to ultraviolet rays continuously.

As a means of preventing ultraviolet rays, the sunscreen is applied directly to the skin, mass production and hats have been used or utilized. However, although the ultraviolet rays received directly from the sun can be prevented, the effect is insufficient, or the ultraviolet rays received by reflecting from the surface or from a wall or the like are defenseless. In addition, ultraviolet rays and the like that pass through the glass in the room also become a problem in recent years.

Because of such a situation, the development of the technique which has a ultraviolet protection effect also in clothing has been performed before (patent document 1-3).

However, these are industrially treated fibers and are not general use for treating favorite clothes at home.

As a general use, the technique of absorbing an ultraviolet-ray by adding the base material which has an ultraviolet absorbing effect to a softening agent composition is disclosed (patent documents 4-7).

However, the compositions disclosed in Patent Literatures 1 to 3 do not have good adsorption properties, and the compositions disclosed in Patent Literature 4 have stains in the adsorption of the ultraviolet absorber, so that a part having a high or low UV absorbing effect exists. In other words, its effectiveness is impaired in areas of low absorption. The composition also has poor storage stability. Thus, there exists a subject to making a ultraviolet absorber adsorb | suck uniformly on clothes. On the other hand, there exists a problem that the composition containing a ultraviolet absorber will discolor over time.

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-147617

Patent Document 2: Japanese Patent Application Laid-Open No. 5-179568

Patent Document 3: Japanese Patent No. 3892916

Patent Document 4: Japanese Patent Application Laid-Open No. 2003-301374

Patent Document 5: Japanese Patent Application Laid-Open No. 2002-161476

Patent Document 6: Japanese Patent Application Laid-Open No. 2002-161475

Patent Document 7: Japanese Patent No. 3871720

Therefore, an object of this invention is to provide the composition which enabled the ultraviolet absorber to adsorb | suck uniformly on clothing, and suppressed discoloration with time.

The present invention provides the ultraviolet absorbent fiber treatment composition comprising the following (A), (B), (C) and (D).

(A) at least one cationic compound selected from the group consisting of: Cationic surfactants and cationic properties having at least one C12-36 hydrocarbon group in the molecule which may be divided into an amide group, an ester group and / or an ether group, and having a tertiary amino group or a salt thereof or a quaternary ammonium group Water soluble high molecular compound

(B) UV absorbers

(C) antioxidant

(D) a water-soluble solvent selected from the group consisting of:

Monohydric or polyhydric alcohols having 2 to 6 carbon atoms and a glycol ether compound represented by the following general formula (I) or (II)

R ¹ -O- (R ² O) mH (I)

[In formula, R <^1> is a C2-C6 alkyl group or a phenyl group, R <^2> is a C2 or 3 alkylene group, m shows an average added mole number and is a number of 2-3.]

R ³ -O- (R ² O) nR ⁴ (II)

[Wherein, R ³ and R ⁴ each independently represent an alkyl group having 1 or 2 carbon atoms, R ² is an alkylene group having 2 or 3 carbon atoms, n represents an average added mole number and is a number of 1 to 3. ]

According to the present invention, since the ultraviolet absorber can be uniformly adsorbed without staining on the fiber product to be treated, it is excellent in the ultraviolet blocking effect. The composition of the present invention is difficult to discolor even when subjected to sunlight.

(A) ingredient

(A) A component is a cationic compound which improves the adsorption property to (B) component to a fiber or a fiber product, and C12-36 hydrocarbon group which may be segmented with an amide group, an ester group, and / or an ether group in a molecule | numerator It is a cationic surfactant which has one or more tertiary amino groups or salts or quaternary ammonium groups, or is a water-soluble high molecular compound having cationic properties. You may use together a cationic surfactant and the water-soluble polymer which has cationic property.

As a cationic surfactant which can be used by this invention, the amine compound shown below, the neutralization by the organic or inorganic acid, and its quaternized material can be illustrated. These can all be used as 1 type or in mixture of 2 or more types. When two or more kinds are mixed, the flexibility of the finished fiber product can be satisfactorily achieved when the mass ratio of the cationic surfactant having two or three long-chain hydrocarbon groups in the cationic surfactant mixture is 50% or more. It is preferable because it can be done. In order to give biodegradability after discarding in a natural environment after use, it is preferable that it is a cationic surfactant containing an ester group in the middle of the said long-chain hydrocarbon group.

[Formula 1]

R constituting the cationic surfactant is a hydrocarbon group having 10 to 24 carbon atoms, preferably C14 to 18 carbon atoms, preferably a saturated or unsaturated straight or branched chain group, more preferably a straight or branched alkyl group or an alkenyl group. . In the case of having an unsaturated group, a cis body and a trans body are present, and the mass ratio thereof is preferably cis / trans = 25/75 to 100/0, and particularly preferably 40/60 to 80/20. Moreover, it is preferable that the ratio of saturated and unsaturated hydrocarbon group is 95/5-50/50 (wt / wt).

R1 constituting the cationic surfactant is a residue excluding a carboxyl group from fatty acids having 10 to 24 carbon atoms, and is a long-chain hydrocarbon group derived from any one of saturated fatty acids, unsaturated fatty acids, straight chain fatty acids and branched fatty acids. . In the case of unsaturated fatty acids, cis and trans are present, with the mass ratio of cis / trans = 25/75 to 100/0 being preferred, and 40/60 to 80/20 being particularly preferred. The fatty acid which becomes the basis of R can illustrate the following. Stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, eraidinic acid, partially hydrogenated palm oil fatty acid (iodine 10 to 60), partially hydrogenated tallow fatty acid (iodinated 10 to 60), and the like. . Among them, preferably, a stearic acid, palmitic acid, myristic acid, oleic acid, and erydic acid are combined in predetermined amounts, and the saturation / unsaturation ratio is 95/5 to 50/50 (wt / wt), and the cis / trans body mass ratio is 40 /. The fatty acid composition which adjusted 60-80 / 20, the iodine value 10-50, and the C18 ratio is 80 mass% or more, the C20 fatty acid is 2 mass% or less, and the C22 fatty acid is 1 mass% or less is used. It is desirable to. Here, all of R in the formula may be the same or may be different from each other.

Examples of the acid used for neutralization of the tertiary amine include hydrochloric acid, sulfuric acid and methyl sulfuric acid. The tertiary amine used in the present invention is preferably used in the form of an amine salt neutralized by hydrochloric acid, sulfuric acid or methyl sulfuric acid. In the neutralization step, the neutralized tertiary amine may be previously dispersed in water, or the tertiary amine may be introduced in a liquid or solid phase in an acid aqueous solution. Of course, tertiary amine and acid component may be added simultaneously. Moreover, methyl chloride and dimethyl sulfate are mentioned as a quaternization agent used for quaternization of the said tertiary amine.

Compounds of the general formulas (A-III) and (A-IV) can be synthesized by the condensation reaction of the fatty acid composition or the fatty acid methyl ester composition with methyldiethanolamine. In that case, it is preferable to synthesize | combine so that the existence ratio of the compound of (A-III) and (A-IV) may be 99/1-50/50 by mass ratio from a viewpoint of making dispersion stability favorable. In the case of using the quaternized compound, methyl chloride, dimethyl sulfuric acid, or the like is used as the quaternizing agent, and methyl chloride is more preferable in terms of low molecular weight and low weight of the quaternizing agent required for quaternization. In that case, it is preferable to synthesize | combine so that the presence ratio of the quaternized substance of esteramine represented by (A-III) and (A-IV) may also be 99/1-50/50 by mass ratio from a viewpoint of dispersion stability. In addition, when quaternizing (A-III) and (A-IV), unesterified esteramine generally remains after the quaternization reaction. In that case, it is preferable that the ratio of the esteramine which is not quaternized / quaternized is a mass ratio of 99/1-70/30 by mass ratio from a viewpoint of the hydrolysis stability of an ester group.

The compounds of the general formulas (A-V), (A-VI) and (A-X) can be synthesized by the condensation reaction of the fatty acid composition or the fatty acid methyl ester composition with triethanolamine. In that case, it is preferable to synthesize | combine so that abundance ratio of a compound of [(AV) + (A-VI)] and (A-VIII) may be 99/1-50/50 by mass ratio from a viewpoint of making dispersion stability favorable. Do. In addition, when using the quaternized substance, methyl chloride, dimethyl sulfate, etc. are used as a quaternization agent, but dimethyl sulfuric acid is more preferable from a reactive viewpoint. In that case, the presence ratio of the quaternized substance of the esteramine represented by [(AV) + (A-VI)] and (A-X) is also synthesize | combined so that it may become 99/1-50/50 by mass ratio from a viewpoint of dispersion stability. It is desirable to. In addition, when quaternizing (A-V), (A-VI), and (A-VIII), unquaternized esteramine generally remains after a quaternization reaction. In that case, it is preferable that the ratio of the esteramine which is not quaternized / quaternized is a mass ratio of 99/1-70/30 by mass ratio from a viewpoint of the hydrolysis stability of an ester group.

Compounds of the general formulas (A-VIII) and (A-VIII) are obtained from the adducts of the fatty acid composition, N-methylethanolamine and acrylonitrile. Org. Chem., 26, 3409 (1960) "can be synthesized by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized by a known method. In that case, it is preferable to synthesize | combine so that the existence ratio of the compound of (A-VIII) and (A-VIII) may be 99/1-50/50 by mass ratio. In the case of using the quaternized compound, it is quaternized with methyl chloride, and the presence ratio of the quaternized compound of the esteramine represented by (A-X) and (A-X) is also 99/1 to 50/50 by mass ratio. It is preferable to synthesize as much as possible. In addition, in the case of quaternizing (A-VIII) and (A-VIII), unquaternized esteramine generally remains after the quaternization reaction. In that case, it is preferable that the ratio of the esteramine which is not quaternized / quaternized is a mass ratio of 99/1-70/30 by mass ratio from a viewpoint of the hydrolysis stability of an ester group.

As the cationic surfactant usable in the present invention, it is also possible to use fatty acid amidealkyl tertiary amines derived from higher fatty acids having 10 to 22 carbon atoms or salts thereof, and the fatty acids may be saturated or unsaturated.

As a specific example of this fatty acid amide alkyl tertiary amine, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid Fatty acid amide alkyl tertiary amines, such as dimethylaminopropylamide and oleic acid dimethylaminopropylamide, or its salt, etc. are mentioned. Among them, since the smell of itself is small and good, dimethyl aminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, Hennin dimethylaminopropylamide and oleic acid dimethylaminopropylamide are preferable, and palmitic acid dimethylaminopropylamide and stearic acid dimethylaminopropylamide are more preferable.

As a specific commodity of a long chain amine, For example, Kachinal MPAS-R (brand name, the mass ratio 3/7 mixture of dimethylaminopropylamide and palmitate dimethylaminopropylamide) by Toyo Chemical Co., Ltd., Lion Arc Co., Ltd. Amine APA168-65E (brand name, 65 mass% ethanol solution of 3/7 mass ratio of the dimethylaminopropylamide of palmitate and dimethylaminopropylamide), etc. are used preferably.

In addition, said "fatty acid amide alkyl tertiary amine or its salt", for example, condensation reaction of fatty acid derivatives, such as fatty acid or fatty acid lower alkyl ester, animal and vegetable fats and oils, and a dialkylaminoalkylamine, and thereafter, , Unreacted dialkylaminoalkylamine is obtained by distilling under reduced pressure or nitrogen blow.

Here, as the fatty acid or fatty acid derivative, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, leruca acid, 12-hydroxystearic acid, palm oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid, Uji fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid, etc., or these methyl ester, ethyl ester, glyceride, etc. are mentioned specifically ,. Among them, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid are preferable because they are excellent in adsorption performance to a fiber product in a washing rinse stroke. These fatty acids or fatty acid derivatives may be used individually by 1 type, or may use 2 or more types together.

As a cationic surfactant, the quaternized substance of the amine compound represented by said formula (A-II), (AV), (A-VI), or (A-VII), and fatty acid derived from a C14-18 higher fatty acid Preferred are amidealkyl tertiary amines or salts thereof.

The compounding quantity of said cationic surfactant is 0.1-50 mass%, Preferably it is 0.5-30 mass%. By carrying out the compounding quantity of a cationic surfactant in such a range, it can improve the adsorption | suction accelerating effect of the ultraviolet absorber which is (B) component, and can suppress a raise of a viscosity and can be made favorable in terms of usability.

The cationic polymer which can be used in the present invention is a polymer having a solubility in 100 g of water at 25 ° C of 1 g or more and a weight average molecular weight of 1,000 to 5,000,000. The weight average molecular weight can be measured by gel permeation chromatography under conditions using polyethylene glycol as a standard substance. Any polymer compound having cationicity at the time of dissolving in water may be used, and specifically, DIDOL EC-004, DIDOL HEC, DIDOL EC (Daedong Chemical Co., Ltd.) MERQUAT100 (Nalco), Adekakachio PD PD-50 ( Dimethyl diallyl ammonium acrylate copolymers such as polymers of dimethyl diallyl ammonium chloride such as Asahi Kogyo Co., Ltd., dimethyl diallyl ammonium acrylamide copolymer such as MERQUAT550 (Nalco), and MERQUAT280 (Nalco Co.) Polyethylenimine, such as imidazolinium chloride vinylpyrrolidone copolymer, LUGALVAN-G15000 (BASF), such as cationic cellulose, such as KGA (Lion), LUVIQUAT-FC905 (BASF), and foaming M318 (Kurare) Natural polymer derivatives having amino groups such as cationized polyvinyl alcohol, chitosan and the like, copolymers with vinyl monomers having a hydrophilic group to which diethylaminomethacrylate-ethylene oxide and the like are added. Among these, polymers of dimethyldiallyl ammonium chloride are preferable. All can be used as 1 type, or 2 or more types of mixtures.

Although the compounding quantity of a cationic polymer is not specifically limited, It is preferable to set it as the range which does not provide rigidity to a fiber product, For example, it is good to set it as 0.1-30 mass% based on the total mass of a composition, More preferably, it is good to set it as 0.5-10 mass%. By carrying out the compounding quantity of a cationic polymer in such a range, it can improve the adsorption | suction accelerating effect of the said (B) component, and can suppress a raise of a viscosity and can be made favorable in terms of usability.

(B) ingredient

In general, as an effect of protecting ultraviolet rays, it can be roughly classified into an ultraviolet scattering agent, which is an inorganic powder, and an ultraviolet absorber, which is an organic compound. Inorganic powder mainly exerts effects by a physical mechanism of scattering and blocking. On the other hand, the ultraviolet absorber which is an organic compound has an effect by the mechanism which converts the absorbed light energy into other energy efficiently. When used at a sufficient concentration to protect against ultraviolet rays, the above-described sunscreen effect of both substrates is expressed.

As the ultraviolet scatterer which is an inorganic powder, titanium oxide, zinc oxide, etc. which are highly stable inorganic pigments are used, and it is effective in the whole wavelength range of an ultraviolet-ray for the mechanism of scattering and blocking of light. However, incorporating the amount of the level at which the effect can be expressed, not only makes the powder easily clogged in the tube during spraying, but also the whiteness of the garment surface.

On the other hand, the ultraviolet absorber, which is an organic compound, is an aromatic compound having a carbonyl group, and absorbs high-energy ultraviolet rays at short wavelengths, and converts and emits them into harmless low-energy rays having long wavelengths. Even a small amount shows a high ultraviolet absorption effect, and does not cause troubles, such as clogging at the time of spraying and whitening on a textile product like inorganic powder.

Preferred ultraviolet absorbers are derivative compounds of stilbene, benzophenone and benzotriazole. In particular, stilbene derivatives are preferred. The stilbene derivative is a compound having a stilbene structure represented by the following General Formulas (B-I) to (B-IV).

General formula (B-I)

[Formula 2]

Wherein M is a cation formed of hydrogen, an alkali metal atom, ammonium or an amine, R 1 is hydrogen or a hydroxy group, R 2 is a C1 to C4 alkyl or phenyl group, and Y is -C (= 0) -NR 3 R 4 (R 3 and R 4 Are independently hydrogen or a C1 to C4 alkyl group), -SO2-NR3R4, -C (= 0) -NR2 or -C (= 0) -OM, and X is NH, O or one with R2 Morpholino group.)

General formula (B-Ⅱ)

[Formula 3]

Wherein M is a cation formed of hydrogen, an alkali metal atom, ammonium or an amine, R 1 is a substituted aryl group, R 2 is hydrogen, optionally a substituted aryl group, morpholine group, alkylamine group, hydroxide Time, n1 and n2 are 0 or 1 independently of each other.)

General formula (B-Ⅲ)

[Formula 4]

(Wherein M is a cation formed of hydrogen, an alkali metal atom, ammonium or an amine, and R 1 is a group represented below).

[Formula 5]

(In formula, R2 is NH2, N (CH2CH2OH) 2, etc., R3 is NR4R5 etc., R4, R5 is hydrogen, an alkyl group.)

General formula (B-IV)

[Formula 6]

(Wherein R1, R2, R3, and R4 are groups represented by -NR5R6, and they may be the same or different. Here, R5 and R6 may be the same or different, and each of hydrogen atoms, C1 to C3, respectively. The aryl group which may have an alkyl group, a hydroxyalkyl group, or a substituent, or the heterocyclic ring which R <5>, R <6> connected through the hetero atom may be formed. M is an organic or inorganic cation.)

Among these, stilbene derivatives represented by the formula (B-I) are preferred.

Specific examples of stilbene derivative ultraviolet absorbers that can be used in the present invention include the compounds described in the examples of Japanese Patent Application Laid-Open Nos. 9-3052, 10-81672, and 10-87638. Among these, the brand names Tinosorb FD and Tinosorb FR manufactured by Chiba Specialty Chemicals Co., Ltd. are preferable, and Tinosorb FD is particularly preferable.

A benzophenone derivative is a copolymer of the polymerizable vinyl monomer shown below alone or with another copolymerizable vinyl monomer.

General formula (B-V)

[Formula 7]

(Wherein R represents hydrogen or a methyl group, X represents -O-, -OCH2CH2O- or -OCH2CHCH3HO-)

As a benzophenone derivative which can be used by this invention, ULS-700 etc. which are marketed from Ipposha Oil Industry Co., Ltd. are mentioned.

The benzotriazole derivative is a copolymer of the polymerizable vinyl monomer represented by the following general formula (B-VI) alone or with another copolymerizable vinyl monomer.

General formula (B-Ⅵ)

[Formula 8]

(Wherein Y is hydrogen, halogen or methyl group, R1 is hydrogen or C1 to C6 alkyl group, R2 is C1 to C6 straight or branched alkylene group, R3 is hydrogen or methyl group.)

Examples of the benzotriazole derivatives that can be used in the present invention include ULS-1700 (ipposha oil industry Co., Ltd.), NCI-905-20EM (Nico Chemical Research Institute), and the like.

In the present invention, polyamide-2 derivatives can also be used as ultraviolet absorbers. As a polyamide-2 derivative which can be used by this invention, the Solamer GR8 etc. marketed from NALCO company can be mentioned.

Moreover, in this invention, a silicone derivative ultraviolet absorber can be used. As a silicone derivative ultraviolet absorber which can be used by this invention, PARSOL SLX marketed from DSM Nutrition Japan is mentioned.

Content of (B) component is 0.001-10 mass% normally with respect to composition whole quantity, Preferably it is 0.01-10 mass%, More preferably, it can mix | blend 0.1-5 mass%.

If the quantity of (B) component exists in such a range, it is preferable from an ultraviolet absorption effect and economical point.

(C) component

The component (C) is an antioxidant capable of preventing discoloration due to aging of the component (B), and as the antioxidant, both generally known natural antioxidants and synthetic antioxidants can be used. Specifically, ascorbic acid, ascorbic acid derivatives (e.g., ascorbic acid and phosphoric acid derivatives, ascorbic acid and saccharides derivatives). Any sugar may be used, and monosaccharides, disaccharides, oligosaccharides, and polysaccharides may be used, and the constituent sugars are preferably pentose sugar and land saccharide, and glucose is preferred among them), ascorbic acid and palmitic acid derivatives), and Mixtures, BHT (dibutylhydroxytoluene), BHA (butylated hydroxyanisole), mixtures of citric acid, hydroquinones, tertiary butylhydroquinones, natural tocopherol compounds, long chain esters of molar assets (C8 to C22), for example Molded asset dodecyl and bisphenols (for example, thiobisphenol-based (manganox® compound available from Chivas Specialty Chemical Co., Ltd.), for example, 2,2'-methyl Bis (4-ethyl-6-t-butylphenol (bisphenol-based compound (antage series) which can be purchased from Kawaguchi Chemical Co., Ltd.), citric acid isopropyl, 4,5-dihydroxy-m-benzenesulfonic acid / Sodium salt, dimethoxyphenol, catechol, methoxyphenol, carotenoids, frans, amino acids and the like.

Among them, BHT, methoxyphenol, ascorbic acid derivatives, bisphenols, and tocopherol derivatives are preferable from the viewpoint of the appearance and storage stability of the ultraviolet absorbent fiber treatment composition.

It is preferable that the compounding quantity of antioxidant is used in 0.001-10 mass% on the basis of the whole quantity of a composition. Preferably it is 0.05%-5%, Especially preferably, it exceeds 0.01% and it is the range of 5% or less. If it exists in this range, discoloration of a composition can be suppressed effectively.

(D) component

(D) component is essential for uniformly applying the ultraviolet absorber of (B) component to a fiber thru | or a fiber product surface. However, in the general formula (I), R ¹ : 2 to 4, R ² : So-called cellosolves having an ethylene group and a point of m = 1 are preferable because they are intended to be displayed on the basis of a global harmonization system (GHS) relating to the classification and labeling of chemicals in terms of danger and danger. Not.

As (D) component, the C2-C6 monohydric alcohol or polyhydric alcohol, or the glycol ether compound represented by Formula (I) is preferable. As monohydric alcohol or polyhydric alcohol, a C2-C4 thing is more preferable. As a glycol ether compound represented by Formula (I), the compound whose R <^1> is a C2-C6 alkyl group is more preferable. Specifically, ethanol, ethylene glycol, propylene glycol, pentanediol, hexanediol, hexylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol diethyl ether, and the like And diethylene glycol monobutyl ether, ethanol and ethylene glycol are more preferable in these.

Content of (D) component is 0.1-90 mass% normally with respect to composition whole quantity, Preferably it is 1-50 mass%, More preferably, it can mix | blend 1-20 mass%. If the quantity of (D) component exists in such a range, it is preferable at the point of the composition stability of a ultraviolet absorber, and a uniform adsorption property.

[Optional ingredients]

(E) component

(E) component of this invention is a silicone compound. This silicone compound will not be specifically limited if it can improve the uniform adhesiveness of (B) component. Silicone compounds generally used for fiber treatment include dimethyl silicone, polyether modified silicone, methylphenylsilicone, alkyl modified silicone, higher fatty acid modified silicone, methylhydrodiene silicon, fluorine modified silicone, epoxy modified silicone, carboxy modified silicone, and carbinol. Modified silicone, amino modified silicone, etc. are mentioned, These 1 type can be used individually or as mixture of 2 or more types.

Among these, as a particularly preferable silicone compound, polyether modified silicone is mentioned. Compared with the dimethyl silicone which does not have a polyether group, this silicone can be finished with the fiber with less active feeling and a favorable activity. As a preferable polyether modified silicone, the copolymer of alkyl (C1-C3) siloxane and polyoxyalkylene (C2-C5 of an alkylene group is preferable) is mentioned. Of these, copolymers of dimethylsiloxane and polyoxyalkylene (such as random or block copolymers of polyoxyethylene, polyoxypropylene, ethylene oxide and propylene oxide) are preferable.

The molecular structure of the silicone compound may be linear or branched or crosslinked. The modified silicone compound may be modified by one type of organic functional group or may be modified by two or more types of organic functional groups.

The silicone compound may be used as an oil, or may also be used as an emulsion dispersed by any emulsifier.

Polyether modified silicone is especially preferable at the point which improves the uniform coating property and activity of (B) component. As preferable polyether modified silicone, the copolymer of alkyl (polyoxyethylene, polyoxypropylene, random or block copolymer of ethylene oxide and a propylene oxide, etc.) is preferable. As such a thing, the compound represented with the following general formula (E-I) is mentioned.

[Formula 9]

In formula, -Z is respectively independently -R, -OR, -OH, -OXR, -OXH, R may be same or different, and all are saturated or unsaturated linear or branched C1-C4 hydrocarbon groups to be. As -Z, -R and -OH are preferable, As R, saturated hydrocarbon groups (alkyl groups), such as a methyl group, an ethyl group, a propyl group, and a butyl group, are preferable, and a methyl group is especially preferable.

X is a polyoxyalkylene group. Specifically, polyoxyethylene, polyoxypropylene, polyoxybutylene group, etc. can be mentioned, One of these may be added, or other, such as an oxyethylene unit, an oxypropylene unit, or an oxybutylene unit, may be mentioned. A kind of oxyalkylene groups may be arranged in a block shape or randomly. In any case, however, the mass ratio of the polyoxyethylene chain portion in X is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, more preferably based on the mass of the entire molecule. Is 20-35 mass%.

Specific examples of commercially available polyether-modified silicone that can be used in the present invention include SH3772M, SH3775M, SH3748, SH3749, SF8410, SH8700, BY22-008, SF8421, SILWET L-7001, manufactured by Toray Dow Corning Co., Ltd. SILWET L-7002, SILWET L-7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1 -009-01, ABN SILWET FZ-F1-009-02, ABN SILWET FZ-F1-009-03, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1-009-09, ABN SILWET FZ-F1 -009-11, ABN SILWET FZ-F1-009-13, ABN SILWET FZ-F1-009-54, ABN SILWET FZ-2222, KF352A, KF6008, KF615A, KF6016, KF6017, made by Shinwol Chemical Co., Ltd. TSF4450, TSF4452 by Toshiba Silicone Co., Ltd., etc. are mentioned, These can be used individually by 1 type or as a mixture of 2 or more types.

The silicone compound which can be used in the present invention is generally polyoxyalkylene having an organohydrodienepolysiloxane having a Si—H group and a carbon-carbon double bond such as polyoxyalkylene allyl ether at the terminal. It can be prepared by addition reaction of alkyl ether. As a preferable polyether modified silicone, the copolymer of alkyl (C1-C3) siloxane and polyoxyalkylene (C2-C5 of an alkylene group is preferable) is mentioned. Among them, a copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, random or block copolymer of ethylene oxide and propylene oxide, etc.) is preferable. As such a compound, the compound represented by the following general formula (E-II) is mentioned.

[Formula 10]

(Wherein M, N, a and b are average degrees of polymerization and R represents hydrogen or an alkyl group.)

Where M is dimethylsiloxane, N is polyoxyalkylene, a is polyoxyethylene, and b is the number of polyoxypropylene. M is 10-10000, Preferably it is 50-1000, More preferably, it is 100-300, N is 1-1000, Preferably it is 5-300, It is preferable that M> N. a is 2 to 100, preferably 5 to 50, more preferably 5 to 20, and b is 0 to 50, preferably 0 to 10. As R, a hydrodiene or a C1-C4 alkyl group is preferable, and it is more preferable that it is a C1-C4 alkyl group.

Although the compounding quantity of the silicone compound used by this invention is not specifically limited, 0.1-50 mass% is preferable based on the total mass of a composition from the point of uniform adsorption of the (B) component of the processed fiber product, Furthermore, Preferably it is 0.3-40 mass%, Especially preferably, it is 0.5-30 mass%. Thereby, the uniform adsorption of (B) component can be made favorable, and also the rise of the viscosity of a composition can be suppressed and it can be made easy to use.

[Random component: nonionic surfactant]

In addition, in this invention, in order to maintain a stable state of a composition, in addition to the said component, a nonionic surfactant can be used and the nonionic surfactant represented by following General formula (1) is preferable.

R ⁵ -T-[(R ² O) _p -H] _q (1)

(Wherein R ⁵ is a C10-20 hydrocarbon group, preferably an alkyl group or an alkenyl group of 12-18, R ² is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group.p: average added mole number) And 2 to 100, preferably 10 to 80, particularly preferably 20 to 60. T is -O-, -N-, -NH-, -N (C ₂ H ₄ OH)-, -CON-,- CONH- or CON (C ₂ H ₄ OH)-, T is -O-, -NH-, -N (C ₂ H ₄ OH)-, -CONH-, or -CON (C ₂ H ₄ OH)- When q is 1, when T is -N- or -CON-, q is 2.)

As a specific example of the compound of the said General formula (1), the compound represented by the following general formula (1-1) is mentioned.

R ⁵ -O- (C ₂ H ₄ O) _s (C ₃ H ₆ O) _t -R ⁶ (1-1)

(Wherein, R ^5: as the average addition mol number, s:: same meanings as defined above, s, t a number from 2 to 100, preferably from 20 to 80 and, t: is the number of 0 or 1 to 5 (C _2. H ₄ O) and (C ₃ H ₆ O) may be random or block adducts. R ⁶ : H or an alkyl group having 1 to 3 carbon atoms.)

For example, polyoxyethylene alkyl ethers having one or more alkyl groups or alkenyl groups having 12 to 18 carbon atoms are preferable, and those having an average of 20 to 80 moles of oxyethylene groups added are particularly preferable.

It is preferable to contain a nonionic active agent, since storage stability improves further. It is preferable to make the compounding quantity into 0.01-20 mass% on the basis of the total mass of a composition, Especially 0.5-15 mass% and 1-10 mass% are preferable. By setting it as such a compounding quantity, the improvement effect of storage stability can be made sufficient, and it becomes possible to suppress the extra addition when the effect reaches saturation, and to aim at economical efficiency.

[Random Ingredients: Water]

As the water to be used, for example, tap water, ion-exchanged water, pure water, distilled water and the like can all be used. Among them, water from which hardness components such as calcium and magnesium, which are present in trace amounts in water, and heavy metals such as iron are preferred, and ion exchange water is most preferable because it is advantageous in terms of cost.

[Random component: fragrance composition]

Although it does not specifically limit as a fragrance | flavor, A list of the fragrance raw materials which can be used is various documents, for example, "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994) and Synthetic Fragrance Chemistry and Product Knowledge, by Umotoichi India, Chemical Daily (1996) and Perfume and Flavor Materials of Natural Origin, Steffen Arctander, Allured Pub. Co. (1994) and Encyclopedia of Fragrances, Japan Flavors Association, Asakura Bookstore (1989) and Perfumery Material Performance V. 3. 3, Boelens Aroma Chemical Information Service (1996), and FlowR oils and Floral Compounds In Perfumery, ”Danute Lajaujis Anonis, Allured Pub. Co. (1993) and the like.

[Random Ingredients: Preservative]

Preservatives are mainly used to maintain the preservation during long-term storage, specifically, isothiazolone type organic sulfur compound, benzisothiazolone type organic sulfur compound, benzoic acid, 2-bromo-2-nitro And propane-1,3-diol. Examples of isothiazolone-based organic sulfur compounds include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolone and 2-benzyl-3-isothiazolone , 2-phenyl-3-isothiazolone, 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazoline-3- Warm and mixtures thereof. More preferred antiseptic and disinfectant is an aqueous mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, still more preferably about 77 Water-soluble mixture of% 5-chloro-2-methyl-4-isothiazolin-3-one with about 23% 2-methyl-4-isothiazolin-3-one. In addition, examples of the benzisothiazoline-based organic sulfur compound include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and the like. Dithio-2, 2-bis (benzmethylamide) etc. can also be used as a leucine compound, They can be used in arbitrary mixing ratios. Of these, 1,2-benzisothiazolin-3-one is particularly preferred. Examples of benzoic acids include benzoic acid or salts thereof, palahydroxy benzoic acid or salts thereof, methyl palaoxybenzoic acid, ethyl palaoxybenzoic acid, propyl palaoxybenzoic acid, butyl palaoxybenzoic acid, benzyl palaoxybenzoic acid, and the like. The compounding quantity is 0.0001-1 mass% with respect to the whole composition.

[Random component: antifoaming agent, other additives]

Examples of the antifoaming agent include silicone antifoaming agents such as dimethyl silicone containing fine powder such as silica, alcohol antifoaming agents, ester antifoaming agents, mineral oil antifoaming agents, vegetable oil antifoaming agents, and synthetic oil antifoaming agents. Examples of the silicone antifoaming agent include oil type antifoaming agents, compound type antifoaming agents, self-emulsifying antifoaming agents, emulsion type antifoaming agents, powder type antifoaming agents, solid antifoaming agents and the like. Among these, self-emulsifying antifoaming agents and emulsion antifoaming agents Is preferred. Although the compounding quantity of an antifoamer is not specifically limited, Based on the total mass of a composition, it can be 0.1 ppm-1 mass%, More preferably, it can be 1 ppm-0.05 mass%. Other additives include salts, ammonium chloride, calcium chloride, water-soluble salts such as magnesium chloride, potassium chloride and sodium citrate, emulsions such as liquid paraffin and higher alcohols, urea, hydrocarbons, nonionic cellulose derivatives and fluorescent lamps. Brighteners, pH adjusters and the like.

Target Textile Products

Although it does not specifically limit as a target fiber product using the composition of this invention, For example, sportswear, a T-shirt, a polo shirt, a blouse, a chino pants, a suit, slacks, a skirt, etc. are mentioned. In addition, the material of the target fiber product is not particularly limited, for example, natural fibers such as cotton, wool, hemp, synthetic fibers such as polyester, nylon, acrylic, semisynthetic fibers such as acetate, Recycled fibers, such as rayon, tencel, and polyinosity, and blends, blends, and blends of these various fibers.

EXAMPLE

[Preparation of UV Absorbing Fiber Treatment Composition]

The components shown below were used with the compounding quantity shown in Table 7, and the composition of the Example and the comparative example was prepared.

TABLE 1

[(A) Component: Cationic Compound]

A quaternary ammonium salt (a mixture of (a) monoesters, (b) diesters, and (C) triesters) synthesized according to Example 1 of Japanese Patent Application Laid-Open No. 2003-12471), suspended with an ester group. A long-chain hydrocarbon group-containing quaternary ammonium methyl sulfate [(a) monoester: (b) diester: (C) triester mass ratio = 25:55:20] was used.

[(B) component: UV absorber]

B-1 UV absorber TINOSORB FD Chiba specialty chemical topic stilbene derivative

B-2 UV absorber TINOSORB FR Chiba specialty chemical topic stilbene derivative

B-3 UV Absorber ULS-1700 Benzotriazole Derivatives

B-4 UV Absorber ULS-700 Bipphenone Derivatives

B-5 UV absorber Solamer GR8 manufactured by Nalco

[(C) Component: Antioxidant]

TABLE 2

TABLE 3

[(D) component: Water-soluble solvent]

TABLE 4

[Component (E): Silicone Compound]

E-1; Laboratory Synthesis Method of Silicone Compound

(E-1) was synthesized as follows. That is, 828 g of hydrodienesiloxane represented by (CH ₃ ) ₃ SiO (CH ₃ CH ₃ SiO) ₂₁₀ (CH ₃ HSiO) ₉ Si (CH ₃ ) ₃ , average composition CH ₂ = CHCH ₂ O (CH ₂ CH ₂ O ) ₉ screen allyl represented by H polyether about 210g, ethyl alcohol 726g and platinum is allylated polyether that is neutralized Cl of chloroplatinic acid were weighed such that the 5ppm by weight lead, and stirred to the reaction temperature 80 ℃, and 5 The reaction was time. After completion of the reaction, polyether-modified silicone was obtained by distillation under reduced pressure.

As the polyether modified silicone, silicone having an average structure represented by formula (E-II) was used.

[Formula 11]

E-2 silicone compound dimethyl silicone emulsion BY22-034 (product made in Toray Dow Corning Silicone)

E-3 Silicone Compound Amino Modified Silicone Emulsion Polon MF-14 (manufactured by Shinwol Chemical Co., Ltd.)

TABLE 5

[Common Ingredients]

TABLE 6

[Examples 1 and 21]

(B), (C), (D), (E) and common component-1 (a) were filled in the 500 ml beaker, and it fully stirred using the stirring blade. Next, ion-exchanged water is added while stirring, and while stirring again, (A) and remaining common component (-1 (b)) are added, and after stirring, it fully stirs until it becomes uniform, and it absorbs 400g of ultraviolet absorbers A fiber treatment composition was prepared.

Example 2-20 and Comparative Example 1-4

(A), (B), (C), (D), and (E) component and common component (-2 (a)) which were previously heated and melted at 55 ° C were taken in a glass container having an inner diameter of 120 mm, While stirring at 1000 rpm using a motor (manufactured by Shindo Science Co., Ltd.), ion-exchanged water, which had been warmed to 50 ° C. in advance, was added thereto, stirred for 3 minutes, and an emulsion was obtained. Thereafter, the common component (-2 (b)) was added to prepare a 1000 g ultraviolet absorbent fiber treatment composition. When adding the silicone emulsified previously, it was added last and the ultraviolet absorbent fiber processing composition was prepared. As a stirring blade, the paddle blade which has three wings of length 100mm by 30 mm space | interval was used. When adding the silicone emulsified beforehand and adding a C-3 component, it added last at the same timing as a common component (-2 (b)), and prepared the ultraviolet absorbent fiber processing composition.

In addition, when adding common component (-2 (b)), the thing diluted with ion-exchange water so that calcium chloride might be 10% was used for mix | blending. As other components were also regarded as 100% products, each of which was used as a 1% aqueous solution with ion-exchanged water was used for the formulation.

<Evaluation of UV Blocking Effect (UPF)>

As the evaluation cloth, a test fabric made by Test Fabric Co., Ltd., 437W, was cut to 10 × 10 cm. Washing is commercially available medical detergent "top" of standard usage (product made from Lion, ingredient: surfactant (alpha olefin sulfo fatty acid sodium salt, fatty acid sodium, linear alkylbenzene type, polyoxyethylene alkyl ether), water softening agent) , Alkaline agent, enzyme stabilizer, enzyme, fluorescent brightener)) was added to water to prepare 666 ppm of detergent solution, and 16 test cloths (approximately 24 g) were added thereto, followed by a ride torometer [Tergot-O-Meter]. The test cloth was washed at 120 rpm for 10 minutes, then rinsed for 3 minutes, and after centrifugal dehydration, the composition of Example or Comparative Example was added to the rinse solution so as to be 333 ppm, rinsed again for 3 minutes, and then centrifuged. The cycle of washing → rinse → centrifugal dewatering → rinsing in water containing the composition of the example or comparative example → centrifugal dehydration was repeated three times. Then, the test cloth was dried for 12 hours on condition of room temperature 20 degreeC, and 50% RH of relative humidity, and the test cloth provided for a test was obtained. The water used for washing | cleaning and rinsing is 900 ml, hardness 1.7 degrees DH, and water temperature 25 degreeC.

Using the test cloth obtained in this way, the measurement of UPF for one composition was limited to four.

UPF divides one piece into four pieces, and before and after washing at four places of each center neighborhood

UPF was measured using the UV meter (the Chiba Specialty company make, ISO-MET (trademark)). The difference (WHΔUPF) of UPF before and after washing in four places (16 places in total) of each of four evaluation cloths was computed using the formula shown below. The average value of all (triangle | delta) UPF of all 16 places was calculated | required, and it determined by the following criteria. The results are shown in Table 7.

(Equation 1) △ UPF = after washing three times UPF value-before washing UPF value

Determination of Uniformity

The variation coefficient of 16 places which measured UPF was calculated | required, and it judged by the criterion shown below. The results are shown in Table 7.

※ Average value of △ UPF of variation coefficient (CV%) = standard deviation (SD) / 16 places

<Evaluation of Discoloration of Composition>

100 ml of the composition prepared by the Example and the comparative example was put into photo-sphere standard bottle No.11, and the color change after 7 days was observed in the place where the daylight of summer season easily touches (total amount of ultraviolet irradiation 6.2) MJ / m 2). A comparative control product was prepared in the same manner except that the product was put in a cold dark place for 7 days. The external appearance of the bottle which injected the composition of an Example and a comparative example was compared with the external appearance of the bottle of a comparative control, and the following references | standards evaluated. The results are shown in Table 7.

○: Appearance equivalent to the control product (pale yellow to pale orange)

(Triangle | delta): A hue becomes slightly darker in comparison with a control product.

×: Compared with the control, the color tone is clearly darker

TABLE 7

Claims (5)

(A), (B), (C) and (D), The ultraviolet absorbent fiber treating agent composition characterized by the above-mentioned. (A) at least one cationic compound selected from the group consisting of: Cationic surfactants and cationic properties having at least one C12-36 hydrocarbon group in the molecule which may be divided into an amide group, an ester group and / or an ether group, and having a tertiary amino group or a salt thereof or a quaternary ammonium group Water soluble high molecular compound (B) UV absorbers (C) antioxidant (D) a water-soluble solvent selected from the group consisting of: Monohydric alcohol or polyhydric alcohol having 2 to 6 carbon atoms and a glycol ether compound represented by the following general formula (I) or (II) R ¹ -O- (R ² O) mH (I) [In formula, R <^1> is a C2-C6 alkyl group or a phenyl group, R <^2> is a C2 or 3 alkylene group, m shows an average added mole number and is a number of 2-3.] R ³ -O- (R ² O) nR ⁴ (II) [Wherein, R ³ and R ⁴ are each independently an alkyl group having 1 or 2 carbon atoms, R ² is an alkylene group having 2 or 3 carbon atoms, n represents an average added mole number and is a number of 1 to 3. ] The method of claim 1, (B) A component is a derivative of any one of stilbene, benzophenone or benzotriazole, The ultraviolet absorbent fiber treating composition characterized by the above-mentioned. The method of claim 1, (B) A component is a derivative of stilbene, The ultraviolet absorbent fiber treating composition characterized by the above-mentioned. The method according to any one of claims 1 to 3, (C) A component is selected from the group consisting of dibutylhydroxytoluene (BHT), methoxyphenol, ascorbic acid derivatives, bisphenols and tocopherol derivatives, UV absorbing fiber treatment composition. The method according to any one of claims 1 to 4, Moreover, (E) UV absorbing fiber treatment agent composition containing a silicone compound.