JP6573548B2 - Water repellent for textiles - Google Patents

Description

  The present invention relates to a water repellent for fibers.

  Conventionally, a water-repellent agent containing a silicone-based water-repellent substrate and a metal alkoxide is known (for example, Patent Document 1 and Patent Document 2). These water repellents are applied to the fiber by means such as spraying. The fiber is coated with a water-repellent film formed from a silicone-based water-repellent substrate and a metal alkoxide, thereby imparting water repellency to the fiber. In these water repellents, titanium alkoxide is used as a metal alkoxide from the viewpoint of excellent reactivity and water repellent effect.

JP 2000-186279 A Japanese Patent Laid-Open No. 7-305053

However, when a water repellent containing a titanium compound is applied to the fiber, yellowing may occur. In particular, when the object to which the water repellent is applied is a white or light-colored fiber product, yellowing may be noticeable and cause a problem. Further, the water repellent is required to have a superior water repellency, for example, a sufficient water repellency effect even with a smaller coating amount.
This invention is made | formed in view of the said situation, and it aims at the water-repellent agent for fibers which is excellent in the suppression effect of yellowing, and excellent in the water-repellent effect.

The water repellent for fibers of the present invention contains the following components (A), (B) and (C).
(A) component: At least 1 sort (s) chosen from the following (A1) component and (A2) component.
Component (A1): A silicone alkoxy oligomer (a1) having an alkoxy group and not having a phenyl group, and a silicone alkoxy oligomer (a2) having an alkoxy group and a phenyl group.
(A2) Component: Polyorganosilsesquioxane having RSiO _3/2 as a structural unit. In the formula, R is an organic group.
(B) Component: _{Polyorganosiloxane} having R ′ ₃ SiO _1/2 and SiO _4/2 as structural units. In the formula, R ′ is an organic group.
(C) component: Titanium alkoxide and / or its partial hydrolysis condensate.
The component (A) is preferably the component (A1). As for the mass ratio represented by (a1) component / (a2) component in said (A1) component, 0.1-9 are preferable.

  The water repellent for fibers of the present invention is excellent in yellowing suppression effect and excellent in water repellent effect.

(Water repellent for textiles)
The water repellent for fibers of the present invention (hereinafter simply referred to as “water repellent”) is a composition containing components (A) to (C).

<(A) component>
The component (A) is at least one selected from the following components (A1) and (A2).
The water repellent of this invention contains (A) component, and yellowing at the time of apply | coating to a fiber is suppressed. Furthermore, the water repellent effect is enhanced.

≪ (A1) component≫
The component (A1) is a silicone alkoxy oligomer (a1) having an alkoxy group and not having a phenyl group, and a silicone alkoxy oligomer (a2) having an alkoxy group and a phenyl group. In the present invention, the term “oligomer” means a polymer having a mass average molecular weight of 100 to 10,000. The said mass mean molecular weight is a polystyrene conversion value by GPC (gel permeation chromatography).
The component (a1) is excellent due to the yellowing suppression effect. The component (a2) is excellent in yellowing suppression effect and excellent in water repellency. By using the component (a1) and the component (a2) as the component (A1), the yellowing suppression effect and the water repellent effect are enhanced.

  (A1) As a component, the silicone alkoxy oligomer shown by General formula (1) is mentioned.

R ¹ O [(Si (CH ₃ ) (X) O) _n (Si (X) ₂ O) _m ] R ² (1)
Formula (1), R ^1, R ² are each independently a methyl or ethyl group, X is a methyl group, an ethyl group, a methoxy group or an ethoxy group, n represents the number of 1 to 20 Where m is a number from 0 to 19 and n + m is a number from 1 to 20. All Xs may be the same group or different groups. when m is greater than _{zero, [(Si (CH 3)} (X) O) n (Si (X) 2 O) m] in _{(Si (CH 3) (X} ) O) and (Si _(X) 2 O ) May be arranged in blocks or randomly. (Si (CH ₃ ) (X) O) and (Si (X) ₂ O) may be bonded to R ¹ O by (Si (CH ₃ ) (X) O), X) ₂ O) may be bonded to R ¹ O. As for (Si (CH ₃ ) (X) O) and (Si (X) ₂ O), (Si (CH ₃ ) (X) O) may be bonded to R ² or (Si (X) ₂ O) may be attached to ^{R 2.}

R ¹ and R ² are each preferably a methyl group, and X is preferably a methyl group or a methoxy group. That is, as the component (a1), a silicone methoxy oligomer having no phenyl group is preferable.
n + m is preferably 2 to 20, more preferably 2 to 15, and still more preferably 2 to 11.
Moreover, 0-50 mass% is preferable in a molecule | numerator, and, as for the amount of alkoxy groups in (a1) component, 10-35 mass% is more preferable. When the amount of alkoxy groups in the component (a1) is in the above preferred range, the yellowing suppression effect and the water repellent effect are easily improved. In particular, the yellowing suppression effect can be further enhanced.
(A1) a viscosity at 25 ° C. component is preferably 1 to 500 mm ² / s, more preferably 3~500mm ² / s, more preferably 50 to 300 mm ² / s, particularly preferably less than 100 300 mm ² / s . When the viscosity of the component (a1) at 25 ° C. is in the above preferred range, the yellowing suppression effect is easily enhanced.
The viscosity in the present invention is a value measured with an Ubbelohde viscometer at 25 ° C. in accordance with JIS Z8803.
The mass average molecular weight of the component (a1) is preferably 200 to 3000.

As the component (a1), for example, KC-89S, KR-500, KR-515, X-40-9225, X-40-9246, X-40-9250 (above trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Is mentioned. Among these, X-40-9250 is preferable.
As the component (a1), any one type may be used alone, or two or more types may be used in combination.

  (A2) As a component, the silicone alkoxy oligomer shown by General formula (2) is mentioned.

R ³ O [(Si (CH ₃ ) (Y) O) _p (Si (C ₆ H ₅ ) (Y) O) _q (Si (Y) ₂ O) _r ] R ⁴ (2)
In the formula (2), R ³ and R ⁴ are each independently a methyl group or an ethyl group, Y is a methyl group, an ethyl group, a phenyl group, a methoxy group, or an ethoxy group, and p and q are , Each is a number from 1 to 20, r is a number from 0 to 18, and p + q + r is a number from 2 to 20. Y may be the same group or different groups.
when r is _0, and _{[(Si (CH 3) (} Y) O) p (Si (C 6 H 5) (Y) O) q] in _{(Si (CH 3) (Y} ) O) (Si ( C ₆ H ₅ ) (Y) O) may be arranged in blocks or randomly. In addition, (Si (CH ₃ ) (Y) O) and (Si (C ₆ H ₅ ) (Y) O) can be combined even if (Si (CH ₃ ) (Y) O) is bonded to R ³ O. Alternatively, (Si (C ₆ H ₅ ) (Y) O) may be bonded to R ³ O. (Si (CH ₃ ) (Y) O) and (Si (C ₆ H ₅ ) (Y) O) may have (Si (CH ₃ ) (Y) O) bonded to R ⁴ , (Si (C ₆ H ₅ ) (Y) O) may be bonded to R ⁴ .
when r is greater than _{zero, [(Si (CH 3)} (Y) O) p (Si (C 6 H 5) (Y) O) q (Si (Y) 2 O) r] in (Si (CH ₃ ) (Y) O), (Si (C ₆ H ₅ ) (Y) O), and (Si (Y) ₂ O) may be arranged in blocks or randomly. In addition, any one of (Si (CH ₃ ) (Y) O), (Si (C ₆ H ₅ ) (Y) O), and (Si (Y) ₂ O) may be bonded to R ³ O. Good. Any of (Si (CH ₃ ) (Y) O), (Si (C ₆ H ₅ ) (Y) O), and (Si (Y) ₂ O) may be bonded to R ⁴ .

R ³ and R ⁴ are each preferably a methyl group, and Y is preferably a methyl group, a phenyl group or a methoxy group. That is, as the component (a2), a silicone methoxy oligomer having a phenyl group is preferable.
As for p + q + r, 2-15 are preferable and 2-11 are more preferable.
Moreover, 10-50 mass% is preferable in a molecule | numerator, and, as for the amount of alkoxy groups in (a2) component, 15-35 mass% is more preferable. When the amount of alkoxy groups in the component (a2) is in the above preferred range, the yellowing suppression effect and the water repellent effect are easily enhanced.
(A2) a viscosity at 25 ° C. components preferably 1 to 500 mm ² / s, more preferably 3~500mm ² / s, more preferably ^{10~300mm 2 / s, 10~200mm 2 /} s is particularly preferred. When the viscosity of the component (a2) at 25 ° C. is in the above preferred range, the handling property when the water repellent is applied by spraying or the like is easily improved.
The mass average molecular weight of (a2) is preferably from 200 to 10,000, more preferably from 300 to 5,000, and even more preferably from 300 to 3,000.

Examples of the component (a2) include KR-213, KR-401N, KR-510, KR-9218, X-40-9227 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Among these, KR-401N and X-40-9227 are preferable.
As the component (a2), any one type may be used alone, or two or more types may be used in combination.

The content of the component (a1) and the component (a2) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, respectively, relative to the total mass of the water repellent. 2% by mass is more preferable. When the contents of the component (a1) and the component (a2) are each equal to or higher than the lower limit, the yellowing suppression effect is easily enhanced. When the content of the component (a1) and the component (a2) is less than or equal to the above upper limit value, the water repellent effect is easily enhanced.
Mass ratio of (a1) component to (a2) component [mass ratio represented by (a1) component / (a2) component, hereinafter also referred to as “a1 / a2 ratio”. ] Is preferably 0.1-9, more preferably 0.1-4, and still more preferably 0.2-4. When the a1 / a2 ratio is in the above-described preferable range, the yellowing suppression effect and the water repellent effect are easily enhanced.

≪ (A2) component≫
The component (A2) is polyorganosilsesquioxane having RSiO _3/2 (T unit) as a structural unit. Here, R represents an organic group. In this specification, the “organic group” is a group containing a carbon atom, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine atom, chlorine atom, etc.), etc.) You may have. R is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms. More preferred are a methyl group, an ethyl group, an alkyl group of a propyl group, and an aryl group of a phenyl group, and most preferred is a propyl group.
Examples of the component (A2) include polymethylsilsesquioxane and polypropylsilsesquioxane. Among these, polypropylsilsesquioxane is preferable because it is more excellent in yellowing suppression effect and water repellent effect.
As the component (A2), for example, trade name “670 Fluid” manufactured by Toray Dow Corning Co., Ltd. (polypropylsilsesquioxane diluted with cyclopentasiloxane [concentration 50 mass%], viscosity 200 mm ² / s), trade name "680 ID Fluid" (polypropylsilsesquioxane diluted with isododecane [concentration: 75% by mass], viscosity: 900 mm ² / s) and the like.

As the component (A2), any one type may be used alone, or two or more types may be used in combination.
The content of the component (A2) is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, and still more preferably 0.5 to 2% by mass with respect to the total mass of the water repellent. . When the content of the component (A2) is not less than the above lower limit, the yellowing suppression effect is easily enhanced. When the content of the component (A2) is not more than the above upper limit value, the water repellent effect is easily enhanced.

The content of the component (A) is preferably 0.02 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.1 to 2.5% by mass with respect to the total mass of the water repellent. Further preferred.
When the content of the component (A) is not less than the above lower limit, the yellowing suppression effect is easily enhanced. When the content of the component (A) is not more than the above upper limit value, the water repellent effect is easily enhanced.

The reason why the water repellent of the present invention contains the component (A) to suppress yellowing when applied to the fiber is not clear in detail, but is estimated as follows.
When a water repellent containing a titanium compound is applied to the fiber, if there is an excess of the titanium compound, a colored substance is formed from titanium in the titanium compound, or a reaction product is formed by reacting titanium with impurities, etc. Yellow).
The component (A) is highly reactive with titanium, and reacts with excess titanium when the water repellent is applied to the fiber to capture titanium. Thereby, formation of a coloring substance is suppressed and it is estimated that yellowing is suppressed.

In addition, although (a1) component and (a2) component are components which can respectively provide the yellowing suppression effect and the water-repellent effect, (a1) component is excellent by the yellowing suppression effect, (a2) component is Excellent water repellent effect. In the present invention, by using the (a1) component and the (a2) component together as the component (A1), the yellowing suppression effect and the water repellent effect are sufficiently enhanced.
In addition, both the component (A1) and the component (A2) are components that can impart a yellowing suppressing effect and a water repellent effect. However, the component (A2) tends to give a hard feel to the fiber when applied to the fiber. Therefore, when it is not preferable that the fiber has a hard feel, the component (A1) is preferably used as the component (A).

<(B) component>
The component (B) is a polyorganosiloxane having R ′ ₃ SiO _1/2 (M unit) and SiO _4/2 (Q unit) as constituent units. Here, R ′ represents an organic group. R ′ is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms. More preferred are a methyl group, an ethyl group, an alkyl group of a propyl group, and an aryl group of a phenyl group, and most preferred is a methyl group. A plurality of R ′ may be the same or different.
When the water repellent of the present invention contains the component (B), a water repellent film is firmly formed and water repellency is improved.

The component (B) is a network resin. The component (B) may be used after diluted or dissolved with a solvent.
Examples of the solvent include alcohol solvents, silicones such as dimethicone, cyclopentasiloxane, and methyltrimethicone, and hydrocarbons such as isododecane.
Component (B) has a viscosity (25 ° C.) of diluting liquid when used in diluted or dissolved in a solvent, preferably ^{10~10000mm 2 / s, 20~5000mm 2 /} s is more preferable. For example, by diluting with cyclopentasiloxane so that the concentration of the component (B) is 30 to 60% by mass, a diluted solution having the above preferred viscosity range can be obtained.

As the component (B), for example, trade name “MQ-1600 SOLID RESIN” (trimethylsiloxysilicic acid, solid [concentration 100% by mass]) manufactured by Toray Dow Corning Co., Ltd., trade name “DC593” (trimethylsiloxysilicate) Acid, dimethicone diluted product [concentration 33% by mass], viscosity 560 mm ² / s), trade name “BY11-018” (trimethylsiloxysilicic acid, cyclopentasiloxane diluted product [concentration 30% by mass], viscosity 20 mm ² / s) ,; Trade name “KF-7312K” manufactured by Shin-Etsu Chemical Co., Ltd. (trimethylsiloxysilicic acid, dimethicone diluted product [concentration 60% by mass], viscosity 5000 mm ² / s), trade name “KF-7312J” (trimethylsiloxysilicate) Acid, cyclopentasiloxane diluted product [concentration 50% by mass], viscosity 120 mm ² / s), Examples include the product name “KF-7312T”, the product name “KF-7312L”, the product name “X-21-5249”, the product name “X-21-5595”, and the like. However, the component (B) is not limited to these.

As the component (B), any one type may be used alone, or two or more types may be used in combination.
The content (B) of the component (B) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and more preferably 0.5 to 3% with respect to the total mass of the water repellent. More preferred is mass%.
When the content of the component (B) is equal to or more than the above lower limit value, a water-repellent film is firmly formed and the water repellency is easily increased. When the content of the component (B) is equal to or less than the above upper limit value, the blending stability of the water repellent is easily increased.

  Mass ratio of component (A) to component (B) [mass ratio represented by component (A) / component (B), hereinafter also referred to as “A / B ratio”. ] Is preferably 0.1 to 3, more preferably 0.2 to 2.5, and still more preferably 0.4 to 2. Further, 0.7 to 2 is most preferable. When the A / B ratio is in the above preferred range, the water repellent effect is further enhanced, and sufficient water repellency is easily obtained even when the amount of the water repellent applied is reduced.

<(C) component>
Component (C) is a titanium alkoxide and / or a partial hydrolysis condensate thereof.
When the water repellent of the present invention contains the component (C), a water repellent film is satisfactorily formed.
Examples of the component (C) include tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, titanium tetranormal butoxide, tetra (2-ethylhexyloxy) titanium, titanium butoxy dimer, and the like. Among these, titanium tetranormal butoxide and titanium butoxy dimer are preferable.
(C) As a component, a commercial item may be used. Examples of commercially available products of component (C) include Matsumoto Fine Chemical Co., Ltd. trade name “Orga Tix TA-22” (titanium butoxy dimer), trade name “Orga Tix TA-25” (titanium tetranormal butoxide), and the like. .

As the component (C), any one type may be used alone, or two or more types may be used in combination.
The content of the component (C) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and still more preferably 0.1 to 3% by mass with respect to the total mass of the water repellent. 0.1 to 2% by mass is particularly preferable. When the content of the component (C) is not less than the lower limit of the above preferable range, the water-repellent film is firmly formed, and the water repellency is easily increased. When the content of the component (C) is not more than the upper limit of the above preferable range, yellowing is easily suppressed. Furthermore, the blending stability of the water repellent is easily increased.

  Mass ratio of component (B) to component (C) [mass ratio represented by component (B) / component (C), hereinafter also referred to as “B / C ratio”. ] Is preferably 9/1 to 1/9, more preferably 9/1 to 3/7, and still more preferably 7/3 to 4/6. When the B / C ratio is in the above preferred range, the yellowing suppression effect and the water repellent effect are easily enhanced.

  Mass ratio of component (A) to component (C) [mass ratio represented by component (A) / component (C), hereinafter also referred to as “A / C ratio”. ] Is preferably 0.05 to 20, and more preferably 0.5 to 5. When the A / C ratio is at least the lower limit value of the above preferred range, the yellowing suppression effect is likely to be enhanced. When the A / C ratio is not more than the upper limit of the above preferred range, the water repellent effect is easily enhanced.

<Solvent>
The water repellent of the present invention preferably contains an alcohol solvent as a solvent from the viewpoint of excellent handling properties during production and use.
Examples of the alcohol solvent include monohydric alcohols, dihydric alcohols, and the like, for example, methanol, ethanol, isopropyl alcohol (2-propanol), n-butanol, propylene glycol, isoprene glycol, hexylene glycol, and the like. It is done. As the alcohol solvent, a lower alcohol is preferable because it is easily available and the odor is reduced during use. Examples of the lower alcohol include lower alcohols having 4 or less carbon atoms, and among them, isopropyl alcohol is preferable.
Any one alcohol-based solvent may be used alone, or two or more alcohol-based solvents may be used in combination.
Although content of a solvent is not specifically limited, 80-99.5 mass% is preferable with respect to the total mass of a water repellent from the point from which favorable mixing | blending stability becomes easy to be obtained.

<Other ingredients>
The water repellent of this invention may contain the other component normally used for a water repellent other than said (A)-(C) component.
Examples of other components include silicone compounds other than the components (A) and (B), fragrances, ultraviolet absorbers, and antioxidants.

Examples of silicone compounds other than the components (A) and (B) include dimethyl silicone, methylphenyl silicone, methyl hydrogen silicone, cyclic silicone, amino-modified silicone, epoxy-modified silicone, carbinol-modified silicone, mercapto-modified silicone, poly Examples include ether-modified silicone, methylstyryl-modified silicone, alkyl-modified silicone, fluorine-modified silicone, higher fatty acid-modified silicone, methacryl-modified silicone, phenol-modified silicone, and dimethiconol.
Any one of these silicone compounds may be used alone, or two or more thereof may be used in combination.
When the water repellent of the present invention contains the silicone compound, the content of the silicone compound is preferably more than 0 to 10% by mass and 0.01 to 5% by mass with respect to the total mass of the water repellent. % Is more preferable, 0.1 to 3% by mass is further preferable, and 0.1 to 2% by mass is particularly preferable. When the content of the silicone compound is within the above preferable range, the yellowing suppression effect and the water repellent effect are easily enhanced.
Although it does not specifically limit as said fragrance | flavor, For example, a floral fragrance | flavor, a citrus fragrance | flavor, a musk fragrance | flavor, a mint fragrance | flavor, etc. are mentioned.
The total content of the components (A) to (C), the solvent, and the optional component in the water repellent of the present invention does not exceed 100% by mass.

<Method for producing water repellent>
The water repellent of the present invention is produced, for example, by dissolving the components (A) to (C) and optional components as necessary in isopropyl alcohol as a solvent. Moreover, you may manufacture by melt | dissolving all the components of (A) component-(C) component, or one part component in the isopropyl alcohol which is a solvent separately, and mixing this.

  The water repellent of the present invention is accommodated in a generally used container. The material of the container is not particularly limited, and examples thereof include metals. Examples of the metal include tinplate, aluminum, and aluminum alloy. In order to prevent corrosion of the metal, the surface of the metal may be coated with a resin. Examples of the resin include epoxy resin, acrylic resin, butyral resin, phenol resin, polyamide resin, polyimide resin, polyamideimide resin, alkyd resin, amino resin, and polyester resin.

Examples of the container include, but are not limited to, a container in which a water repellent is usually contained. For example, an aerosol spray container, a trigger spray container (direct pressure type or pressure accumulation type), a finger spray container, or a dispenser type pump spray. A container etc. are mentioned.
Examples of the aerosol spray container include containers described in JP-A-9-3441, JP-A-9-58765, and the like.
Examples of the trigger spray container include containers described in JP-A-9-268473, JP-A-9-256272, JP-A-10-76196, and the like.
Examples of the pump spray container include containers described in JP-A-9-256272.

<How to use water repellent>
Examples of the method of using the water repellent of the present invention include a method of applying a water repellent to fibers. The method for applying the water repellent is not particularly limited, and examples thereof include a spray coating method, a brush coating method, and a dip coating method.
Among these, from the viewpoint of excellent usability, a method in which a water-repellent agent is filled in an aerosol spray container and sprayed onto fibers is preferable.
When filling the aerosol spray container with the water repellent of the present invention, a propellant (hereinafter also referred to as “component (D)”) is added to the water repellent of the present invention, and an aerosol type water repellent ( Hereinafter, it is also simply referred to as “aerosol type water repellent”).

The component (D) is not particularly limited, and examples thereof include liquefied petroleum gas, dimethyl ether, liquefied carbon dioxide gas, and liquefied nitrogen gas.
As the component (D), any one type may be used alone, or two or more types may be used in combination.
In the case of a propellant having a high solubility in an organic solvent such as liquefied petroleum gas and dimethyl ether, the blending amount of the component (D) is based on the total mass of the aerosol-type water repellent, 5-50 mass% is preferable and 10-40 mass% is more preferable. In the case of a propellant having low solubility in an organic solvent such as liquefied carbon dioxide gas or liquefied nitrogen gas, 1 to 10% by mass is preferable and 1 to 5% by mass is more preferable with respect to the total mass of the aerosol-type water repellent. preferable.

  Examples of the object to which the water repellent of the present invention is applied include textiles such as clothes, umbrellas, bags, shoes, curtains and sofas. Since the water repellent of the present invention is excellent in the yellowing suppression effect, the water repellent may be used for white or light-colored textiles that have been defective until now.

  As described above, since the water repellent of the present invention contains the components (A) to (C), yellowing is suppressed when applied to fibers, and the water repellent effect is excellent.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In this example, “%” indicates “% by mass” unless otherwise specified.
The raw materials used in this example are as follows.

<A component>
≪A1 ingredient≫
(A1) Component: Silicone alkoxy oligomer having an alkoxy group and not having a phenyl group a1-1: KC-89S (trade name) [Amount of methoxy group: 45 mass%, viscosity (25 ° C.): 5 mm ² / s] Made by Shin-Etsu Chemical Co., Ltd.
a1-2: KR-500 (trade name) [methoxy group amount: 28% by mass, viscosity (25 ° C.): 25 mm ² / s], manufactured by Shin-Etsu Chemical Co., Ltd.
a1-3: X-40-9225 (trade name) [methoxy group amount: 24 mass%, viscosity (25 ° C.): 100 mm ² / s], manufactured by Shin-Etsu Chemical Co., Ltd.
a1-4: X-40-9246 (trade name) [methoxy group amount: 12% by mass, viscosity (25 ° C.): 80 mm ² / s], manufactured by Shin-Etsu Chemical Co., Ltd.
a1-5: X-40-9250 (trade name) [methoxy group amount: 25% by mass, viscosity (25 ° C.): 160 mm ² / s], manufactured by Shin-Etsu Chemical Co., Ltd.

Component (a2): Silicone alkoxy oligomer having an alkoxy group and a phenyl group a2-1: KR-401N (trade name) [methoxy group amount: 33% by mass, viscosity (25 ° C.): 20 mm ² / s], Shin-Etsu Chemical Co., Ltd. Made by Co., Ltd.
a2-2: X-40-9227 (trade name) [methoxy group amount: 15% by mass, viscosity (25 ° C.): 15 mm ² / s], manufactured by Shin-Etsu Chemical Co., Ltd.
a2-3: X-40-9247 (trade name) [methoxy group amount: 16% by mass, viscosity (25 ° C.): 100 mm ² / s], manufactured by Shin-Etsu Chemical Co., Ltd.
a2-4: KR-510 (trade name) [methoxy group amount: 17% by mass, viscosity (25 ° C.): 100 mm ² / s], manufactured by Shin-Etsu Chemical Co., Ltd.
a2-5: KR-9218 (trade name) [methoxy group amount: 15% by mass, viscosity (25 ° C.): 40 mm ² / s], manufactured by Shin-Etsu Chemical Co., Ltd.
a2-6: KR-213 (trade name) [methoxy group amount: 20% by mass, viscosity (25 ° C.): 16 mm ² / s], manufactured by Shin-Etsu Chemical Co., Ltd.

≪A2 ingredient≫
A2-1: Polyorganosilsesquioxane (trade name “670 Fluid”, manufactured by Toray Dow Corning Co., Ltd.).

<B component>
B-1: KF-7312K (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.

<C component>
C-1: Titanium butoxy dimer, ORGATICS TA-22 (trade name), manufactured by Matsumoto Fine Chemical Co., Ltd.
C-2: Titanium tetranormal butoxide, ORGATICS TA-25 (trade name), manufactured by Matsumoto Fine Chemical Co., Ltd.

<Optional component>
Solvent: isopropyl alcohol.

(Examples 1-22, Comparative Examples 1-8)
<Manufacture of water repellent>
Isopropyl alcohol was collected in a 1 L beaker, and the components (B) and (C) were added and mixed to obtain a solution. Next, component (A1) [component (a1) and component (a2)] was collected in a 300 mL beaker. The said solution was added and mixed in this, and the water repellent of Examples 1-10, 12-18, 20-22 was manufactured.
The water repellents of Examples 11 and 19 were produced in the same manner as Example 1 except that the component (A2) was used instead of the component (A1).
Moreover, the water repellent of Comparative Examples 1-4 was manufactured like Example 1 except not having added any one or both of (a1) component and (a2) component.
A water repellent of Comparative Example 5 was produced in the same manner as in Example 11 except that the components (B) and (C) were not added.
The water repellents of Comparative Examples 6 and 7 were produced in the same manner as in Example 1 except that either the component (a1) or the component (a2) and the component (B) were not added.
The water repellent of Comparative Example 8 was produced in the same manner as in Example 11 except that the component (C) was not added.

Tables 1 to 3 show the compositions (formulation components, content (% by mass)) of the water repellents of the obtained examples.
In the table, when there is a blank blending component, the blending component is not blended.
In the table, the content of the compounding component indicates a pure equivalent amount.
“Balance” indicating the content of the solvent means the balance added so that the total amount (mass%) of all the ingredients contained in the water repellent is 100 mass%.

  For each of the water repellents, an aerosol type water repellent was prepared as described below, and the water repellent effect and the yellowing suppression effect were evaluated as follows. The evaluation results are shown in Tables 1-3.

≪Preparation of aerosol type water repellent≫
100 g of the water repellent of each example and liquefied petroleum gas (propellant) were stored in an aerosol spray container having the following specifications according to a conventional method to obtain an aerosol type water repellent (85% by mass of water repellent, liquefied Petroleum gas (0.39 MPa) 15 mass%).
[Specifications of aerosol container]
Can: BL35 × 110 B2 modified coat (trade name, manufactured by Toyo Seikan Co., Ltd., material of can; aluminum alloy, material of inner surface resin coat: epoxy polyamideimide).
Valve: S13- (70P) 78HG7183ALPS “26” × 76R (trade name, manufactured by Mitani Valve Co., Ltd.).
Button: D94WIB03735N "3" -A (trade name, manufactured by Mitani Valve Co., Ltd.).

<Evaluation of water repellency>
[Preparation of test cloth]
A commercially available cotton broad (trade name: color broad (blue, 100% cotton) GM502-117) was prepared. 30L of 40 ° C tap water is put into a household washing machine (two-tank washing machine, manufactured by MITSUBISHI, CW-C30A1-H), and powder detergent for clothing (trade name: deodorant blue diamond, manufactured by Lion Corporation) ) 25 g was added and dispersed. Next, 1 kg of the above cotton broad was added, stirred for 15 minutes, washed, and then dehydrated for 3 minutes. Next, running water was rinsed with tap water for 15 minutes and dehydrated for 3 minutes. The running water rinse and dehydration were repeated three times. Thereafter, the cotton broad was dried at room temperature, cut into 20 cm × 20 cm and ironed to obtain a test cloth.
[Water repellency test (1)]
The aerosol-type water repellent was sprayed uniformly on the entire test cloth. The coating amount was 0.5 times the mass of the test cloth before coating (50% OWF). Then, what was dried indoors for 1 day was made into the "water-repellent-treated test cloth."
The water repellency was evaluated according to the JIS L-1092 water repellency test (spray test). That is, the water-repellent-treated test cloth was attached to a frame having a diameter of about 15 cm so as not to be wrinkled, and was fixed on a table so as to have an angle of 45 degrees with respect to a horizontal plane. Thereto, 5 L of ion-exchanged water of 27 ± 1 ° C. was sprayed on the water-repellent-treated test cloth from a spray nozzle set at a height of 15 cm from the center of the water-repellent-treated test cloth. Next, remove the frame from the base, hold one end of the frame, hit the other end with the surface (water repellent application surface) facing down, and drop off excess water drops, then the water-repellent treated fabric Was scored in increments of 0.5 according to the following criteria to evaluate the water repellent effect of the water repellent of each example.
(Criteria)
5 points: No wetting of water or adhesion of water droplets observed on the surface.
4.5 points: No wetness of water was observed on the surface, but very small water droplets were observed.
4 points: No wetness of water was observed on the surface, but a small amount of water droplets was observed.
3.5 points: Slight wetting of small individual water droplets was observed on the surface.
3 points: Slight wetting of small individual water droplets was observed on the surface.
2.5 points: water was observed in an area of about 1/4 of the surface.
2 points: Water observed to be about half the surface area.
1.5 points: Water observed to be about 3/4 of the surface area.
1 point: Water was observed to be observed on the entire surface.
0.5 points: Water was observed on the entire surface, and water was also observed slightly on the back.
0 point: Water was observed to be observed on the entire front and back surfaces.

[Water repellency test (2)]
The amount of the aerosol-type water repellent applied was 0.25 times the mass of the test cloth before application (25% OWF), and ion-exchanged water sprayed on the water-repellent-treated test cloth. The water repellency test (2) was conducted in the same manner as the water repellency test (1) except that the water repellency of each example was evaluated.

<Evaluation of yellowing suppression effect>
A commercially available white cloth (nylon tricot) was cut into 10 cm × 10 cm to obtain a test cloth. The aerosol-type water repellent was sprayed for 1 second at a distance of 20 cm from the test cloth, and then allowed to stand at room temperature for 1 day. The b value of the test cloth after standing and the above-mentioned test cloth (test cloth before applying the water repellent) is measured using a color difference meter (trade name: SE200 type, manufactured by Nippon Denshoku Co., Ltd.). From this, the Δb value was calculated and the yellowing suppression effect of the water repellent of each example was evaluated according to the following criteria. In addition, it can be evaluated that yellowing was suppressed, so that Δb value was small. Δ to ◎◎ were regarded as acceptable.
Δb value = (b value of the evaluation cloth after being left) − (b value of the evaluation cloth)
(Criteria: Δb value)
◎◎: Less than 1
: 1 or more and less than 2.
○○: 2 or more and less than 4.
○: 4 or more and less than 6.
Δ: 6 or more and less than 8.
X: 8 or more.

From the results shown in Tables 1 to 3, the water repellents of Examples 1 to 22 to which the present invention was applied scored 2.5 points or more in the water repellency test (1) and one or more points in the water repellency test (2). It was a result. Furthermore, it was evaluation result of (triangle | delta)-(double-circle) about the yellowing suppression effect.
On the other hand, the water repellent (Comparative Example 1) which does not contain the component (a2) and does not contain the component (a2) and the component (B) (Comparative Example 6) The water repellent (Comparative Example 7) that does not contain the component (a1) and the component (B) and the water repellent (Comparative Example 8) that does not contain the component (C) have a score of 0 in the water repellency test (2). Thus, the water repellent effect was not sufficient.
The water repellent (Comparative Example 2) that does not contain the component (a1) and the two components (a2) are used together, and the water repellent that does not contain the component (A) (Comparative Examples 3 and 4) suppresses yellowing. The effect was not enough.
The water repellent (Comparative Example 5) containing no component (B) or component (C) was scored 0 in the water repellency test (2), and the water repellency effect was not sufficient.
From the above results, it was confirmed that the water repellent to which the present invention was applied was excellent in the yellowing suppression effect and excellent in the water repellent effect.

Claims (10)

A water repellent for fibers comprising the following component (A), component (B) and component (C).
The (A) component is at least one selected from the group consisting of the following (A1) component and (A2) component , and the (A1) component includes the following (a1) component and the following (a2) component: The mass ratio represented by component (a1) / component (a2) is 0.1 to 9, and the content of component (a2) is 0.01 to the total mass of the water repellent for fibers. -10 mass%.
Component (A1): A silicone alkoxy oligomer (a1) having an alkoxy group and not having a phenyl group, and a silicone alkoxy oligomer (a2) having an alkoxy group and a phenyl group.
(A2) Component: Polyorganosilsesquioxane having RSiO _3/2 as a structural unit.
In the formula, R is an organic group.
(B) Component: _{Polyorganosiloxane} having R ′ ₃ SiO _1/2 and SiO _4/2 as structural units. In the formula, R ′ is an organic group.
(C) component: Titanium alkoxide and / or its partial hydrolysis condensate. The water repellent for fibers according to claim 1, wherein the content of the component (a1) is 0.01 to 10% by mass with respect to the total mass of the water repellent for fibers.   The component (A) includes the component (A2), and the content of the component (A2) is 0.1 to 5% by mass with respect to the total mass of the water repellent for fibers. 2. A water repellent for fibers according to 2.   The water repellent for fibers according to any one of claims 1 to 3, wherein the content of the component (B) is 0.1 to 10% by mass with respect to the total mass of the water repellent for fibers. .   The water repellent for fibers according to any one of claims 1 to 4, wherein the content of the component (C) is 0.01 to 10% by mass with respect to the total mass of the water repellent for fibers. .   The water repellent for fibers according to any one of claims 1 to 5, wherein a mass ratio represented by (A) component / (B) component is 0.1-3.   The water repellent for fibers according to any one of claims 1 to 6, wherein a mass ratio represented by (B) component / (C) component is 9/1 to 1/9.   The water repellent for fibers according to any one of claims 1 to 7, wherein a mass ratio represented by (A) component / (C) component is 0.05 to 20.   The water repellent for fibers according to any one of claims 1 to 8, further comprising a solvent.   The water repellent for aerosol type fibers, wherein the water repellent for fibers according to any one of claims 1 to 9 further contains the following component (D).
(D) component: propellant.