JP2008150498A - Water repellent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-repellent composition which is a silicone-based water-repellent composition, can impart water repellency and water repellency persistence, has rapid drying properties, and leaves little residual odor. <P>SOLUTION: The water-repellent composition comprises a polyorganosiloxane (A) alkoxy-blocked at both ends, a metal alkoxide and/or a condensate of a partial hydrolyzate thereof (B), a 3-6C paraffinic hydrocarbon (C), and a 2-4C monohydric alcohol (D). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a water repellent composition that imparts water repellency to textiles and leather.

Conventionally, water repellent compositions using various fluorine-based bases have been used as those for imparting water repellency to textiles and leather. As such a fluorine-based base, for example, a polymer of a monomer containing a perfluoro group or a fluoroalkyl group in the molecule, or a copolymer of these monomers with other monomers is used.
However, the water repellent composition using such a (co) polymer has a good water repellency effect, but it is cited as a cause of the destruction of the ozone layer in the atmosphere as a solvent for dilution, and for protecting the global environment. There was a problem that a compound whose use was restricted from the viewpoint had to be used. In addition, although an alternative solvent free from such problems has been studied, satisfactory results have not yet been obtained.

Therefore, recently, a water repellent composition using a silicone base that does not require the use of a solvent that causes ozone layer destruction has been studied.
Examples of the water repellent composition using a silicone base include a water repellent component comprising, for example, a specific organic solvent-soluble silicone resin and / or organic solvent-soluble silicone graft acrylic resin, a metal alkoxide, and an organopolysiloxane. An aerosol-type water-repellent treatment agent containing an organic solvent and a jet gas (see Patent Document 1), a polyorganosiloxane blocked at both ends with an alkoxy group, a metal alkoxide or a partially hydrolyzed condensate thereof, Water repellent compositions containing ethanol or isopropanol (see Patent Document 2) have been proposed. In addition, a specific polyorganosiloxane resin, a linear dipolyorganosiloxane, an organic titanate ester, an organic zirconate ester, an organic germanate ester, an antibacterial silane having a quaternary ammonium base, a solvent, A water repellent composition comprising a water repellent composition (see Patent Document 3), a specific polyorganosiloxane resin, an alkyl-alkoxypolysiloxane resin, a condensation catalyst, and an aromatic solvent (Patent Document) 4) has been proposed.
JP 2000-186279 A Japanese Patent No. 3496976 Japanese Patent No. 3187445 JP-A 63-170484

However, a water repellent composition using a silicone base generally has insufficient water repellency and water repellency compared to a water repellent composition using a fluorine base. Even when the water repellent composition described in the literature is used, sufficient water repellency and water repellency persistence may not always be obtained. If the water repellency persistence is insufficient, even if the water repellent composition is used for an object such as a textile product, intermittent rainwater may penetrate into the object, and the object is particularly In the case of clothing, there may be a case where sweat permeates due to permeation of sweat.
In addition to water repellency and water repellency, the water repellent composition is required to have quick-drying properties and no odor residue after use. No liquid composition has been found in the past.

The present invention has been made in view of the above circumstances, and in a water repellent composition using a silicone base material, it can impart excellent water repellency and water repellency, and has quick drying properties and odor. It aims at providing the water repellent composition in which the remainder was suppressed.

The water repellent composition of the present invention comprises a polyorganosiloxane (A) having both ends blocked with alkoxy groups, a metal alkoxide and / or a partially hydrolyzed condensate (B) thereof, and a paraffin having 3 to 6 carbon atoms. It contains a C-type hydrocarbon (C) and a monohydric alcohol (D) having 2 to 4 carbon atoms.
The mass ratio between the component (D) and the component (C) is preferably (D) / (C) = 0.2 or more and less than 20.

  According to the present invention, in a water repellent composition using a silicone base, a water repellent which can impart excellent water repellency and water repellency, has quick drying properties, and has a suppressed odor residue. A composition can be provided.

Hereinafter, the present invention will be described in detail.
The water repellent composition of the present invention comprises a polyorganosiloxane (A) having both ends blocked with alkoxy groups, a metal alkoxide and / or a partially hydrolyzed condensate (B) thereof, and a paraffin having 3 to 6 carbon atoms. Containing a hydrocarbon based hydrocarbon (C) and a monohydric alcohol (D) having 2 to 4 carbon atoms, and as a specific form, is an aerosol-type water repellent accommodated in an aerosol spray container at high pressure Liquid spray type water repellent composition that is contained in a liquid form in an agent composition, a trigger spray container, a finger spray container, a pump spray container (for example, a dispenser type, etc.), and the like.
Hereinafter, these components may be referred to as (A) component, (B) component, (C) component, and (D) component, respectively.

[Component (A) and Component (B)]
The component (A) and the component (B) are components that are used as a silicone base of the water repellent composition and exhibit excellent water repellency and water repellency persistence.
As the component (A), for example, those represented by the following general formula (I) can be preferably used.

R ¹ _n X _(3-n) SiO— [SiR ² ₂ O] _m —SiR ³ _n X _(3-n) (I)
(In the formula (I), R ^{1 to} R ³ each represent a monovalent hydrocarbon group or a substituted hydrocarbon group which may be the same or different, X represents an alkoxy group, and m represents a compound of the formula (I). The viscosity at 25 ° C. is a value of 5 to 1000 mPa · s, and n represents an integer of 0 to 2.)

Examples of the monovalent hydrocarbon group include a linear or branched alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and a hexadecyl group, a cyclohexyl group, and a cyclooctyl group. A cycloalkyl group such as a phenyl group, an aryl group such as a phenyl group, a tolyl group and a naphthyl group, an aralkyl group such as a benzyl group, a β-phenylethyl group and a methylbenzyl group, and an alkenyl group such as a vinyl group and an allyl group. .
Examples of the monovalent substituted hydrocarbon group include a fluoroalkyl group such as 3,3,3-trifluoropropyl group, an amino group such as γ-aminopropyl group and N- (β-aminoethyl) -γ-aminopropyl group. An alkyl group etc. are mentioned.
Among these, as R ^{1 to} R ³ , since a water repellent composition exhibiting good water repellency can be easily obtained, both of them are preferably alkyl groups and aryl groups, and particularly methyl groups and phenyl groups. preferable.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, and the like. When X is a methoxy group, a water repellent composition having a high water-repellent film formation rate is easily obtained, which is preferable.

  As such polyorganosiloxane, both terminal monoalkoxy blocked polyorganosiloxane (n = 2) and both terminal dialkoxy blocked polyorganosiloxane are selected depending on the number of alkoxy groups determined by the value of n in formula (I). (N = 1), both-terminal trialkoxy-capped polyorganosiloxane (n = 0) are mentioned, and these may be used alone or in a mixture of two or more.

  In the formula, the value of m is a value at which the viscosity of the compound of formula (I) at 25 ° C. is 5 to 1000 mPa · s. Since the solubility is good and the properties of the water repellent film formed from the water repellent composition are good, the viscosity at 25 ° C. is 5 to 500 mPa · s, more preferably 5 to 200 mPa · s. It is preferably a value.

  The polyorganosiloxane having both ends alkoxy-blocked as component (A) can be produced by a known method. That is, a method of hydrolyzing and alkoxylating dimethyldichlorosilane in water and methanol, a method of dialkoxylating a hydroxyl-blocked polyorganosiloxane at both ends with methyltrimethoxylane in the presence of an acid or alkali, etc. It is done.

The (B) component metal alkoxide is a compound in which an alkoxy group is bonded to a metal atom, and examples thereof include titanium alkoxide, silicon alkoxide, aluminum alkoxide, and zirconium alkoxide. These partial hydrolysis condensates are also component (B). Can be used as The alkoxy group may be linear or branched, and the carbon number thereof is preferably 1 to 10, more preferably 3 to 8.
Specific examples of such metal alkoxides include tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra (n-butoxy) titanium, tetra (2-ethylhexyloxy) titanium, tetramethoxysilane, tetraethoxysilane, tetra Examples thereof include isopropoxysilane, tetrabutoxysilane, trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, tributoxyaluminum, tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium and the like. Among these, titanium alkoxide is preferable, and further, the curable property of the water-repellent film and the storage stability of the water-repellent composition are good, so that tetraisopropoxy titanium, tetra (n-butoxy) titanium, tetra (2-ethylhexyl) are particularly preferable. Oxy) titanium is preferred.
These titanium alkoxides are obtained from Nippon Soda, Mitsubishi Gas Chemical, and Matsumoto Pharmaceutical Industries under the trade names A-1, B-1, TOT, tetra n-butyl titanate, TBT, ORGATIC TA-10, and ORGATIC TA-25. be able to.

When such a component (A) and component (B) are used as a base, since a polyorganosiloxane having both ends blocked with alkoxy groups is selected as the component (A), It is presumed that a synergistic effect due to the combined use with the component (B) is exhibited, and excellent water repellency and water repellency persistence can be obtained.
That is, the metal alkoxide of component (B) or a partially hydrolyzed condensate thereof is hydrolyzed by the influence of moisture in the air to release alcohol and form a cured film on the object. It acts as a crosslinking reaction catalyst for the polymer having For this reason, when the polyorganosiloxane (A) having an alkoxy group as a reactive group at both ends is present together with the component (B), the portions at both ends are involved in the crosslinking reaction. As a result, the formed water-repellent film is more penetrated and fixed to the object, and it is considered that excellent water repellency and water repellency persistence can be obtained.

[Component (C)]
The component (C) is used as a solvent for dissolving the component (A) and the component (B) described above. In the present invention, the component (C) is a paraffinic hydrocarbon having 3 to 6 carbon atoms (C). C) is adopted. Therefore, it is possible to obtain a water repellent composition that is excellent in quick-drying after use and has a reduced odor residue, and can be used easily without causing any inconvenience even in ordinary households with poor ventilation facilities. If, for example, a paraffinic hydrocarbon having 7 or more carbon atoms or an aromatic solvent is used instead of the component (C), the quick-drying property is deteriorated and the odor residue cannot be suppressed. The simple use of is difficult.

  As the component (C), one or more of propane, butane, pentane, hexane and isomers thereof can be used. The water repellent composition of the present invention is accommodated in a pressure vessel such as a tin can or an aluminum can. In the case of an aerosol type water repellent composition to be sprayed, it is preferable to use at least propane and / or butane as the component (C) because these also act as a propellant. For example, propane and / or butane is used as the component (C), and these are allowed to act as a propellant, or pentane or hexane is selected as the component (C) and propane and / or butane is used. And / or butane can also act as a propellant. However, by selecting pentane or hexane as the component (C) and simultaneously using other general propellants (dimethyl ether, liquefied carbon dioxide gas, liquefied nitrogen gas, etc.), an aerosol-type water repellent composition may be used. . On the other hand, when the water repellent composition of the present invention is a liquid spray type water repellent composition, it is preferable to use pentane and / or hexane which is liquid at room temperature as the component (C). As the component (C), it is preferable to use a branched hydrocarbon from the viewpoint of safety.

[(D) component]
The component (D) is a component that imparts excellent water repellency to the water repellent composition and is one or more of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and secondary butanol. Can be used. Of these, ethanol or isopropanol is preferably used from the viewpoint of quick drying. In the water repellent composition not containing the component (D), the water repellency persistence is insufficient.

[Water repellent composition]
(Amount of each component)
The water repellent composition of the present invention contains the above-mentioned components (A) to (D), and the amount of each component is not particularly limited, but is preferably as follows.
That is, the compounding quantity of (A) component is 0.01-10 mass% in a water repellent composition, Preferably it is 0.05-5 mass%, More preferably, it is the range of 0.1-3 mass%. Water repellency improves more as it is 0.01 mass% or more. When it is 10% by mass or less, a stain derived from the water repellent composition is less likely to occur, and when used in a textile product such as clothing, the texture is not deteriorated and deteriorated.
(B) The compounding quantity of a component is 0.01-10 mass% in a water repellent composition, Preferably it is 0.05-5 mass%, More preferably, it is the range of 0.08-2 mass%. When the content is 0.01% by mass or more, the curability of the water repellent film formed by the water repellent composition is good, and the water repellency and water repellency persistence can be improved. The storage stability of a water repellent composition can be improved as it is 10 mass% or less.
The mass ratio of the component (A) to the component (B) is not particularly limited, but preferably (A) / (B) = 95/5 to 40/60. When the ratio of (A) exceeds 95, that is, when the ratio of (B) is less than 5, the effect as the above-mentioned crosslinking reaction catalyst is inferior, so that sufficient film formation may not be performed. On the other hand, when the ratio of (A) is less than 40, that is, when the ratio of (B) exceeds 60, although the effect as a crosslinking reaction catalyst is sufficient, the film becomes relatively brittle. Therefore, in any case, good water repellency and water repellency persistence may not be obtained.

(C) The compounding quantity of a component is 3.5 mass% or more in a water repellent composition. Preferably it is 5.0-90 mass%, More preferably, it is the range of 10-80 mass%. The quick-drying property of a water repellent composition improves more that it is 3.5 mass% or more. In addition, when the water repellent composition of the present invention is an aerosol type water repellent composition, and at least propane and / or butane is used as the component (C), it can also exert an action as a propellant. More preferably, the blending amount of propane and / or butane is 3.5 to 50% by mass in the water repellent composition, and more preferably 5 to 40% by mass.
The blending amount of the component (D) is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more in the water repellent composition from the viewpoint of water repellency persistence. Water repellency persistence improves more that it is 10 mass% or more. If the amount is less than 10% by mass, the water repellent composition is dried too quickly, and the water repellent composition is dried without penetrating into a textile product such as thick clothing. Even if it exists, there exists a possibility that water-repellent sustainability may not be enough.

  Although there is no restriction | limiting in particular in mass ratio of (D) component and (C) component, (D) / (C) = 0.2 or more and less than 20 is preferable, More preferably, it is 0.3 or more and less than 15, More preferably Is in the range of 0.5 or more and less than 10. Within such a range, water repellency and quick drying are excellent in a well-balanced manner. That is, if the (D) / (C) ratio is less than the above range, the water repellent composition may be dried too quickly, and even if the water repellency is good, the water repellency persistence may not be sufficient. On the other hand, if the above range is exceeded, even if the water repellency persistence is good, the quick-drying property becomes insufficient, and there is a possibility that the odor remains.

(Optional component)
The water repellent composition of the present invention may contain an optional component in addition to the components (A) to (D) described above.
For example, when the water repellent composition is an aerosol type water repellent composition, it can further contain a general propellant as described above. Further, the amount of the propellant contained may be appropriately set to an amount capable of appropriate injection, but the propellant is almost dissolved in the component (C) and / or the component (D) such as liquefied carbon dioxide gas and liquefied nitrogen gas. In the case where it is not, it is preferably 1 to 10% by mass, more preferably 1 to 5% by mass in the water repellent composition. On the other hand, when it is a substance that dissolves in a large amount in the component (C) and / or the component (D) such as dimethyl ether, the content of the water repellent composition is preferably 3.5 to 50% by mass, more preferably 5 to 40%. It is 10 mass%, More preferably, it is 10-30 mass%.
Examples of other optional components include silicone compounds and fragrances. Preferred silicone compounds include dimethyl silicone, methylphenyl silicone, cyclic silicone, higher fatty acid-modified silicone, methyl hydrogen silicone, fluorine-modified silicone, and epoxy-modified silicone. Carboxy-modified silicone, carbinol-modified silicone, amino-modified silicone, and the like. These silicone compounds can further improve the water repellency and water repellency of the water repellent composition, and can improve the texture of objects such as textiles. Preferred fragrances include floral fragrances, citrus fragrances, musk fragrances, mint fragrances, and the like.

(Product form and object)
The water repellent composition of the present invention is preferably contained in a suitable container and sprayed onto an object. An aerosol spray container containing an aerosol type water repellent composition is, for example, disclosed in Examples thereof include those described in JP-A-9-3441 and JP-A-9-58765. Examples of the spray container containing the liquid spray type water repellent composition include a trigger spray container (direct pressure or accumulator type), a finger spray container, and a dispenser type pump spray container. Examples of the trigger spray container include Examples described in JP-A-9-268473, JP-A-9-256272, JP-A-10-76196, and the like can be given. Examples of the pump spray container include JP-A-9-256272. The thing described in is mentioned.

  Examples of the object for which the water repellent composition of the present invention is used include clothing, umbrellas, wallpaper, textile products of furniture made of curtains and sofas, products having a soft surface such as leather, and the like. Further, according to the water repellent composition of the present invention, it is possible to prevent discoloration or the like due to sweat wetting, especially when used for textiles, and it is usually difficult to impart water repellency. High water repellency and water repellency persistence can be imparted to a hydrophilic material such as cotton.

  As described above, according to the water repellent composition of the present invention, excellent water repellency and water repellency persistence can be imparted while being a water repellent composition using a silicone base. . Moreover, since it is excellent also in quick-drying and odor remaining, it can be used easily even in ordinary households with poor ventilation facilities.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. Further, “%” means “mass%” unless otherwise specified.

[Examples 1 to 10 and Comparative Examples 1 to 4]
The components shown in Tables 1 and 2 were mixed to prepare an aerosol type water repellent composition. Then, 100 g of these aerosol-type water repellent compositions were stored in an aerosol container having the following specifications according to a conventional method, and the following evaluation was performed. The results are shown in Tables 1 and 2.

<Specifications of aerosol container>
Can: BL45AB150 (trade name, manufactured by Toyo Seikan Co., Ltd.)
Valve: S13- (70P-4) 78HG7183ALPS "26" × R (trade name, manufactured by Mitani Valve Co., Ltd.)
Button: D174W04337N ″ 3 ″ -A (trade name, manufactured by Mitani Valve Co., Ltd.)

<Details of components described in Tables used in Examples and Comparative Examples>
(1) AB-1
(A) Component: (B) Component = 6: 4 (mass ratio) mixture (laboratory synthesized product). The component (A) is represented by the formula (I), and R ^{1 to} R ³ in the formula are all methyl groups, X is a methoxy group, and n is 2 mono-terminated monomethoxy group-blocked polyorgano Siloxane (viscosity at 25 ° C. is 10 mPa · s). The component (B) is tetrabutoxy titanium.
Such a mixture was prepared as follows.
100 g of water and 650 g of methanol were placed in a separable flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, and 1250 g of dimethyldichlorosilane was added dropwise at 40 to 60 ° C. over 2 hours while stirring. After completion of the dropwise addition, stirring was continued for 1 hour at the same temperature and allowed to stand, and then the water layer and the oil layer were separated. Sodium bicarbonate was added to the oil layer for neutralization, and methanol was distilled off at 130 ° C. under reduced pressure to obtain 710 g of a colorless and transparent mono-terminated monomethoxy group-blocked polyorganosiloxane having a viscosity of 10 mPa · s (25 ° C.). By adding 400 g of tetrabutoxytitanium to 600 g of this polyorganosiloxane, a mixture (AB-1) of the component (A) and the component (B) was obtained.

(2) AB-2
(A) Component: (B) Component = 6: 4 (mass ratio) mixture (laboratory synthesized product). The component (A) is represented by the formula (I), and R ^{1 to} R ³ in the formula are all methyl groups, X is a methoxy group, and n is 1, and both ends are dimethoxy group-blocked polyorganosiloxane. (Viscosity at 25 ° C. is 84 mPa · s). The component (B) is tetrabutoxy titanium.
Such a mixture was prepared as follows.
In a separable flask equipped with a condenser, a thermometer, and a stirrer, 1600 g of both end hydroxyl-blocked polyorganosiloxane having a viscosity of 70 mPas and 153 g of methyltrimethoxysilane were placed in a nitrogen atmosphere, and the temperature was raised to 90 ° C. while stirring. Then, 5 ppm of 27% tetramethylammonium hydroxide aqueous solution was added as an active ingredient and reacted at 90 ° C. for 5 hours. After completion of the reaction, the temperature was raised to 140 ° C., and unreacted methyltrimethoxysilane and methanol produced by the reaction were distilled off under reduced pressure to block the colorless and transparent dimethoxy group at both ends with a viscosity of 84 mPa · s (25 ° C.). 1700 g of polyorganosiloxane was obtained. By adding 400 g of tetrabutoxy titanium to 600 g of this polyorganosiloxane, a mixture (AB-2) of the component (A) and the component (B) was obtained.

(3) aB-1
This is a mixture of methylpolysiloxane (TSF451-100A (GE Toshiba Silicone Co., Ltd.)): Tetrabutoxytitanium = 6: 4 (mass ratio).

(4) C-1: Propane (5) C-2: Butane (6) C-3: Isopentane In addition, liquefied petroleum gas which is a mixture of these was used for C-1 and C-2 (liquefaction (The main components used as petroleum gas are propane and butane.)
(7) C-4: Isohexane; Kyowasol C-600M (manufactured by Kyowa Hakko Chemical Co., Ltd.)
(8) C′-1: n-heptane (special grade reagent, manufactured by Kanto Chemical Co., Inc.)
(9) D-1: Ethanol (first grade reagent, manufactured by Kanto Chemical Co., Inc.)
(10) D-2: Isopropanol (purity 99.9%, manufactured by Daishin Chemical Co., Ltd.)
(11) E-1: Liquefied carbon dioxide (propellant)

<Evaluation method>
"Test cloth"
A cotton broad (trade name: 250GM502 116, manufactured by Nisshinbo Industries, Inc.) was used for the test cloth, and the following pretreatment was performed.
"Test cloth pretreatment method"
Put 30 L of 50 ° C. tap water in a household washing machine, add 30 g of powder detergent for clothing (trade name: Top, manufactured by Lion Corporation) and disperse well, and then add 1 kg of test cloth. The mixture was stirred for 15 minutes and then dehydrated with a dehydrator for 5 minutes. Next, after repeating the washing and dehydration once more, the process of rinsing with running water for 15 minutes and then dewatering for 5 minutes was repeated 5 times. After the above treatment, it was dried at room temperature and cut into 20 cm × 20 cm.

(1) Water repellent test The water repellent composition was sprayed uniformly on the entire cloth on the test cloth subjected to the above pretreatment. The spray amount was 0.5 times the mass of the test cloth before spraying. Then, what was dried for one day in a room at 20 ° C. and 50 RH% was used as the “water-repellent-treated test cloth” for the next evaluation. The water repellency was evaluated by 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, held at an angle of 45 degrees with respect to the horizontal plane, and set at a height of 15 cm from the center of the water-repellent-treated test cloth. From the spray nozzle, 250 mL of 27 ± 1 ° C. ion-exchanged water was sprayed on the water-repellent treated cloth. Next, remove the frame from the base, hold one end of the frame, hit the other end with the surface facing down, drop excess water droplets, and determine the wetness of the water-repellent treated cloth according to the following criteria evaluated.
(Criteria)
100 points: No adhesion and wetness on the surface 90 points: A little adhesion wetness on the surface 80 points: A surface showing wetness in the form of water drops 70 points: A surface showing considerable partial wetting 60 points: One showing wetness between 70 and 50 50 points: showing wetness on the entire surface 0 point: showing wetness on both front and back surfaces

(2) Water-repellent durability test A water-repellent-treated test cloth was obtained in the same manner as in the above (1) water-repellent test, and 10 L of ion-exchanged water was sprayed continuously. Thereafter, the sample was dried in a room at 20 ° C. and 50 RH% for one day, and after 10 L of ion-exchanged water was continuously sprayed, it was evaluated according to the criteria for the water repellency test.
In this test, a larger amount of ion-exchanged water is repeatedly sprayed than in the above (1) water repellency test. Even after such spraying, good water repellency is recognized, even when repeatedly exposed to water during actual use, water repellency is good, that is, water repellency persistence is good. Is shown.

(3) Evaluation method of quick drying property After leaving the test cloth pretreated as described in the above-mentioned “Test cloth pretreatment method” at 20 ° C. and 50 RH% for 1 day, the water repellent composition is uniformly applied to the entire cloth. Sprayed. The spray amount was 0.5 times the mass of the test cloth before spraying. Next, the test cloth was dried in a room at 20 ° C. and 50 RH%, and the mass change at that time was measured. The mass of the water repellent composition remaining on the test cloth was 5 with respect to the mass of the test cloth. The time (drying time) required to reach 0.0% was determined. When the evaluation result is “Δ” or more, a sufficient commercial value is recognized.
(Evaluation criteria)
A: The drying time is less than 5 minutes.
○: The drying time is 5 minutes or more and less than 10 minutes.
Δ: Drying time is 10 minutes or more and less than 15 minutes.
X: Drying time is 15 minutes or more.

(4) Evaluation method of absence of odor residue after spray application The water repellent composition was sprayed uniformly on the entire cloth on the pre-treated test cloth described in “Pre-treatment method of test cloth”. The spray amount was 0.5 times the mass of the test cloth before spraying. Subsequently, this test cloth was dried in a room at 20 ° C. and 50 RH% for 10 minutes, and the absence of odor residue at that time was evaluated by the following four evaluation panels by four professional panels. When the evaluation result is “Δ” or more, a sufficient commercial value is recognized.
(Evaluation criteria)
○: All four people feel that there is no odor remaining.
Δ: 2 to 3 people out of 4 feel that there is no remaining odor.
X: Only one person out of four feels that there is no odor residue.

[Examples 11 and 12 and Comparative Example 5]
The components shown in Tables 3 and 4 were mixed to prepare a liquid spray type water repellent composition. And 40g of these liquid spray type water repellent compositions were stored in a dispenser type pump spray container for a style guard suit (trade name, manufactured by Lion Corporation).
The liquid spray type water repellent composition was subjected to the evaluations (1) to (4) above. The results are shown in Tables 3 and 4.

  As is clear from the results of the table, according to each of the examples containing all of the components (A) to (D), water repellency and water repellency persistence can be imparted, and quick-drying can be achieved, and the odor remains. A suppressed silicone-based water repellent composition could be provided.

Claims (2)

  A polyorganosiloxane (A) having both ends blocked with alkoxy groups, a metal alkoxide and / or a partially hydrolyzed condensate thereof (B), a C 3-6 paraffin hydrocarbon (C), and a carbon number A water repellent composition comprising 2 to 4 monohydric alcohols (D).   2. The water repellent composition according to claim 1, wherein a mass ratio of the component (D) to the component (C) is (D) / (C) = 0.2 or more and less than 20. 3.