JP2000186279A - Aerosol-type water repellent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aerosol-type water repellent which does not adversly affect the environment by combining a water repellent component comprising an organic-solvent-soluble solid silicone resin, a metal alkoxide, and an organopolysiloxane with an organic solvent and a propellant gas. SOLUTION: A water repellent component comprising an organic-solvent- soluble solid silcone resin having a molar ratio of (R13SiO1/2+R12SiO+R1SiO3/2)/ SiO2 of 0.5-1.5 and a total content of R13SiO1/2 units and SiO2 units of 80 mol% or higher and/or an organic-solvent-soluble silicone-graft acrylic resin prepared by the polymerization of a monomer component mainly comprising a compound of formula I and (meth)acrylate, a metal alkoxide, and a compound of formula II is combined with an organic solvent and a propellant gas. In the formulas, R1 and R6 are each a 1-10C hydrocarbon group; R2 is H or CH3; R3 is a 1-12C hydrocarbon group; R4 is CH3 or trimethylsiloxy; R5 is a 1-4C hydrocarbon group; n is 3-200; m is 1-3; and x is such a number as to imparts a kinematic viscosity of 5-1,000,000 cSt at 25 deg.C to the compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aerosol-type water-repellent agent, which has a low adverse effect on the environment, and which can impart a highly persistent water repellency to fibers and the like by a simple treatment method. The present invention relates to a mold water repellent.

[0002]

2. Description of the Related Art Conventionally, as a method for imparting water repellency to natural or synthetic fibers, a method using a silicone-based water repellent is known. Not only are the types of fibers that can be used limited, but the processing time is long, the productivity is poor, and the durability is not sufficient. In order to solve the above problems, a proposal has been made to cause a crosslinking reaction by heating to express water repellency and its durability.
No. 440, JP-B-51-27465 and JP-B-53-4158), if the processing temperature is low or the processing time is short, the water repellency with sufficient durability cannot be obtained, and it is still satisfactory. No water-repellent agent to be obtained has been obtained. Further, a polymer of a polymerizable monomer containing a perfluoro or fluoroalkyl group in the molecule, or a fluorine-based polymer that is a copolymer of this monomer and another polymerizable monomer is used. It is also known that when treated into fiber fabrics, etc., they exhibit excellent water repellency and antifouling effects even in relatively small amounts, and they are also used as surface treatment agents in the fields of leather and building materials. .

[0003]

In the case where water repellency is to be imparted to textiles, leather, building materials, and the like, the aerosol spray type is most preferable for general users because of its simplicity of use. . However, various restrictions are imposed on the composition of the water repellent in order for the effect of the spray type water repellent of the aerosol to be sufficiently exhibited. That is, (1) the compatibility between the propellant gas of the aerosol and the stock solution is excellent, (2) the water repellent component is uniformly dissolved in the water repellent composition, and (3) When spraying the water repellent composition,
It is necessary to have requirements such as easy wetting of the surface of the object to be treated and appropriate permeability, and when these requirements are satisfied, the aerosol spray is uniformly sprayed and the Good water repellency and antifouling property can be imparted to the object without causing a powder blowing phenomenon, a fluffing phenomenon, a whitening phenomenon and the like.

[0004] Further important for the general user is:
Although they are excellent in safety and have no unpleasant odor, these problems are mainly related to the organic solvent incorporated in the water repellent composition. The known fluorine-based polymer is difficult to dissolve when a solvent having a low toxicity and containing alcohols such as ethanol and isopropyl alcohol as a main component is difficult, so that the requirements for the aerosol spray cannot be satisfied. However, in recent years, environmental hygiene issues have been emphasized, and it has been required to use safer solvents mainly composed of alcohols. In addition, in the aerosol type spray using the fluorine-based polymer, it is necessary to use a solvent having a problem in safety, and depending on the cloth to be treated, there are some which do not easily exhibit water repellency, and more versatility. There is a need for an excellent water repellent.

[0005]

[MEANS FOR SOLVING THE PROBLEMS]
Therefore, the inventors have replaced conventional aerosol sprays.
As a result of intensive studies on specific silicone resins or
Silicone graft acrylic resin, specific organopoly
Water repellent composed of siloxane and metal alkoxide
Dissolved in an organic solvent mainly composed of alcohol
Finds that this problem can be solved
Was. That is, the present invention has little adverse effect on the environment.
It is simple and easy to use, and it is easier to process on fibers and other materials than conventional products.
Can provide excellent water repellency and water repellency
An azole type water repellent is provided. The present invention
(A) a repellent composed of the following three components (a), (b) and (c)
Solution component 0.2-20% by weight, (B) organic solvent 30-98.8% by weight
%, (C) aerosol type consisting of 1 to 50% by weight of propellant gas
It is a water repellent agent. That is, (a) R¹ ₃SiO_1/2 
Unit, R¹ ₂SiO unit, R¹ SiO_{3 / 2} Unit, S
iO₂ Unit (where R¹ Are independent homologs or
Is an unsubstituted or substituted monovalent carbon having 1 to 10 carbon atoms
A hydrogen group), R¹ ₃SiO_{1 / 2} Unit and SiO
₂ The total amount of the units is 80 mol% or more, and
Is represented by (R¹ ₃SiO_1/2 + R¹ ₂SiO + R
¹ SiO_3/2 ) / SiO₂= 0.5 to 1.5 (molar ratio)
Organic solvent soluble solid silicone resin a present in a proportion of
¹ And / or one molecule represented by the following general formula (Formula 3)
Organopolysilo having one radical polymerizable group in it
Xane compounds, acrylates and / or methacrylates
Radical polymerization of radical polymerizable monomers mainly
Organic solvent-soluble silicone rubber
Raft acrylic resin a²

Embedded image (Here, R ² is a hydrogen atom or a methyl group, R ³ is a group having 1 to 1 carbon atoms, which may contain an oxygen atom in the main chain.
12 divalent hydrocarbon groups, R ⁴ is a methyl group or trimethylsiloxy group, R ⁵ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, n is an integer of 3 to 200, m is 1 to 3 100 parts by weight), (b) 2 to 400 parts by weight of a metal alkoxide or a partially hydrolyzed condensate thereof, and (c) 0 to 300 parts by weight of an organopolysiloxane represented by the following general formula (4).

Embedded image (Where R ⁶ is an independent same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, x is an average value, and the kinematic viscosity at 25 ° C. is 5 to 1,000,000 centistokes) Is a number)

[0006]

A ¹ of the Detailed Description of the Invention The present invention (a) is intended to be classified as a silicone resin solid that is commonly referred to as "silicone resin". It is well known that when a silicone resin diluted in a solvent is applied to a substrate, a water-repellent film is formed. Silicone resin of ^{a 1} in (a) component in the present invention are those whose structure is ^identified, _R 1 _{3 SiO 1/2} units (M units), R
¹ ₂ SiO units (D ^unit), R _{1 SiO 3/2} units (T units), which consist of SiO ₂ units (Q units), further the total amount of ^R ₁ 3 _{SiO 1/2} units and SiO ₂ units There are at least 80 mol%, yet these _{^{units, (R 1 3 SiO 1/2 +}} R 1 2 SiO + R 1 Si
This is an organic solvent-soluble solid silicone resin containing O _3/2 ) / SiO _{2 at a} ratio of 0.5 to 1.5 (molar ratio).

[0007] ^{R 1} in the constituent unit of ^{a 1} in the present invention
Are independently the same or different unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group , Isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, cyclohexyl group, phenyl group and other hydrocarbon groups, trifluoropropyl group, heptadecafluorodecyl group, chloropropyl group and chlorophenyl group, etc. Examples include a hydrogen group. Among them, from the viewpoints of water repellency, solubility in an organic solvent, and economy, those in which R ¹ is a methyl group are particularly preferable. Among ^R ₁ 3 _{SiO 1/2} units and SiO ₂ units is of essential among the four kinds of structural units, ^{R 1}
₃ when the total amount of SiO _1/2 units and SiO ₂ units is less than 80 mole percent of total units total amount, or not become silicone resin of a ¹ is the solid, dissolve in organic solvents become solid Sex becomes poor. Therefore, the total amount of both needs to be 80 mol% or more, and preferably 90 mol% or more. R ¹ ₂ SiO units and ^{R 1}
The SiO _3/2 unit may or may not be included.
_{^{Further, (R 1 3 SiO 1/2 +}} R 1 2 SiO + R 1 S
_{iO 3/2) / SiO 2} = is required to be in the range of molar ratio of 0.5 to 1.5. It the molar ratio is poor solubility in an organic solvent a ¹ is less than 0.5, 1.5
If it exceeds 300, the resulting coating will be too sticky and poor in water repellency. Therefore, the molar ratio is 0.5 to
It needs to be 1.5, preferably in the range of 0.7 to 1.2. The average molecular weight of ^{a 1} is 3,000 to 30,000
Is preferably within the range. When the average molecular weight is less than 3,000, the hardness of the resin is reduced, and the coating has large stickiness and low water repellency. Those having an average molecular weight of more than 30,000 are difficult to produce and have poor solubility in organic solvents. Particularly, those having an average molecular weight of 5,000 to 20,000 are preferably used.

[0008] The silicone resin of ^{a 1} is, ^R ₁ 3 SiOH as the M unit ^source, organosilanes such as _R 1 3 ^SiCl, organodisiloxane represented in _R ¹ ₃ SiOSiR 1 3, cyclic siloxanes as a D unit source, Water such as trialkoxysilane or trichlorosilane or a hydrolytic condensate thereof as a T unit source, water glass as an Q unit source, orthoalkyl silicate, alkyl polysilicate, etc.
It is produced by a known method of hydrolysis using an acid. Incidentally, the silicone resin of a ¹ is to be uniformly dissolved in an organic solvent to be described later, it is necessary to form a uniform water repellent film on the fabric.

As a ^{2 in} (a), an organopolysiloxane compound having one radically polymerizable group (acrylic group or methacrylic group) in one molecule represented by the general formula (Chemical Formula 1), acrylate and Alternatively, an organic solvent-soluble silicone graft acrylic resin, which is a copolymer obtained by radical polymerization of a radical polymerizable monomer mainly composed of methacrylate, can be used.
This silicone-grafted acrylic resin is a resin in which the main chain is composed of polyacrylate or polymethacrylate, and the side chain is composed of methylpolysiloxane. Also known as resin.

In the organopolysiloxane having one radical polymerizable group in one molecule represented by the general formula (Chemical Formula 1), R ² is a hydrogen atom or a methyl group, and R ³ is an oxygen atom in the main chain. Sometimes 2 having 1 to 12 carbon atoms
A monovalent hydrocarbon group, R ⁴ is a methyl group or a trimethylsiloxy group, R ⁵ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, n is an integer of 3 to 200, and m is an integer of 1 to 3 .
Specific examples of R ³ _{include, -CH 2 -, - (CH} 2) 2
_{-, - (CH 2) 3} -, - CH 2 (CH 3) CHCH 2
_{-, - (CH 2) 6} -, - (CH 2) 12 -, - (CH
_{2) 2 -O- (CH 2)} 3 -, - (CH 2) 2 -O-
(CH ₂ ) ₂ —O— (CH ₂ ) ₃ — and the like;
Examples of _{^{5, -CH 3, -CH 2 CH}} 3,
_{-CH 2 CH 2 CH 3, -CH} 2 CH 2 CH 2 C
Such as H ₃ are exemplified. If the average degree of polymerization n is less than 3, sufficient water repellency cannot be obtained, and if it exceeds 200, the film-forming properties of the obtained silicone-grafted acrylic resin are deteriorated, and the durability of the formed film is also deteriorated. The organopolysiloxane having one radical polymerizable group in one molecule represented by the chemical formula (1) is obtained by combining a (meth) acrylate-substituted chlorosilane compound and a dimethylpolysiloxane compound containing Li at a terminal according to a conventional method. It can be obtained by a method such as lithium dehydrochlorination reaction.

On the other hand, examples of radical polymerizable monomers mainly composed of acrylate and / or methacrylate include alkyl (meth) acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Hydroxyalkyl (meth) such as hydroxyethyl (meth) acrylate
Examples thereof include acrylates, fluorine-substituted alkyl (meth) acrylates such as perfluorooctylethyl (meth) acrylate, and radically polymerizable silicon compounds such as γ- (meth) acryloxypropyltrimethoxysilane. From the viewpoints of water repellency, solubility in organic solvents, and economy, alkyl (meth) acrylates are particularly preferred.

The copolymerization of an organopolysiloxane having one radical polymerizable group in one molecule represented by the general formula (Chemical Formula 1) with a radical polymerizable monomer mainly composed of acrylate and / or methacrylate is carried out by benzoyl peroxide. And 2,2′-azobis (2-
The polymerization is carried out by a known solution polymerization method, bulk polymerization method, emulsion polymerization method or suspension polymerization method using a radical polymerization initiator such as methylbutyronitrile). Incidentally, the silicone-grafted acrylic resin of a ² is to be uniformly dissolved in an organic solvent to be described later, it is necessary to form a uniform water repellent film on the fabric. Accordingly, in the present invention, it is particularly preferred that the silicone-grafted acrylic resin obtained a ² applies the solution polymerization method can be supplied in the form of a solution. The copolymerization ratio of the organopolysiloxane compound having one radical polymerizable group in one molecule (formula 1) and the radical polymerizable monomer mainly composed of acrylate and / or methacrylate is k by weight ratio, k: by weight ratio m / k = m / m
It is preferably 5/95 to 80/20, particularly 10/90 to 60/20.
/ 40 is preferred. When k / m is less than 5/95, sufficient water repellency may not be obtained, and when k / m exceeds 80/20, the film-forming properties may be insufficient. The weight average molecular weight of the silicone-grafted acrylic resins a ² is 5,000
Preferably it is 500,000. Weight average molecular weight 5,0
If it is less than 00, the film-forming property may be insufficient and the durability may be poor. If it exceeds 500,000, the texture of the fiber may be deteriorated, or it may be difficult to dissolve in an organic solvent described later. Above the silicone resin and silicone-grafted acrylic resin a ² of a ¹ but each variety of a ^1, a ² are obtained by the raw materials used as mentioned above, be used alone these respectively, two These may be used in combination.

The metal alkoxide (b) of the present invention maintains the two functions of the water repellency imparted to the fiber by (a) and the texture imparted to the fiber by (c) described below for a long time. Used for purposes. As the metal alkoxide (b) in the present invention, titanium alkoxide, silicon alkoxide, aluminum alkoxide and the like can be used as appropriate. Specifically, tetramethoxytitanium, tetraethoxytitanium, tetraisoproxytitanium, tetrabutoxytitanium, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, trimethoxyaluminum, triethoxyaluminum, triisopropoxy Aluminum and the like are exemplified, and these may be partially hydrolyzed condensates. Among these, titanium alkoxide and its hydrolytic condensate are preferred from the viewpoint of reactivity. Especially reactivity,
Tetraisopropoxytitanium and tetrabutoxytitanium are preferred from the viewpoint of storage stability.

These metal alkoxides react rapidly with moisture in the air to condense while releasing alcohol,
Form a coating on the surface of the substrate. Although the coating itself is not so excellent in water repellency, the presence of the water repellent component (a) makes the coating made of the mixture excellent in water repellency. In addition, when only the components (a) and (c) are processed into a dough, they are only physically adsorbed on the fiber, so that it is difficult to hold the material on the fiber for a long time. , (B) acts as a so-called binder resin that fixes both components (a) and (c) to the fiber, so that both components (a) and (c) are It is considered that the film is prevented from falling off from the fiber, and as a result, a film having excellent water repellency is obtained.

[0015] Even when the coating comprising (a), (b) and (c) is applied to a fabric made of synthetic and natural fibers, the water repellency is exhibited because the fiber surface is essentially composed of ( Although the surface has poor affinity with a) and (c),
The coating by (b) covers the fiber surface (a), (c)
It is considered that the surface is modified to have high affinity. From the above point of view, (b) requires a specific amount for (a), which is particularly excellent in water repellency, and (b) 2 to 400 parts by weight with respect to (a) 100 parts by weight. preferable. If the amount is less than 2 parts by weight, (a) cannot be uniformly adsorbed on the fiber surface, and the water repellency decreases. If the amount exceeds 400 parts by weight, the distribution of the water-repellent component (a) becomes relatively small, so that the water-repellency also decreases. More preferably, (b) is 30 to 300 parts by weight with respect to (a) 100 parts by weight.

The organopolysiloxane (c) represented by the general formula (Chemical Formula 2) in the present invention is in the form of oil and is generally classified as "silicone oil". Although slightly inferior to (a), water repellency can be imparted. (C) in the present invention is:
It is used for the purpose of giving the texture to the fiber without lowering the excellent water repellency of (a).

In the above general formula (Chemical Formula 2), R ⁶ is independently 1 to 10 unsubstituted or substituted monovalent hydrocarbon groups of the same or different kind. Examples of these are methyl, ethyl, n-propyl, isopropyl,
n-butyl group, isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, cyclohexyl group, hydrocarbon group such as phenyl group, trifluoropropyl group, heptadecafluorodecyl group, chloropropyl group, chlorophenyl group, etc. And amino groups such as halogen atom-substituted alkyl groups, γ-aminopropyl groups, and N-β (aminoethyl) -γ-aminopropyl groups. Among them, in the present invention, from the viewpoints of water repellency, solubility in organic solvents, and economy, R
It is particularly preferred that ⁶ is a methyl group. In the general formula (Formula 2), the average degree of polymerization x is preferably from 5 to 2,500. This is because the kinematic viscosity of the oil at 25 ° C is 5 to 1,000,0
00 centistokes. If x is less than 5, the oil will contain a large amount of volatile components, which will evaporate during drying, resulting in a small amount of application and a reduced texture. When x exceeds 2,500, the state of the oil changes to a rubbery state, the compatibility with (a) becomes small, the coating applied to the fabric becomes uneven, and the texture derived from the oil is impaired. Is not preferred.

The water repellent coating film composed only of (a) in the present invention, when composed of only (a) is particularly a ¹ silicone resins, although excellent in water repellency tend to coat becomes hard, various fibers When processed into a dough consisting of Therefore, by adding (c),
The texture can be improved without lowering the water repellency. When (a) is composed only of a silicone-grafted acrylic resin, the texture is slightly inferior, and the texture is improved by adding the component (c). From the above points (c)
A specific amount is required for (a) having excellent water repellency, and (c) is preferably 1 to 300 parts by weight based on 100 parts by weight of (a). If the content of (c) is less than 1 part by weight, the texture is not improved when processed into a fabric composed of various fibers, and if it exceeds 300 parts by weight, the distribution of the water-repellent (a) to the fabric is relatively high. On the other hand, oily stickiness is generated on the surface while the water repellency is reduced. More preferably, (c) 30 to 200 parts by weight with respect to (a) 100 parts by weight.

The water repellent component (A) composed of the components (a), (b) and (c) is dissolved in an organic solvent (B). Examples of the organic solvent (B) include monohydric alcohols such as ethanol and isopropyl alcohol, dihydric alcohols such as propylene glycol, aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as n-hexane and n-heptane. Hydrocarbons, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, alicyclic hydrocarbons such as cyclohexane, methyl polycyclosiloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane (cyclic dimethyl silicone) Oil) methylpolysiloxane (dimethyl silicone oil) such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, 1,3-diphenyl-1,1,3,3-tetramethyldisiloxane;
Volatile organopolysiloxanes such as phenylmethylpolysiloxane (phenylmethylsilicone oil) may be mentioned, and these may be used alone or in combination of two or more. It is particularly preferable to use an alcohol such as ethanol or isopropanol from the viewpoint of safety, drying property and solubility for (A). Further, the content of these alcohols is preferably at least 50%, particularly preferably at least 80%, of the total weight of the solvent (B).

The aerosol-type water-repellent agent of the present invention can be obtained by adding the propellant gas (C) to the components (A) and (B). The propellant gas (C) is a component necessary for spraying the water repellent composition of the present invention in the form of a mist, and can be appropriately selected from known ones. For example, propane, butane, dimethyl ether, carbon dioxide gas, nitrogen gas and the like can be appropriately selected in consideration of the used gas pressure, and can be used alone or in combination of two or more.

The above-mentioned three components (A), (B) and (C) are mixed to obtain the aerosol-type water-repellent agent of the present invention. The mixing ratio of each component is preferably in the following range. That is, (A) 0.2 to 20% by weight of a water repellent component composed of the three components (a), (b) and (c), and (B) an organic solvent 30 to 9
8.8% by weight and (C) 1 to 50% by weight of the propellant gas.
When the concentration of the component (A) is less than 0.2% by weight, the amount of adhesion to the fiber is too small and the water repellency becomes insufficient. When the concentration is more than 20% by weight, the amount of adhesion is too large and the texture becomes poor. Since the wiping phenomenon easily occurs, the content is preferably 1 to 10%. (C) The use amount of the propellant gas varies greatly depending on the type of the propellant gas and the use amount of (A) and cannot be limited unconditionally. However, if it is less than 1% by weight of all the components of the aerosol type water repellent of the present invention. It is difficult to be aerosol type, conversely 50
If the amount exceeds the weight percentage, a dusting phenomenon or a whitening phenomenon may occur. Preferably it is 5 to 40% by weight. The aerosol-type water repellent of the present invention may optionally contain other water repellents, oil repellents, insect repellents, antistatic agents, additives such as softeners, etc., as long as the properties such as water repellency and texture are not impaired. You may mix.

[0022]

The present invention will be described in more detail with reference to the following examples.
However, the present invention is not limited to these.
Absent. In Examples, “parts” indicates “parts by weight” and “%” indicates “% by weight”.
The viscosity is a value at 25 ° C. (Example 1) As the water repellent component of (A), (a-1): R¹ ₃SiO_1/2 Unit and SiO₂ A functional group R ¹ Are all methyl groups and R¹ ₃SiO_1/2 / SiO₂ = 0.7 (molar ratio), 100 parts of silicone resin having an average molecular weight of 15,000 (b-1): 100 parts of tetrabutoxytitanium (c-1): functional group R⁶ Are all methyl groups, and 100 parts of a silicone oil having a kinematic viscosity of 100 centistokes at 25 ° C.
Isopropyl alcohol (hereinafter abbreviated as IPA)
Color) by dissolving 5 parts of (A) in 70 parts of (B)
A clear stock solution was obtained. This stock solution was filled in a spray can
Then, as (C), 20 parts of dimethyl ether and 5 parts of propane
The injection gas consisting of
And a water repellent. Here, the weight% of each component is represented by (A)
It was adjusted so that / (B) / (C) = 5/70/25.
The aerosol-type water repellent obtained in this way is the following fiber
Spray evenly on each dough composed of
ーThe treatment amount of the water repellent component (A-1) is 0.01 g / cm²
 Met. 25 ° C / 50% humidity / 30 minutes
The sample dried under the conditions of
Was.

The dough used is as follows. Fabric 1: Nylon woven fabric, Fabric 2: TC woven fabric (mixed woven fabric of cotton / polyester), Fabric 3: Cotton woven fabric. (Criteria for Water Repellency Test and Evaluation) A spray-type water repellency test (JIS L-1092-1992) was performed. The sample was mounted on a metal holding frame with a diameter of 15 cm, held at an angle of 45 degrees with respect to the horizontal plane, and sprayed with 250 ml of ion-exchanged water for 25 to 30 seconds from a spray nozzle installed at a height of 15 cm from the center of the sample. Sprayed onto the sample. With the surface of the sample facing downward with the holding frame attached, the edge of the sample was lightly applied to a desk to drop excess water droplets, and then the wet state of the sample was observed and scored according to the following criteria. (Scoring criteria) The water repellency of the surface and the back surface is assumed to be 0 when the entire surface is wet, and the water repellency is assumed to be 50 when only the front surface is entirely wet. It is assumed that water repellency is 70 when the water droplets permeate the cloth and water repellency is 80 when the surface is wetted by small individual water droplets. Assume that water repellency is 90 for those that adhere, and water repellency for those that have no wet or water droplets on the surface.
00 was assumed.

Appearance The treated cloth of the sample was used, and its appearance was visually observed.
Whether the whitening phenomenon occurred was determined based on the following criteria. ：: Same surface state as untreated cloth. Δ: Slight whitening is observed as compared with the untreated cloth. X: Whitening phenomenon is observed.

Texture Test Using the treated cloth of the sample, the texture was determined by the finger of three panelists according to the following criteria. ：: Same texture as untreated cloth. Δ: slightly hard texture compared to untreated cloth. X: Hard texture compared to untreated cloth.

(Examples 2 to 10) Each component was blended as shown in (Table 1) to obtain an aerosol-type water repellent in the same manner as in Example 1, and then in the same manner as in Example 1. evaluated. The evaluation results are shown in (Table 3). In addition, (A-
The compositions of 1) to (A-7) are shown in (Table 2).

[0027]

[Table 1]

The composition ratio of (A) in Table 1 is described below. (A-2) (a-1) / (b-1) / (c-1) = 100 parts / 2 parts / 1 part (A-3) (a-1) / (b-1) / (c) -1) = 100 parts / 400 parts / 300 parts (A-4) (a-1) / (b-1) / (c-1) = 100 parts / 300 parts / 30 parts (A-5) (a -1) / (b-1) / (c-1) = 100 parts / 30 parts / 200 parts (A-6) (a-1): 100 parts described above (b-2): tetraisopropoxy titanium 100 part (c-2): in the functional group ^{R 6} are all methyl groups, 100 parts of a silicone oil of kinematic viscosity of 10,000 centistokes at 25 ℃ (a-7) ( a-1): supra 100 parts (b-1) : 100 parts as described above (c-3): 100 parts of silicone oil having a kinematic viscosity of 1,000,000 centistokes at 25 ° C. with all the functional groups R ² being methyl groups.

[0029]

[Table 2]

[Table 3]

(Examples 11 to 15 and Comparative Examples 1 to 5)
Each component was blended as shown in (Table 4) to produce an aerosol-type water repellent in the same manner as in Example 1, and the same evaluation was performed. Table 6 shows the evaluation results. Details of (A) in (Table 4) are shown in (Table 5).

[0031]

[Table 4]

(A) in Table 4 is as follows. (A-8) (a-1): 100 parts described above (b-1): 100 parts described above (c-4): 99 mol% of the functional groups R ⁶ are methyl groups and 1 mol% is N -Β (aminoethyl) -γ-aminopropyl group, 100 parts of silicone oil having a kinematic viscosity at 25 ° C. of 500 centistokes (A-9) (a-1): 100 parts described above (b-1) : 100 parts supra (c-5): 95 mol% are methyl groups among functional groups R ^6, 5 mol% is a triflate Ruoropuropiru group, 100 parts of a silicone oil of kinematic viscosity 100 Senchisu Stokes at 25 ° C. (a -10) _^(a-2): composed R 1 _{3 SiO 1/2} units and SiO ₂ units, a functional group R ¹ are all methyl _{^{groups, R 1 3 SiO 1/2 / SiO}} 2 = 0.9 ( molar ratio) 100 parts of a silicone resin having an average molecular weight of 5,000 (b-1): 100 parts described above (c-1): 100 parts described above _{^{A-11) (a-3}} ): made of R 1 _{3 SiO 1/2} units and SiO ₂ units, the total amount of ^R ₁ 3 _{SiO 1/2} and SiO ₂ units in 90 mol%, the functional group ^{R 1} 95 mol% is methyl group, 5 mol% are heptadec Furorodeshiru _{^{group, (R 1 3 SiO 1/2 +}} R 1 2 SiO) a / _SiO 2 = 0.8 (molar ratio), 100 parts of a silicone resin having an average molecular weight of 7,000 (B-1): 100 parts described above (c-1): 100 parts described above (A-12) (a-3) / (b-1) / (c-5) = 100 parts / 100 parts / 100 Parts (X-1) (a-1) / (c-1) = 100 parts / 100 parts (X-2) (a-1) / (b-1) = 100 parts / 500 parts (X-3) (B-1) / (c-1) = 100 parts / 100 parts

[0033]

[Table 5]

[0034]

[Table 6]

(Examples 16 to 25) The following components were used as components (Table 7) and blended in the same manner as in Example 1 to obtain an aerosol-type water repellent. The evaluation was performed in the same manner as described above, and the evaluation results are shown in (Table 9). Details of A in (Table 7) are shown in (Table 8).

[0036]

[Table 7]

The composition of (A) in Table 7 is as follows. (A-13) (a-4): an organopolysiloxane of the following formula (formula 5):

Embedded image 100 parts of a silicone graft acrylic resin having a weight average molecular weight of 150,000 obtained by polymerizing methyl methacrylate (MMA) and butyl methacrylate (BMA) at a weight ratio of (Chemical Formula 5) / MMA / BMA = 30/50/20 ( b-1): 50 parts described above (c-1): 50 parts described above (A-14) (a-4) / (b-1) / (c-1) = 100 parts / 2 parts / 1 part (A-15) (a-4) / (b-1) / (c-1) = 100 parts / 400 parts / 300 parts (A-16) (a-4) / (b-1) / (c) -1) = 100 parts / 300 parts / 30 parts (A-17) (a-4) / (b-1) / (c-1) = 100 parts / 30 parts / 200 parts (A-18) (a -4) / (b-2) / (c-2) = 100 parts / 50 parts / 50 parts (A-19) (a-4) / (b-1) / (c-3) = 100 parts / 50/50

[0038]

[Table 8]

[0039]

[Table 9]

(Examples 26 to 30 and Comparative Examples 6 to 9) The following aerosol water repellents were prepared in the same manner as in Example 1 by using the components described later and blending them as shown in Table 10. It was manufactured and evaluated, and the evaluation results are shown in (Table 12).
Details of A in (Table 10) are shown in (Table 11).

[0041]

[Table 10]

The composition of (A) in Table 10 is as follows. (A-20) (a-5): an organopolysiloxane of the following formula (Formula 6):

Embedded image Methyl methacrylate (MMA) and 2-ethylhexyl acrylate (2-EHA) were polymerized at a weight ratio of (Chemical Formula 8) / MMA / 2-EHA = 50/35/15 to obtain a polymer having a weight average molecular weight of 58,000. Silicone graft acrylic resin 100 parts (b-1): 50 parts mentioned above (c-1): 50 parts mentioned above (A-21) (a-4) / (b-1) / (c-4) = 100 Parts / 50 parts / 50 parts (A-22) (a-1) / (a-4) / (b-1) / (c-1) = 90 parts / 10 parts / 100 parts / 100 parts (A- 23) (a-1) / (a-4) / (b-1) / (c-1) = 50 parts / 50 parts / 100 parts / 100 parts (A-24) (a-1) / (a) -4) / (b-1) / (c-1) = 10 parts / 90 parts / 100 parts / 100 parts (X-4) (a-4) / (c-1) = 100 parts / 100 parts ( X-5) (a-4) / (b-1) = 100 parts / 500 parts

[0043]

[Table 11]

[0044]

[Table 12]

[0045]

The aerosol-type water-repellent agent of the present invention has a low adverse effect on the environment and is a simple treatment method.
It is capable of imparting water repellency and water repellency sustainability to fibers and other objects to be treated which is superior to conventional products in durability, and is extremely useful as a water repellent. In addition, water repellency can be imparted to glass, plastic, stone, metal, and the like other than fibers.

Continuation of the front page (72) Inventor Akira Sakakibara 5-3-35 Nishibori, Urawa-shi, Saitama F-term (reference) in Urawa Research Laboratory, Konishi Co., Ltd. 4H020 BA32

Claims (5)

[Claims] (A) 0.2 to 20% by weight of a water repellent component comprising the following three components (a), (b) and (c); (B) 30 to 98.8% by weight of an organic solvent; and (C) injection. An aerosol-type water-repellent agent comprising 1 to 50% by weight of a gas. _^(A) R 1 _{3 SiO 1/2} ^units, _R 1 2 SiO units,
R ¹ SiO _3/2 units, SiO ₂ units (where R ¹
Are independently the same or different carbon atoms of 1 to 10
Made from unsubstituted or substituted monovalent hydrocarbon group), R ¹
₃ The total amount of SiO _1/2 units and SiO ₂ units is 80 mol% or more, yet these ^units, _(R 1 3 SiO
^{_{1/2 + R 1 2 SiO + R}} 1 SiO 3/2) / Si
O ₂ = 0.5 to 1.5 (mole ratio) organic solvent-soluble solid silicone resin a ¹ and or a proportion of the organo having one radical polymerizable group in one molecule represented by the following general formula (Formula 1) Organic solvent-soluble silicone-grafted acrylic resin a ² which is a copolymer obtained by radical polymerization of a polysiloxane compound and a radical polymerizable monomer mainly composed of acrylate and / or methacrylate. (Here, R ² is a hydrogen atom or a methyl group, R ³ is a group having 1 to 1 carbon atoms, which may contain an oxygen atom in the main chain.
12 divalent hydrocarbon groups, R ⁴ is a methyl group or trimethylsiloxy group, R ⁵ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, n is an integer of 3 to 200, m is 1 to 3 100 parts by weight, (b) 2 to 400 parts by weight of a metal alkoxide or a partially hydrolyzed condensate thereof, and (c) 1 to 300 parts by weight of an organopolysiloxane represented by the following general formula (Formula 2). Embedded image (Where R ⁶ is an independent same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, x is an average value, and the kinematic viscosity at 25 ° C. is 5 to 1,000,000 centistokes) Is a number) 2. The aerosol-type water-repellent agent according to claim ¹ , wherein R ¹ of the organic solvent-soluble solid silicone resin a ¹ in (a) is all methyl groups. 3. The aerosol type water repellent according to claim 1, wherein the metal alkoxide (b) is a titanium alkoxide. 4. The aerosol-type water-repellent agent according to claim 1, wherein all of the functional groups R ⁶ of the organopolysiloxane (c) are methyl groups. 5. The aerosol-type water-repellent agent according to claim 1, wherein the organic solvent (B) contains alcohol as a main component.