JP7505551B2 - Water repellent composition and fiber treatment agent - Google Patents

Description

The present invention relates to a water repellent composition. In particular, the present invention relates to a silicone emulsion composition that imparts high water repellency to fibers, and a fiber treatment agent containing the composition.

Fluorine-based compounds have been used traditionally as a method for imparting water repellency to natural fibers, synthetic fibers, leather, paper, etc. Textile products treated with water repellents whose main component is a fluorine compound are characterized by having very excellent water repellency and excellent durability. However, fluorine-based compounds are expensive, and high-temperature treatment is required to achieve high water repellency, so the range of application is limited. In addition, fluorine compounds have a very stable structure and are difficult to decompose in the environment, and they also have a tendency to accumulate, which causes environmental problems, and their use is gradually being restricted both domestically and internationally. In light of the above background, the development of water repellents that do not contain fluorine compounds is being considered.

As water repellents that do not contain fluorine compounds, compositions mainly composed of silicon-based compounds such as silicone have been studied. Japanese Patent No. 2960304 studies a composition mainly composed of an acrylic-silicone graft polymer compound, Japanese Patent Laid-Open No. 2018-104866 studies a composition mainly composed of modified silica, and Japanese Patent No. 6573548 studies a composition using silicone alkoxy oligomers and polyorganosilsesquioxanes.

Silicon-based compounds can impart good flexibility and texture to textile products, while also imparting water repellency. In the above prior art documents, the water repellency effect is enhanced by optimizing the composition of the silicon-based compound and each component, and the treated fibers exhibit excellent water repellency. However, none of the above documents 1 to 3 mentions flexibility or texture, leaving the issue of achieving both high water repellency and flexibility/texture.

Japanese Patent No. 2960304 JP 2018-104866 A Patent No. 6573548

In view of the problems with the conventional techniques described above, the present invention aims to provide a water repellent composition that has excellent water repellency and can impart good flexibility and texture to treated fibers, does not contain fluorine compounds, and has a reduced environmental impact, as well as a fiber treatment agent containing the same.

As a result of intensive research into achieving the above object, the inventors have found that a composition containing the following components (A) to (D) can impart high water repellency to fibers as well as good flexibility and texture. Furthermore, they have found that because this composition does not contain fluorine compounds, it can reduce the environmental impact, which has led to the invention.

（式中、Ｒ¹は互いに独立に、炭素数１～２０の非置換１価炭化水素基であり、Ｒ²は水素原子であり、Ｒ³は互いに独立に、Ｒ¹及びＲ²、ならびに－ＯＨ、－ＯＣＨ₃及び－ＯＣ₂Ｈ₅から選ばれる基であり、ａ、ｂ、ｃ、ｄ及びｅは、２≦ａ≦１０、０≦ｂ≦１，０００、０≦ｃ≦１，０００、０≦ｄ≦５、０≦ｅ≦５の範囲を満たす数である。但し、ｃ＝０の場合、Ｒ³のうち少なくとも一つがＲ²である。）
で表され、２５℃における粘度が５～１０，０００ｍＰａ・ｓであるオルガノハイドロジェンポリシロキサン：１００質量部、
（Ｂ）界面活性剤：０．５～５０質量部、
（Ｃ）縮合反応触媒：０．１～１００質量部、及び
（Ｄ）水：５０～３，０００質量部
を含有し、フッ素化合物を含有しない撥水剤組成物。
２．（Ａ）成分が、Ｒ¹、Ｒ²及びＲ³で表される置換基の合計のうち、１０％以上がＲ²（水素原子）である１記載の撥水剤組成物。
３．（Ｃ）成分が、錫、亜鉛、ビスマス、チタン、ジルコニウム及びアルミニウムから選ばれる１種以上の金属化合物である１又は２記載の撥水剤組成物。
４．さらに、（Ｅ）下記平均組成式（２）

（式中、Ｒ⁴は互いに独立に、炭素数１～２０の非置換１価炭化水素基であり、Ｒ⁵は互いに独立に、Ｒ⁴、－ＯＨ、－ＯＣＨ₃及び－ＯＣ₂Ｈ₅から選ばれる基であり、ｆ、ｇ、ｈ、及びｊは、２≦ｆ≦１０、０≦ｇ≦１，０００、０≦ｈ≦４００、０≦ｉ≦５、０≦ｊ≦５の範囲を満たす数である。但し、Ｒ⁵のうち少なくとも一つが－ＯＨである。）
で表されるオルガノポリシロキサン：１～５０質量部を含有する１～３のいずれかに記載の撥水剤組成物。
５．１～４のいずれかに記載の撥水剤組成物を含む繊維処理剤。 Therefore, the present invention provides the following inventions.
1. (A) The following average composition formula (1):

(In the formula, ^R1 's are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, ^R2 is a hydrogen atom, ^R3 's are each independently a group selected from ^R1 and ^R2 , and -OH, _-OCH3 , and _{-OC2H5 ,} and a, b, c, d, and e are numbers that satisfy the ranges of 2≦a≦10, 0≦b≦1,000, 0≦c≦1,000, 0≦d≦5, and 0≦e≦5, provided that when c=0, at least one of ^R3 's is ^R2 .)
and having a viscosity at 25°C of 5 to 10,000 mPa·s: 100 parts by mass,
(B) Surfactant: 0.5 to 50 parts by mass,
A water repellent composition comprising: (C) a condensation reaction catalyst: 0.1 to 100 parts by mass; and (D) water: 50 to 3,000 parts by mass, and containing no fluorine compound.
2. The water repellent composition according to 1, wherein in the component (A), 10% or more of the total of the substituents represented by R ¹ , R ² and R ³ are R ² (hydrogen atom).
3. The water repellent composition according to 1 or 2, wherein the component (C) is a compound of one or more metals selected from the group consisting of tin, zinc, bismuth, titanium, zirconium and aluminum.
4. Furthermore, (E) the following average composition formula (2)

(In the formula, R ⁴ 's are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ 's are each independently a group selected from R ⁴ , --OH, --OCH ₃ , and --OC ₂ H ₅ , and f, g, h, and j are numbers that satisfy the ranges of 2≦f≦10, 0≦g≦1,000, 0≦h≦400, 0≦i≦5, and 0≦j≦5, with the proviso that at least one of R ⁵ 's is --OH.)
4. The water repellent composition according to any one of 1 to 3, comprising 1 to 50 parts by mass of an organopolysiloxane represented by the formula:
5. A fiber treatment agent comprising the water repellent composition according to any one of 1 to 4.

The water repellent composition of the present invention can impart high water repellency to fibers as well as good flexibility and texture. Furthermore, the water repellent composition of the present invention does not contain fluorine compounds, and can reduce the environmental impact.

（式中、Ｒ¹は互いに独立に、炭素数１～２０の非置換１価炭化水素基であり、Ｒ²は水素原子であり、Ｒ³は互いに独立に、Ｒ¹及びＲ²、ならびに－ＯＨ、－ＯＣＨ₃及び－ＯＣ₂Ｈ₅から選ばれる基であり、ａ、ｂ、ｃ、ｄ及びｅは、２≦ａ≦１０、０≦ｂ≦１，０００、０≦ｃ≦１，０００、０≦ｄ≦５、０≦ｅ≦５の範囲を満たす数である。但し、ｃ＝０の場合、Ｒ³のうち少なくとも一つがＲ²である。）
で表され、２５℃における粘度が５～１０，０００ｍＰａ・ｓであるオルガノハイドロジェンポリシロキサンであり、１種単独で又は２種以上組み合わせて用いることができる。 The present invention will be described in detail below.
[Component (A)]
The component (A) of the present invention is represented by the following average composition formula (1):

(In the formula, ^R1 's are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, ^R2 is a hydrogen atom, ^R3 's are each independently a group selected from ^R1 and ^R2 , and -OH, _-OCH3 , and _{-OC2H5 ,} and a, b, c, d, and e are numbers that satisfy the ranges of 2≦a≦10, 0≦b≦1,000, 0≦c≦1,000, 0≦d≦5, and 0≦e≦5, provided that when c=0, at least one of ^R3 's is ^R2 .)
and has a viscosity at 25° C. of 5 to 10,000 mPa·s. These may be used alone or in combination of two or more.

Each R ¹ is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, and octadecyl; alkenyl groups such as vinyl, allyl, 5-hexenyl, and oleyl; and aryl groups such as phenyl, tolyl, and naphthyl. Among these, methyl, long-chain (6 to 20 carbon atoms) alkyl groups, and phenyl are preferred, with methyl being more preferred.

R ² is a hydrogen atom. R ³ is each independently a group selected from R ¹ and R ² , and -OH, -OCH ₃ and -OC ₂ H _5. However, when c=0, at least one of R ³ is R ² , i.e., a hydrogen atom. Of the total of the substituents represented by R ¹ , R ² and R ³ , it is preferable that 10% or more is R ² (hydrogen atom), more preferably 15% or more is R ² (hydrogen atom), and even more preferably 20% or more is R ² (hydrogen atom).

a is 2≦a≦10, preferably 2≦a≦5, and more preferably 2≦a≦3. If a is less than 2, the viscosity of the organohydrogenpolysiloxane becomes too high, resulting in poor emulsion stability. On the other hand, if a exceeds 10, the viscosity of the organohydrogenpolysiloxane becomes too low, resulting in poor water repellency.

b is 0≦b≦1,000, preferably 0≦b≦100, and more preferably 0≦b≦50. If b exceeds 1,000, the viscosity of the organohydrogenpolysiloxane becomes too high, resulting in poor emulsion stability.

c is 0≦c≦1,000, preferably 10≦c≦500, and more preferably 20≦c≦200. If b exceeds 1,000, the viscosity of the organohydrogenpolysiloxane becomes too high, resulting in poor emulsion stability.

d is 0≦d≦5, and preferably d=0. If d exceeds 5, the viscosity of the organohydrogenpolysiloxane becomes too high, resulting in poor emulsion stability.

e is 0≦e≦5, and preferably e=0. If e exceeds 5, the viscosity of the organohydrogenpolysiloxane becomes too high, resulting in poor emulsion stability.

The viscosity of component (A) at 25°C is 5 to 10,000 mPa·s, preferably 5 to 8,000 mPa·s, more preferably 10 to 5,000 mPa·s, and even more preferably 10 to 100 mPa·s. If the viscosity is below the lower limit, the texture of the fibers will be poor. If the viscosity exceeds the upper limit, the emulsion stability will be poor. In the present invention, the viscosity is a value measured using a BM type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.). The rotor and rotation speed are appropriately selected depending on the viscosity.
Examples of the component (A) include compounds represented by the following formula.

（ａ，ｂ及びｃは、２≦ａ≦１０、０≦ｂ≦１，０００、０≦ｃ≦１，０００の範囲を満たす数である。）

(a, b, and c are numbers that satisfy the ranges of 2≦a≦10, 0≦b≦1,000, and 0≦c≦1,000.)

[Component (B)]
The surfactant of component (B) is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. These can be used alone or in appropriate combination of two or more kinds.

Examples of nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, polyoxyalkylene alkyl esters, polyoxyalkylene sorbitan alkyl esters, polyethylene glycols, polypropylene glycols, diethylene glycols, etc. Among these, polyoxyalkylene alkyl ethers represented by the following general formula (3) are preferred.
^R6O (EO) _n (PO) _mH (3)
(In the formula, ^R6 is a linear or branched alkyl group having 8 to 30 carbon atoms, preferably 8 to 12 carbon atoms, n and m are each an integer of 0 to 50, preferably an integer of 0 to 25, and n+m=5 to 50. EO is a polyoxyethylene group, and PO is a polyoxypropylene group.)

As the anionic surfactant, an alkyl sulfate represented by the following general formula (4) and an alkyl benzene sulfonate represented by the following general formula (5) are preferred.
R ⁷ -OSO ₃ M (4)
R ⁷ -C ₆ H ₄ -SO ₃ M (5)
(In the formula, ^R7 is a linear or branched alkyl group having 8 to 30 carbon atoms, preferably 8 to 12 carbon atoms, and M is a hydrogen atom or a metal element, preferably a hydrogen atom, an alkali metal element, or an alkaline earth metal element.)

Examples of alkyl sulfates include sodium lauryl sulfate. Examples of alkyl benzene sulfonates include salts of hexyl benzene sulfonic acid, octyl benzene sulfonic acid, decyl benzene sulfonic acid, dodecyl benzene sulfonic acid, cetyl benzene sulfonic acid, and myristyl benzene sulfonic acid.

Further examples of the anionic surfactant include higher fatty acids such as lauric acid, stearic acid, oleic acid, and linoleic acid and salts thereof, polyoxyethylene monoalkyl ether sulfates represented by the following general formula (6), and polyoxyethylene alkyl phenyl ether sulfates represented by the following general formula (7).
R ⁸ O(EO) _{n '} (PO) _{m '} SO ₃ M (6)
R ⁸ -C ₆ H ₄ -O(EO) _{n '} (PO) _{m '} SO ₃ M (7)
(In the formula, ^R8 is a straight or branched alkyl group having 8 to 30 carbon atoms, preferably 8 to 12 carbon atoms; M is a hydrogen atom or a metal element, preferably a hydrogen atom, an alkali metal element or an alkaline earth metal element; n' and m' are each an integer of 0 to 30, preferably an integer of 0 to 20, and n'+m'=5 to 50; EO is a polyoxyethylene group, and PO is a polyoxypropylene group.)

Examples of cationic surfactants include anionic emulsifiers such as alkylbenzene sulfonates and alkyl phosphates, and cationic emulsifiers such as quaternary ammonium salts and alkylamine salts.

Examples of amphoteric surfactants include alkyl betaines, alkyl imidazolines, etc.

The amount of component (B) is 0.5 to 50 parts by mass, preferably 1.0 to 45 parts by mass, and more preferably 1.5 to 40 parts by mass, per 100 parts by mass of component (A). If the amount of component (B) is too small, emulsification becomes difficult, and if the amount is too large, the water repellency decreases.

[Component (C)]
The (C) component is a condensation reaction catalyst for promoting the reaction between the hydrogen atom directly bonded to the silicon atom of the (A) component and the reactive functional group on the fiber. The (C) component can be used alone or in combination of two or more. Examples of the condensation reaction catalyst include compounds of various metals such as tin, zinc, bismuth, titanium, zirconium, aluminum, iron, tin, and lead. Among them, from the viewpoints of high catalytic activity and easy availability, compounds of one or more metals selected from tin, zinc, bismuth, titanium, zirconium, and aluminum are preferred, and compounds of one or more metals selected from tin, zinc, and titanium are more preferred.

The compound is a salt and/or complex having the above metal ion as a central element, and preferably has at least one selected from carboxylic acids, ketones, and esters having an alkyl group having 1 to 30 carbon atoms as a counter ion and/or ligand. Examples of the alkyl group include methyl, isopropyl, butyl, 2-ethylhexyl, octyl, isodecyl, isostearyl, decanyl, and cetyl groups.

Specific examples of the component (C) include metal salts of carboxylates such as tin bis(2-ethylhexanoate), zinc bis(2-ethylhexanoate), zinc laurate, zinc acetate, zirconium acetate, zinc formate, iron bis(2-ethylhexanoate), iron tris(2-ethylhexanoate), zirconium bis(2-ethylhexanoate), zirconium tetra(2-ethylhexanoate), bismuth tris(2-ethylhexanoate), and tin versatate, dibutyltin dilaurate, dibutyltin maleate, and dibutyltin. Phthalate, dibutyltin dioctanoate, dibutyltin bis(2-ethylhexanoate), dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin bis(benzyl maleate), dibutyltin diacetate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dibutyltin di tetravalent organic tin compounds such as dibutyltin methoxide, dibutyltin bis(nonylphenoxide), dibutenyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(ethylacetoacetate), reaction products of dibutyltin oxide with silicate compounds , reaction products of dialkyltin dicarboxylates such as dioctyltin dilaurate, dibutyltin dineodecane, and dioctyltin dineodecane with silicate compounds, and reaction products of dibutyltin oxide with phthalic acid esters Examples of the organic titanium compounds include titanium tetraisopropoxy, titanium tetra n-butoxy, diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), and other organic titanium compounds; aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate, and other organic aluminum compounds; and zirconium compounds such as zirconium tetrakis(acetylacetonate).

The content of the component (C) is 0.1 to 100 parts by mass, preferably 5 to 80 parts by mass, and more preferably 10 to 70 parts by mass, per 100 parts by mass of the component (A). If the amount of the component ( C ) is too small, the water repellency decreases, and if it is too large, the flexibility and feel decrease.

The effect of component (C) is not limited, but the inventor believes it to be as follows. The hydrogen atoms directly bonded to silicon atoms contained in component (A) and functional groups such as hydroxyl groups on the treated fiber can form bonds by dehydrogenation reaction. Therefore, by using a condensation catalyst of component ( C ) in combination, the above reaction is promoted, and the fiber and component (A) can be more firmly bonded. Therefore, it is possible to impart higher water repellency to the fiber, and further, the flexibility imparting effect of the polysiloxane component is strongly expressed, and it is also possible to impart good flexibility to the fiber.

[Component (D)]
The water repellent composition of the present invention contains water (D) in an amount of 50 to 3,000 parts by mass, and preferably 50 to 2,000 parts by mass, per 100 parts by mass of component (A).

The water repellent composition of the present invention does not contain fluorine compounds, but may contain trace amounts of fluorine compounds contained in the raw materials.

（式中、Ｒ⁴は互いに独立に、炭素数１～２０の非置換１価炭化水素基であり、Ｒ⁵は互いに独立に、Ｒ⁴、－ＯＨ、－ＯＣＨ₃及び－ＯＣ₂Ｈ₅から選ばれる基であり、ｆ、ｇ、ｈ、ｉ及びｊは、２≦ｆ≦１０、０≦ｇ≦１，０００、０≦ｈ≦４００、０≦ｉ≦５、０≦ｊ≦５の範囲を満たす数である。但し、Ｒ⁵のうち少なくとも一つが－ＯＨである。）
で表されるオルガノポリシロキサンであり、１種単独で又は２種以上組み合わせて用いることができる。 [Component (E)]
The water repellent composition of the present invention may contain a component (E). The component (E) is a compound represented by the following average composition formula (2):

(In the formula, R ⁴ 's are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ 's are each independently a group selected from R ⁴ , --OH, --OCH ₃ , and --OC ₂ H ₅ , and f, g, h, i, and j are numbers that satisfy the ranges of 2≦f≦10, 0≦g≦1,000, 0≦h≦400, 0≦i≦5, and 0≦j≦5, with the proviso that at least one of R ⁵ 's is --OH.)
These organopolysiloxanes can be used alone or in combination of two or more.

^Each R4 is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, and octadecyl; alkenyl groups such as vinyl, allyl, 5-hexenyl, and oleyl; and aryl groups such as phenyl, tolyl, and naphthyl. Among these, methyl, long-chain (6 to 20 carbon atoms) alkyl groups, and phenyl are preferred, with methyl being more preferred.

R ⁵ 's are each independently a group selected from R ⁴ , --OH, --OCH ₃ and --OC ₂ H ₅ , with --OH being preferred.
f is 2≦f≦10, preferably 2≦f≦5, and more preferably f=2.
The value of g satisfies 0≦g≦1,000, preferably 5≦b≦800, and more preferably 5≦b≦500. If b exceeds 1,000, the viscosity of the organopolysiloxane becomes too high, resulting in poor emulsion stability.
h is 0≦h≦400, preferably 0≦h≦30, and more preferably 0≦h≦250.
The value of i is 0≦h≦5, and it is preferable that h = 0. If h exceeds 5, the viscosity of the organopolysiloxane becomes too high, resulting in poor emulsion stability.
j is 0≦i≦5, and preferably i = 0. If i exceeds 5, the viscosity of the organopolysiloxane becomes too high, resulting in poor emulsion stability.
Specific examples of the component (E) include the following:

（ｆ、ｇ、ｈ、ｉ、ｊは上記と同じである。）

(f, g, h, i, j are the same as above.)

When component (E) is blended, the blending amount is 1 to 50 parts by mass, preferably 2 to 45 parts by mass, and more preferably 5 to 40 parts by mass, per 100 parts by mass of component (A).

[Water repellent composition]
The water repellent composition of the present invention may be appropriately blended with various thickeners, pigments, dyes, penetrating agents, antistatic agents, defoamers, flame retardants, antibacterial agents, preservatives, crosslinking agents, adhesion improvers, other silicone oils, silicone resins, acrylic resins, urethane resins, and the like, within the scope of not impairing the effects of the present invention.

The method for preparing the water repellent composition of the present invention is not particularly limited, and may be any of the conventionally known emulsion polymerization methods and phase inversion emulsification methods. The emulsifier is not particularly limited, and for example, a homomixer, homogenizer, colloid mill, universal mixer, combimix, line mixer, etc. may be used. The type of the obtained emulsion is not particularly limited, and may be any of O/W type, W/O type, etc.

The water repellent composition of the present invention is used by treating the surface of various substrates such as fibers, paper, metal, wood, rubber, plastic, and glass. The method of application to the substrate can be any of the various conventional coating methods, including dipping, spraying, roll coating, bar coating, and brush coating.

Furthermore, the amount of the water repellent composition to be applied is not particularly limited, but typically the amount applied is 0.1 to 200 g/m ² , and particularly 1 to 100 g/m ² , of the water repellent composition. After application, an organopolysiloxane coating can be obtained simply by drying, which may be performed under conditions that allow water to volatilize, such as drying at room temperature for 1 to 3 days, or at 100 to 180° C. for about 1 to 30 minutes when heated.

[Textile treatment agent]
The water repellent composition of the present invention is useful as an active ingredient of a fiber treatment agent since the treated fiber surface has excellent water repellency. The water repellent composition may be used as a fiber treatment agent as it is, or may be appropriately blended in a fiber treatment agent, for example, in the range of 0.01 to 99 mass %. Here, other ingredients in the fiber treatment agent include fiber agents such as wrinkle inhibitors, flame retardants, antistatic agents, and heat resistance agents, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, curing accelerators, deodorants, and antibacterial agents.

When treating fibers, the fiber treatment agent may be diluted before use, and the amount of water repellent composition in the diluted fiber treatment agent used to treat fibers is preferably 0.01 to 5 mass % in terms of solids, and more preferably 0.1 to 3 mass %.

The water repellent composition and textile treatment agent of the present invention are effective not only for natural fibers such as cotton, silk, hemp, wool, angora, and mohair, but also for synthetic fibers such as polyester, nylon, acrylic, urethane, and spandex, and textile products made from these. There are also no limitations on the form or shape, and the textile treatment agent of the present invention can treat not only raw materials such as staples, filaments, tow, and threads, but also various processed forms such as woven fabrics, knitted fabrics, wadding, nonwoven fabrics, paper, sheets, and films.

The water repellent composition and fiber treatment agent of the present invention can also be applied to substrates other than fibers. Substrates to which the water repellent composition and fiber treatment agent can be applied include inorganic porous materials such as concrete, lightweight concrete, lightweight aerated concrete (ALC), mortar, various cement boards, gypsum boards, calcium silicate boards, bricks, roofing tiles, tiles, and stones. They can also be used on walls made primarily of diatomaceous earth, clay, plaster, etc., and organic porous materials such as paper, wood, and leather.

The present invention will be specifically described below with examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, unless otherwise specified, "%" in the composition indicates mass %.

（Ｂ）ノニオンＫ－２０４：１．２０質量部、
ノニオンＫ－２３０：０．３０質量部、
（Ｄ）イオン交換水：３８．５０質量部
をホモミキサーを用いて混合して乳化分散し、その後、高圧ホモジナイザーにて３０ＭＰａの条件下にて高圧処理を行い、シリコーンエマルション組成物（Ｉ－１）を得た。 [Production Example 1]
(A) an organohydrogenpolysiloxane represented by the following average composition formula (A-1) (viscosity at 25° C.: 20 mPa s): 60.00 parts by mass,

(B) Nonion K-204: 1.20 parts by mass,
Nonion K-230: 0.30 parts by mass,
(D) Ion-exchanged water: 38.50 parts by weight were mixed and emulsified using a homomixer, and then subjected to high-pressure treatment at 30 MPa using a high-pressure homogenizer to obtain a silicone emulsion composition (I-1).

（Ｂ）ノニオンＫ－２０４：１．２０質量部、
ノニオンＫ－２３０：０．３０質量部、
（Ｄ）イオン交換水：３８．５０質量部
をホモミキサーを用いて混合して乳化分散し、その後、高圧ホモジナイザーにて３０ＭＰａの条件下にて高圧処理を行い、シリコーンエマルション組成物（Ｉ－２）を得た。 [Production Example 2]
(A) 60.00 parts by mass of an organohydrogenpolysiloxane represented by the following average composition formula (A-2) (viscosity at 25° C.: 45 mPa·s),

(B) Nonion K-204: 1.20 parts by mass,
Nonion K-230: 0.30 parts by mass,
(D) Ion-exchanged water: 38.50 parts by weight were mixed and emulsified using a homomixer, and then subjected to high-pressure treatment at 30 MPa using a high-pressure homogenizer to obtain a silicone emulsion composition (I-2).

（Ｂ）コータミン２４Ｐ：８．１８質量部、
ニューコール１３１０：０．２０質量部、
（Ｄ）イオン交換水：６１．６２質量部を、ホモミキサーを用いて混合して乳化分散し、その後、高圧ホモジナイザーにて３０ＭＰａの条件下にて高圧処理を行い、シリコーンエマルション組成物（Ｉ－３）を得た。 [Production Example 3]
(A) Organohydrogenpolysiloxane represented by the above average composition formula (A-1): 27.00 parts by mass,
(E) an organopolysiloxane represented by the following average composition formula (E-1): 3.00 parts by mass,

(B) Cortamine 24P: 8.18 parts by mass,
Newcol 1310: 0.20 parts by mass,
(D) Ion-exchanged water: 61.62 parts by weight was mixed and emulsified using a homomixer, and then subjected to high-pressure treatment at 30 MPa using a high-pressure homogenizer to obtain silicone emulsion composition (I-3).

（Ｂ）コータミン２４Ｐ：８．１８質量部、
ニューコール１３１０：０．２０質量部、
（Ｄ）イオン交換水：６１．６２質量部を、ホモミキサーを用いて混合して乳化分散し、その後、高圧ホモジナイザーにて３０ＭＰａの条件下にて高圧処理を行い、シリコーンエマルション組成物（Ｉ－４）を得た。 [Production Example 4]
(A) Organohydrogenpolysiloxane represented by the above average composition formula (A-1): 27.00 parts by mass,
(E) an organopolysiloxane represented by the following average composition formula (E-2): 3.00 parts by mass,

(B) Cortamine 24P: 8.18 parts by mass,
Newcol 1310: 0.20 parts by mass,
(D) Ion-exchanged water: 61.62 parts by weight were mixed and emulsified using a homomixer, and then subjected to high-pressure treatment at 30 MPa using a high-pressure homogenizer to obtain silicone emulsion composition (I-4).

[Production Example 5]
(C) zinc formate: 10.00 parts by mass,
Potassium acetate: 10.00 parts by mass,
0.50 parts by weight of acetic acid,
(D) Ion-exchanged water: 79.50 parts by mass were mixed and dissolved to obtain an aqueous solution of zinc compound (II-1).

[Production Example 6]
(C) zinc acetate: 24.00 parts by mass,
(D) Ion-exchanged water: 76.60 parts by mass were mixed and dissolved to obtain an aqueous solution of a zinc compound (II-2).

[Production Example 7]
(C) Neostan U-830: 42.00 parts by mass,
Sonneborn Kaydol (liquid paraffin, viscosity 350): 8.00 parts by mass,
(B) Emulgen 104P: 4.80 parts by mass,
(B) Emulgen 123P: 0.70 parts by mass,
(D) Ion-exchanged water: 44.50 parts by mass was mixed and emulsified using a homomixer to obtain a tin compound emulsion composition (II-3).

[Production Example 8]
(C) Neostan U-810: 31.20 parts by mass,
Sonneborn Kaydol (liquid paraffin, viscosity 350): 5.80 parts by mass,
(B) Emulgen 1108: 3.00 parts by mass,
(D) Ion-exchanged water: 60.00 parts by mass was mixed and emulsified using a homomixer to obtain a tin compound emulsion composition (II-4).

（Ｂ）ノニオンＫ－２０４：１．２０質量部、
ノニオンＫ－２３０：０．３０質量部、
（Ｄ）イオン交換水：６８．５０質量部
をホモミキサーを用いて混合して乳化分散し、その後、高圧ホモジナイザーにて３０ＭＰａの条件下にて高圧処理を行い、シリコーンエマルション組成物（ＩＩＩ－１）を得た。 [Production Example 9]
(E) an organopolysiloxane represented by the following average composition formula (E-1): 30.00 parts by mass,

(B) Nonion K-204: 1.20 parts by mass,
Nonion K-230: 0.30 parts by mass,
(D) Ion-exchanged water: 68.50 parts by weight were mixed and emulsified using a homomixer, and then subjected to high-pressure treatment at 30 MPa using a high-pressure homogenizer to obtain a silicone emulsion composition (III-1).

The raw materials used are shown below.
(B) Surfactant Nonion K-204 (trade name): manufactured by NOF Corporation, polyoxyethylene lauryl ether, HLB value 9.7
Nonion K-230 (product name): NOF Corporation, polyoxyethylene lauryl ether, HLB value 17.5
Kotamine 24P (trade name): manufactured by Kao Chemical Co., Ltd., lauryl trimethyl ammonium chloride Newcol 1310 (trade name): manufactured by Nippon Nyukazai Co., Ltd., polyoxyethylene tridecyl ether, HLB value 13.7
Emulgen 104P (product name): manufactured by Kao Chemical Co., Ltd., polyoxyethylene lauryl ether, HLB value 9.6
Emulgen 123P (product name): manufactured by Kao Chemical Co., Ltd., polyoxyethylene lauryl ether, HLB value 16.9
Emulgen 1108 (product name): manufactured by Kao Chemical Co., Ltd., polyoxyethylene alkyl ether, HLB value 13.5

(C) Condensation reaction catalyst Neostan U-810 (trade name): dioctyltin dineodecane manufactured by Nitto Kasei Co., Ltd. Neostan U-830 (trade name): dioctyltin dilaurate manufactured by Nitto Kasei Co., Ltd. The composition of the obtained composition is shown in the table below.

[Examples and Comparative Examples]
The compositions obtained in the above Production Examples were mixed in the amounts shown in the following table to obtain water repellent compositions of Examples and Comparative Examples (the amount of each component per 100 parts by mass of component (A) is shown for each mix). The water repellent compositions obtained were subjected to the following evaluation tests. The results are also shown in the table.

[Evaluation test]
1. Flexibility The water repellent composition was added with ion-exchanged water and stirred, and diluted to 2% of the (A) component to prepare a test liquid. A cotton broadcloth and a polyester/cotton broadcloth (65%/35%) were immersed in this test liquid for 10 seconds, and then squeezed with a roll under the condition of 100% squeezing rate, and dried at 150°C for 2 minutes to prepare a treated cloth for flexibility evaluation. The treated cloth was touched by three panelists, and compared with an untreated cloth, and the flexibility was evaluated by the following score. The results are shown according to the following evaluation criteria based on the total score of the three panelists.
<Score>
3 points: Feels very good to the touch compared to untreated cloth.
2 points: Feels better to the touch than untreated cloth.
Score 1: Feels the same as untreated cloth.
0 points: Feels bad to the touch compared to untreated cloth.
<Evaluation criteria>
◎: Total of 7 points or more○: Total of 5 to 6 points△: Total of 3 to 4 points×: Total of 2 points or less

2. Water repellency The water repellent composition was added with ion-exchanged water and stirred, and diluted to 2% of component (A) to prepare a test liquid. A cotton broadcloth and a polyester/cotton broadcloth (65%/35%) were immersed in this test liquid for 10 seconds, and then squeezed with a roll at a squeeze rate of 100%, and dried at 150°C for 3 minutes to prepare treated cloth for softness evaluation. The treated cloth was tested according to the spray method of JIS-L 1092. The results were visually evaluated according to the following grades.
Water repellency: Condition 5: No adhesion or wetting on the surface 4: Slight adhesion or wetting on the surface 3: Partial wetting on the surface 2: Wetting on the surface 1: Wetting on the entire surface 0: Complete wetting on both the front and back surfaces

As shown in the table above, the water repellent composition of the present invention has excellent water repellency and the treated fabric has good flexibility. Furthermore, since it does not contain fluorine compounds, it has a low environmental impact.

The water repellent composition of the present invention has excellent water repellency and the treated fabric has good flexibility. Furthermore, since it does not contain fluorine compounds, it has a low environmental impact.

Claims (5)

(A) The following average composition formula (1)

(In the formula, ^R1 is a methyl group, ^R2 is a hydrogen atom, ^R3 is each independently a group selected from ^R1 and ^R2 , and a, b, c, d, and e are numbers that satisfy the ranges of a=2 , 0≦b≦50, 20≦c≦200, d=0, and e=0.)
and having a viscosity at 25°C of 5 to 10,000 mPa·s: 100 parts by mass,
(B) Nonionic surfactant: 0.5 to 50 parts by mass,
(C) Tin bis(2-ethylhexanoate), zinc bis(2-ethylhexanoate), zinc laurate, zinc acetate, zirconium acetate, zinc formate, iron bis(2-ethylhexanoate), iron tris(2-ethylhexanoate), zirconium bis(2-ethylhexanoate), zirconium tetra(2-ethylhexanoate), bismuth tris(2-ethylhexanoate), tin versatate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin Phthalate, dibutyltin dioctanoate, dibutyltin bis(2-ethylhexanoate), dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin bis(benzyl maleate), dibutyltin diacetate, dioctyltin bis(ethyl maleate), dioctyltin 10 to 100 parts by mass of a condensation reaction catalyst selected from bis(octylmaleate), dibutyltin dimethoxide, dibutyltin bis(nonylphenoxide), dibutenyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(ethylacetoacetate), a reaction product of dibutyltin oxide and a silicate compound , dioctyltin dilaurate, dibutyltin dineodecane, dioctyltin dineodecane, a reaction product of dibutyltin oxide and a phthalic acid ester, tetraisopropoxytitanium, tetra-n-butoxytitanium, diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate, and zirconium tetrakis(acetylacetonate),
(D) water: 50 to 3,000 parts by mass, and (E) a composition represented by the following average formula (2):

(In the formula, ^R4 is a methyl group; ^R5 is each independently _a group selected from ^R4 , --OH, _--OCH3 , and _--OC2H5 ; and f, g, h, and j are numbers that satisfy the ranges of 2≦f≦10, 0≦g≦1,000, 0≦h≦400, 0≦i≦5, and 0≦j≦5, with the proviso that at least one of ^R5 is --OH.)
and containing no fluorine compound (however, excluding those containing a diorganopolysiloxane whose molecular chain terminals are blocked with hydroxyl groups or alkoxy groups having 1 to 3 carbon atoms and having at least one functional group selected from the group consisting of epoxy groups, carboxyl groups and mercapto groups in the side chain). 2. The fiber treatment agent according to claim 1, wherein in the component (A), at least 20% of the total of the substituents represented by R ¹ , R ² and R ³ in formula (1) are R ² (hydrogen atom). The component (C) is tin bis(2-ethylhexanoate), zinc bis(2-ethylhexanoate), zinc laurate, zinc acetate, zinc formate, tin versatate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis(2-ethylhexanoate), dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin bis(benzyl maleate), dibutyltin 3. The fiber treating agent according to claim 1 or 2, wherein the condensation reaction catalyst is selected from the group consisting of dibutyltin diacetate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dibutyltin dimethoxide, dibutyltin bis(nonylphenoxide), dibutenyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(ethyl acetoacetate), a reaction product of dibutyltin oxide with a silicate compound , dioctyltin dilaurate, dibutyltin dineodecane, dioctyltin dineodecane and a reaction product of dibutyltin oxide with a phthalic acid ester. The fiber treatment agent according to any one of claims 1 to 3, wherein the viscosity of component (A) at 25°C is 10 to 100 mPa·s. The fiber treatment agent according to any one of claims 1 to 4, wherein component (B) is a polyoxyalkylene alkyl ether.