JP2907726B2 - Reactive emulsifier and aqueous composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to reactive emulsifiers and aqueous compositions.

[0002]

2. Description of the Related Art Stable aqueous emulsions of organosilicon compounds and organosilicon resins having a hydrolyzable / polycondensable functional group have been developed as water-based water-absorption inhibitors without using organic solvents, and some of them have already been put into practical use. Have been. As an aqueous emulsion of an organosilicon compound, for example, an aqueous emulsion using a nonionic emulsifier is known (Japanese Patent Application Laid-Open No.
2-197369, JP-A-1-29289, JP-A-3
174378, JP-A-3-18886). There is also known an example in which a silicone-based or fluorine-based emulsifier is used as an emulsifier in order to improve water repellency and water absorption prevention (Japanese Patent Application Laid-Open No. 3-115485). further,
Examples of using a silicon compound containing a quaternary ammonium base together with an alkoxy group, and a nonionic or anionic silicon compound having an emulsifying ability, such as an alkoxysilane or an emulsifier having a reactivity with civil engineering building materials, are also used. Known (JP-A-3-159975, JP-A-3-2
00793, JP-A-4-164877, JP-A-5-22
1748).

On the other hand, as an aqueous emulsion of an organic silicon resin, there is known an aqueous emulsion of a hydrolyzed / polycondensed product of a methylmethoxysilicone resin or an alkyltrialkoxysilane (JP-A-57-92561; 58-213046, JP-A-60-20959, JP-A-63-305132, and JP-A-4-255759. Further, in addition to the silicone emulsifier, there is also known an example in which a reactive emulsifier comprising an organopolysiloxane having an alkoxy group and a basic nitrogen and an acid and an acid is used (JP-A-5-156164).

However, the aqueous emulsions of organosilicon compounds and organosilicon resins disclosed in the above-mentioned known documents require a large amount of an emulsifier to obtain stability during emulsification and stability over time. For this reason, there is a problem that the effect of water repellency and water absorption prevention of the civil engineering building material is reduced. If the amount of the emulsifier used is reduced in order to improve water repellency and water absorption prevention, the problem that the organic silicon compound or the organic silicon resin gradually condenses with the passage of time, thereby deteriorating the stability over time and the emulsion stability. Occurs.

Aqueous emulsions using a silicone-based or fluorine-based emulsifier as the emulsifier increase the water repellency due to the silicone or fluorine. The quality is improved, but it is still insufficient, and
Emulsion stability and stability over time are poor. As for an aqueous emulsion using the above-mentioned reactive emulsifier having an alkoxysilyl group, there has not been obtained an aqueous emulsion which simultaneously satisfies both water repellency and anti-water absorption, emulsion stability and temporal stability. For example, when a silane compound having a surface activity described in JP-A-5-221748 is used as an emulsifier, there are the following problems, and the resulting aqueous emulsion has emulsion stability and stability over time. Poor nature. The alkoxysilyl group in the silane compound is bonded to the hydrophilic polyethylene oxide terminal, or the bond between the alkoxysilyl group and the polyethylene oxide is Si—O—C
Since it is a bond, it is highly hydrolyzable and unstable to water. Since the alkoxysilyl group is easily hydrolyzed and polycondensed, the aqueous emulsion of the organosilicon compound containing such a silane compound becomes a thickened gel.

Further, when an aqueous emulsion of an organosilicon compound or an organosilicon resin disclosed in each of the above-mentioned known documents is used as a water-absorbing agent for civil engineering and building materials, durability is poor, and water repellency and water-absorbing property are poor. There is a problem of early decline.

[0007]

The problem to be solved by the present invention is to provide a novel alkoxysilane compound having a surface activity and to produce it easily and with good reproducibility. Another problem to be solved by the present invention is to provide an aqueous composition containing an organosilicon compound or an organosilicon resin, while maintaining high emulsification stability, stability over time, water repellency and anti-water absorption properties while maintaining durability. Is to improve.

[0008]

The alkoxysilane compound and its production method The alkoxysilane compound (A) of the present invention has a structure represented by the following general formula (1).

[0009]

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(Provided that R ^{1 is} H or C 6-18)
Alkyl group, R ² : alkyl group having 1 to 6 carbon atoms, R ³ :
Alkyl group of from 1 to 6 carbon, A: A Ruki <br/> alkylene group having 2 to 4 carbon _{atoms, B: H, SO 3 NH} 4, SO 3 Na, CO 2 N
H ₄ or CO ₂ Na, m: 1~200 integer, n: 0
In the general formula (1) , B : H, SO
₃ NH ₄ or SO ₃ Na, m: preferably an integer of 1 to 100.

The method for producing the alkoxysilane compound (A) of the present invention comprises a compound (B) represented by the following general formula (3) and a compound (C) represented by the following general formula (4)
And performing a humanrosilylation reaction using

[0012]

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(Provided that R ¹ : H, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, A: an alkylene group having 2 to 4 carbon atoms which may be substituted, B: H, SO ₃ NH ₄ , SO _Three
Na, CO ₂ NH ₄ or CO ₂ Na, m: 1 to 200
Is an integer. )

[0014]

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(Where R ^{2 is} a hydrocarbon group having 1 to 10 carbon atoms, R ³ is an alkyl group which may be substituted and has 1 to 10 carbon atoms, and n is an integer of 0 to 2). The alkoxysilane compound (A) of the present invention and a method for producing the same will be described in detail. The alkoxysilane compound (A) of the present invention is mainly composed of a phenyl group or an alkylphenyl group having hydrophobicity, and a hydrophilic (poly) group.
Alkylene oxide group, ammonium sulfonate group of (poly) alkylene oxide, sodium sulfonate group of (poly) alkylene oxide, ammonium carboxylate group of (poly) alkylene oxide or (poly)
It is composed of a sodium carboxylate base of alkylene oxide and a reactive alkoxysilyl group capable of binding to various materials. In particular, since the alkoxysilyl group is not directly bonded to the (poly) alkylene oxide group, it is protected by a hydrophobic group such as a phenyl group or an alkylphenyl group. For this reason, hydrolysis / polycondensability is suppressed even in water, and it is more stable than the above-mentioned silane compound in which an alkoxysilyl group is bonded to the polyethylene oxide terminal.

A phenyl group or an alkylphenyl group is
It is a portion exhibiting hydrophobicity and acts as a lipophilic group when the alkoxysilane compound (A) is used as a reactive emulsifier. In addition, the phenyl group or the alkylphenyl group is a group that protects an alkoxysilyl group described below from water. And a group that imparts anti-water absorption properties.

[0017] wherein R ¹ is an alkyl group selected sparse in terms of an aqueous H or C 6-18, preferably
And an alkyl group having 6 to 18 carbon atoms , more preferably an alkyl group having 9 to 18 carbon atoms. Specific examples of the alkyl group having 6 to 18 carbon atoms include a hexyl group, an octyl group,
2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group, pentadecyl group, hexadecyl group,
An octadecyl group;

(Poly) alkylene oxide group, (poly)
Ammonium sulfonate bases of alkylene oxides,
A sodium sulfonate group of a (poly) alkylene oxide, an ammonium carboxylate group of a (poly) alkylene oxide or a sodium carboxylate group of a (poly) alkylene oxide is a portion exhibiting hydrophilicity and reacts with the alkoxysilane compound (A). When used as a hydrophilic emulsifier, it is used as a hydrophilic group. Where A, from the viewpoint of a parent aqueous, an alkylene group having 2 to 4 carbon atoms, preferred
Properly is an alkylene group, more preferably <br/> ethylene group having 2 to 3 carbon atoms.

B is H, SO ₃ NH ₄ , SO ₃ Na, CO
₂ NH ₄ or CO ₂ Na, and when the alkoxysilane compound (A) is used as one component of the aqueous composition of the present invention, hydrolysis and hydrolysis of an alkoxysilyl group described later
H is preferable from the viewpoint of suppression of polycondensability. The alkoxysilyl group is a moiety exhibiting reactivity capable of bonding to various materials, particularly inorganic materials. When the alkoxysilane compound (A) is used as a reactive emulsifier as one component of the aqueous composition of the present invention, It is a group that improves water repellency and water absorption prevention as a result of suppressing bleeding of the emulsifier due to reaction with various materials.

[0020] wherein R ² is discussed later is alkoxysilyl group, in that it does not excessively reduce the hydrolyzable Nachi Suwa R ³ O group, an alkyl group having 1 to 6 carbon atoms, preferably <br An alkyl group having 1 to 3 carbon atoms , more preferably 1 alkyl group
To 2 alkyl groups, and most preferably a methyl group.

Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. R ³ is an alkoxysilyl group, i.e. the point binding is greater with higher inorganic materials hydrolyzable R ³ O group, an alkyl group having a carbon number of 1-6, preferably alkyl of 1 to 3 carbon atoms Ki , Sara
Preferably an alkyl group having 1 to 2 carbon atoms , most preferably
Is an ethyl group. In the case of using an alkoxysilane compound (A) as one component of the aqueous composition of the present invention, the methyl group has a very high hydrolyzability of the methoxy group. May decrease.

Specific examples of R ³ include the same groups as those exemplified for R ² above. m is not particularly limited as long as it is an integer of 1 to 200, but 1 of the aqueous composition of the present invention.
When the alkoxysilane compound (A) is used as a component, it is preferably an integer of 1 to 100, and m is 2 to 50 from the viewpoint of the emulsion stability and the stability over time of the aqueous composition. More preferably an integer, m
Is more preferably an integer of 4 to 30, and m is 5 to 2
Even more preferably, it is an integer of 0. Most preferably, m is an integer from 7 to 15.

Although n is not particularly limited as long as it is an integer of 0 to 2, n is 0 or 1 from the viewpoint of high hydrolyzability of the above-mentioned alkoxysilyl group and bonding with inorganic materials.
Is preferable, and 0 is most preferable. The alkoxysilane compound (A) of the present invention is stable in water even when it is hardly hydrolyzed / polycondensed, particularly polycondensed with an alkoxysilyl group. This is, as mentioned earlier,
A (poly) alkylene oxide group, an ammonium sulfonate group of a (poly) alkylene oxide or a sodium sulfonate group of a (poly) alkylene oxide are compatible with water, and a phenyl group or an alkylphenyl group is formed by hydrolysis of an alkoxysilyl group. This is for suppressing and stabilizing polycondensation, particularly polycondensation. For these reasons, when the alkoxysilane compound (A) is mixed with water, it can be uniformly dispersed in water.

The method for producing the alkoxysilane compound (A) of the present invention is not particularly limited. For example, a compound (B) represented by the following general formula (3) and a compound represented by the following general formula (3) in the presence of a hydrosilylation reaction catalyst: There is a method of subjecting the compound (C) represented by (4) to a hydrosilylation reaction. According to this method, the alkoxysilane compound (A) can be obtained easily and with good reproducibility.

[0025]

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(Provided that R ¹ : H, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, A: an alkylene group having 2 to 4 carbon atoms which may be substituted, B: H, SO ₃ NH ₄ , SO _Three
Na, CO ₂ NH ₄ or CO ₂ Na, m: 1 to 200
Integer. )

[0027]

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(Provided that R ^{2 is} a hydrocarbon group having 1 to 10 carbon atoms, R ³ is an alkyl group which may be substituted and has 1 to 10 carbon atoms, and n is an integer of 0 to 2). As specific examples of the compound (B) represented by (3), the number of repeating units of oxyethylene is 1 to 10
Polyoxyethylene allyl glycidyl phenyl ether in the range of 0;
Polyoxyethylene allyl glycidyl octyl phenyl ether in the range of from 100 to 100, polyoxyethylene allyl glycidyl nonyl phenyl ether in which the number of repeating units of oxyethylene is in the range of 1 to 100, and the number of repeating units of oxyethylene in the range of from 1 to 100 A polyoxyethylene allyl glycidyl decyl phenyl ether, a polyoxyethylene allyl glycidyl decyl phenyl ether having a number of repeating units of 1 to 100, a polyoxyethylene having a number of repeating units of oxyethylene of 1 to 100 Ethylene allyl glycidyl tridecyl phenyl ether, polyoxyethylene allyl glycidyl tetradecyl phenyl ether having a repeating unit number of oxyethylene in the range of 1 to 100, oxyethylene Polyoxyethylene allyl glycidyl hexadecyl phenyl ether having a number of repeating units of 1 to 100, polyoxyethylene allyl glycidyl octadecyl phenyl ether having a number of repeating units of 1 to 100, and the number of repeating units of oxyethylene Is a sulfonate ammonium salt of polyoxyethylene allyl glycidyl nonyl phenyl ether in the range of 1 to 100, a sodium sulfonate of polyoxyethylene allyl glycidyl nonyl phenyl ether in which the number of repeating units of oxyethylene is in the range of 1 to 100, In place of the polyoxyethylene group in which the number of repeating units of the oxyethylene is in the range of 1 to 100, a polyoxypropylene group in which the number of repeating units of oxypropylene is in the range of 1 to 100, A polyoxybutylene group in which the number of repeating units of xylene is in the range of 1 to 100, or a poly (oxyethylene-oxypropylene) group in which the total number of repeating units of oxyethylene-oxypropylene is in the range of 1 to 100; The total number of repeating units of ethylene and oxybutylene is 1 to
Compounds having a poly (oxyethylene-oxybutylene) group in the range of 100 and a poly (oxypropylene-oxybutylene) group in which the total number of repeating units of oxypropylene and oxybutylene is in the range of 1 to 100 are exemplified.

Here, for each of R ¹ , A, B and m, R ¹ is preferably H or an alkyl group having 6 to 18 carbon atoms, and R 6 is an alkyl group having 6 to 18 carbon atoms.
An alkyl group having 8 carbon atoms is more preferable, and an alkyl group having 9 to 18 carbon atoms is most preferable. A is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms, and most preferably an ethylene group. Also, B
Is preferably H. Further, m is preferably an integer of 1 to 100, more preferably m is an integer of 2 to 50, and m is more preferably an integer of 4 to 30.
Is more preferably an integer of 5 to 20. m is 7
Most preferably, it is an integer of ~ 15.

The compound (C) represented by the general formula (4) is not particularly limited as long as it is a silane compound having a Si—H bond in a molecule. Specific examples of the compound (C) include trimethoxysilane, Dimethoxymethylsilane, dimethoxyethylsilane, dimethoxypropylsilane, dimethoxybutylsilane, dimethylmethoxysilane, triethoxysilane, diethoxymethylsilane, dimethylethoxysilane, tripropoxysilane, dipropoxymethylsilane, dimethylpropoxysilane, tribubutoxysilane, Examples include dibutoxymethylsilane, dimethylbutoxysilane, dimethoxyethoxysilane, and diethoxymethoxysilane.

Here, R ² , R ³ and n each represent, for the above-mentioned reason, R ² has 1 to 1 carbon atoms.
An alkyl group having 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, an alkyl group having 1 to 2 carbon atoms is more preferable, and a methyl group is most preferable. R ³ has 1 to 1 carbon atoms
An alkyl group having 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, an alkyl group having 1 to 2 carbon atoms is more preferable, and an ethyl group is most preferable.

Further, n is preferably 0 or 1, and most preferably 0. The compound (B) and the compound (C) can be used in any amount, but it is preferable to use 1 to 3 mol of the compound (C) per 1 mol of the compound (B). . When used more, unreacted compound (C) increases. Next, the hydrosilylation reaction catalyst is not particularly limited as long as it is a conventionally known one. Specifically, a peroxide catalyst; an azo compound catalyst;
H ₂ PtCl ₆ , PtCl ₂ (C ₂ H ₄ ) ₂ , PtCl
₂ (py) (C ₂ H ₄ ) (however, py = pyridine), P
tCl ₂ [P (C ₂ H ₅ ) ₃ ] ₂ , Pt [P (C
₆ H _{5) 3] 4,} Pt [P (C ₆ H _{5) 3] 2} (C ₂ H
₄ ), PtClH [P (C ₂ H ₅ ) ₃ ] ₂ , PtH (S
platinum-based catalysts such as iCH ₃ Cl ₂ ) [P (C ₆ H ₅ ) ₃ ] ₂ ; RhCl [P (C ₆ H ₅ ) ₃ ] ₃ , PhH (CO)
Rhodium-based catalysts such as [P (C ₆ H ₅ ) ₃ ] ₂ and [PhCl (CO) ₂ ] ₂ ; Co ₂ (CO) ₈ , HCo (CO)
Cod catalyst such as ₄ ; Pd [P (C ₆ H ₅ ) ₃ ] ₃ L
₂ (where L is a ligand such as maleic anhydride or P-benzoquinone), Pd [P (C ₆ H ₅ ) ₃ ] ₄ , PdC
l ₂ [P (C ₆ H _{5) 3] 2} and the like of a palladium-based catalyst; - Various Nickel Nickel catalysts, such as phosphine complexes; trialkyl amines. Among them, a platinum-based catalyst is preferable, and chloroplatinic acid is more preferable because the hydrosilylation reaction can be promoted and the alkoxysilane compound (A) can be produced with a high yield.

The amount of the hydrosilylation catalyst to be used is not particularly limited, but may be from 10 ^-2 to 10 based on 1 mol of the compound (B).
^-10 mol, preferably 10 ^-3 to 10 ^-7 mol. If the amount is small, the reaction hardly proceeds, and if the amount is large, the catalyst is expensive, which is not preferable. Next, the hydrosilylation reaction is performed by mixing the compound (B), the compound (C) and the hydrosilylation catalyst under an inorganic solvent or in an organic solvent. Examples of the organic solvent include alcohols, ketones, ethers, esters, cerolylbs, aliphatic hydrocarbons, and aromatic hydrocarbons.

The reaction temperature and the reaction time for the hydrosilylation reaction are not particularly limited. However, depending on the type of the compound (B), the compound (C) and the hydrosilylation reaction catalyst, the reaction temperature is usually from room temperature to 2 hours.
It is in the range of 00C, preferably 50-150C. The reaction time is 10 minutes to 50 hours, preferably 1 hour to 20 hours.
Time range. The reaction pressure may be normal pressure, reduced pressure or increased pressure.

As another method for producing the alkoxysilane compound (A) of the present invention, for example, the compound (B) represented by the above general formula (3) is converted into the following general formula (5)
A hydrosilylation reaction in the presence of a hydrosilylation reaction catalyst with a halogenated silane compound (D) represented by formula (1), and then converting the halogenated silyl group into an alkoxysilyl group.

[0036]

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(Provided that X is a halogen atom, R ^{2 is} a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 2). As still another method for producing the alkoxysilane compound (A) of the present invention, Reacts, for example, a compound (E) represented by the following general formula (6) with a compound (F) represented by the following general formula (7) and a compound (G) represented by the following general formula (8) Method and the like.

[0038]

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(Provided that R ^{2 is} a hydrocarbon group having 1 to 10 carbon atoms, R ³ is an alkyl group which may be substituted and has 1 to 10 carbon atoms, and n is an integer of 0 to 2).

[0040]

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(However, R ^{1 is} H, a halogen atom or a hydrocarbon group having 6 to 18 carbon atoms.)

[0042]

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(However, A: may be substituted having 2 to 4 carbon atoms)
Alkylene group, B: H, SO_ThreeNH _Four, SO_ThreeNa,
CO_TwoNH_FourOr CO_TwoNa, m: 1 to 200
number. ) *********Reactive emulsifier The reactive emulsifier of the present invention is represented by the following general formula (1).
Alkoxysilane compound (A), its hydrolyzate and
And at least one selected from polycondensates thereof.

[0044]

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(However, R¹: H, halogen atom or charcoal
A hydrocarbon group having a prime number of 1 to 20, R^Two: Charcoal having 1 to 10 carbon atoms
Hydride group, R^Three: Al having 1 to 10 carbon atoms which may be substituted
Kill group, A: alkylene having 2 to 4 carbon atoms which may be substituted
Group, B: H, SO_ThreeNH_Four, SO_ThreeNa, CO_TwoNH_Four
Or CO_TwoNa, m: an integer of 1 to 200, n: 0 to 2
Integer. In the general formula (1), R¹: H or carbon number 6 to
18 alkyl groups, R ^Two: An alkyl group having 1 to 6 carbon atoms,
R^Three: An alkyl group having 1 to 6 carbon atoms, A: having 2 to 4 carbon atoms
Alkylene group, B: H, SO_ThreeNH_FourOr SO_ThreeN
a and m are preferably integers of 1 to 100.

Hereinafter, the reactive emulsifier of the present invention will be described in detail. The reactivity in the present invention means that it can be bonded to various materials, particularly inorganic materials, by an alkoxysilyl group or a silanol group. Alkoxysilane compound (A)
Has a lipophilic portion and a hydrophilic portion and thus acts as an emulsifier.

The alkoxysilane compound (A) is relatively stable because it is difficult to hydrolyze and polycondensate, particularly, polycondensate an alkoxysilyl group in water.
Alternatively, even those obtained by polycondensation have surface activity and act as an emulsifier. However, if the polycondensation proceeds and no alkoxysilyl group or silanol group is present, no reactivity is exhibited.

The hydrolyzate of the alkoxysilane compound (A) and its polycondensate can be obtained by hydrolyzing and polycondensing the alkoxysilane compound (A) by a conventionally known method. For example, the reaction is carried out without a solvent or in an organic solvent capable of dissolving the alkoxysilane compound (A) and water. Examples of the organic solvent include alcohols, ketones, ethers, and cellolobs. The amount of water is not particularly limited. However, if the amount of water is too large, the resulting polycondensate becomes a high molecular weight substance, so that the action as an emulsifier may decrease. In the polycondensation, a conventionally known acid catalyst or base catalyst may be used.

For the above reasons, the molecular weight of the polycondensate is preferably such that the number average molecular weight is 20,000 or less, more preferably 10,000 or less, and even more preferably 5,000 or less. When the reactive emulsifier of the present invention is used for an inorganic material, the water resistance is improved. When a reactive emulsifier is used in an aqueous composition containing an organosilicon compound or an organosilicon resin,
Durability is improved while maintaining high emulsion stability, stability over time, water repellency and water absorption prevention.

The alkoxysilane compound (A) contained in the reactive emulsifier of the present invention is represented by the general formula (1), wherein R ^{1 is} H or an alkyl group having 6 to 18 carbon atoms, and R ^{2 is} 1 to 6 carbon atoms.
R ³ : an alkyl group having 1 to 6 carbon atoms, A:
An alkylene group having 2 to 4 carbon atoms, B: H, SO ₃ NH ₄ or SO ₃ Na, and m: an integer of 1 to 100 increases the hydrophobicity and hydrolyzability of the alkoxysilane compound (A). When the reactive emulsifier of the present invention is used for an inorganic material, the water resistance is further improved. Further, when used in an aqueous composition containing an organosilicon compound or an organosilicon resin, durability is further improved while maintaining all of emulsification stability, aging stability, water repellency and water absorption prevention properties higher.

The reactive emulsifier of the present invention is useful as an additive for various emulsions, paints and coatings.
Especially when the material is used for a material made of inorganic material,
Since the reactive emulsifier of the present invention is bonded and fixed to the material, bleeding of the emulsifier is suppressed, and the water resistance is improved.
When used in the aqueous composition described below, it is particularly useful.

******** Aqueous Composition The aqueous composition of the present invention comprises the following (a), (b) and (c).

(A) An organosilicon component comprising at least one selected from the group consisting of a silane compound (S) represented by the general formula (2), a hydrolyzate thereof and a polycondensate thereof.

[0054]

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(However, R ⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ is an alkyl group having 1 to 6 carbon atoms, and 1 is 1 or 2.) (b) The reactive emulsifier. (C) water. The organic silicon component is 1 to the entire aqueous composition.
60 wt%, and the content of the reactive emulsifier is preferably 0.01 to 20 wt% with respect to the organosilicon component.

R ⁴ is at least one selected from the group consisting of a saturated alkyl group having 4 to 18 carbon atoms, an aryl group, and an aralkyl group; R ⁵ is a methyl group or an ethyl group;
It is preferable that l is 1. Hereinafter, the aqueous composition of the present invention will be described in detail. The organosilicon component has water repellency and water absorption prevention properties, and binds to various materials, especially inorganic materials, or hydrolyzes / polycondenses itself to form a water repellent layer or a water absorption prevention layer on the material. It is a component that can be.

In the general formula (2), R ⁴ is a group exhibiting water repellency and water absorption preventing property, and is not particularly limited as long as it is a monovalent hydrocarbon group having 1 to 20 carbon atoms. And at least one selected from aralkyl groups, and these groups having 4 to 18 carbon atoms are even more preferable in that water repellency, water absorption prevention, filtration salt resistance and alkali resistance are remarkably improved. Among them, a saturated alkyl group having 4 to 18 carbon atoms is most preferable in terms of excellent weather resistance. If R ⁴ is plural, a plurality of R ⁴ may be the same as each other or may be different.

Specific examples of R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
A saturated alkyl group such as an isobutyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group; an aralkyl group such as a phenyl group and an aryl group such as a naphthyl group and a benzyl group; a vinyl group and a hexenyl group;
An alkenyl group such as an octenyl group is exemplified.

In the general formula (2), R ⁵ is a group capable of binding to various materials, particularly inorganic materials, or hydrolyzing / polycondensing by itself, and is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. There is no particular limitation as long as the alkyl group has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, and a hexyl group. Among them, a methyl group or an ethyl group is preferred because of high hydrolysis / polycondensability, and an ethyl group is most preferred. Hydrolysis and polycondensation properties of methyl groups are too high, so that the aqueous composition of the present invention thickens with time.
There may be a problem in storage stability such as gelation. Further, a plurality of R ⁵ may be the same or different. l is 1 or 2, and is preferably 1 in that it can contain many hydrolyzable / polycondensable functional groups.

Specific examples of the silane compound (S) include methyltrimethoxysilane, methyltriethoxysilane,
Methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-butyltrimethoxysilane, n- Butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, Tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane,
Octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dibutyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxy Examples include silane, diphenylsilanediol, vinyltrimethoxysilane, hexenyltrimethoxysilane, and octenyltrimethoxysilane. One or more of these silane compounds (S) may be used.

In the general formula (2), R ⁴ has 4 to 4 carbon atoms.
At least one selected from the group consisting of 18 saturated alkyl groups, aryl groups, and aralkyl groups, a trialkoxysilane compound in which R ⁵ is a methyl group or an ethyl group, and 1 is 1 is preferable. In particular, in the general formula (2), R ⁴ has 4 to 1 carbon atoms.
Further preferred is a trialkoxysilane compound wherein the saturated alkyl group is 8, R ⁵ is an ethyl group, and 1 is 1. this is,
This is because the aqueous composition can contain a large amount of hydrolyzable / polycondensable functional groups and is excellent in water repellency, water absorption prevention properties, salt barrier properties, alkali resistance and weather resistance.

The hydrolyzate of the silane compound (S) and its polycondensate can be obtained by the same method as the hydrolyzate of the alkoxysilane compound (A) and its polycondensate. When the aqueous composition of the present invention is used as a water-absorbing inhibitor for civil engineering building materials, it may have poor permeability to civil engineering building materials, so the number average molecular weight of the organosilicon component is preferably 5,000 or less, More preferably, 20
00 or less, more preferably 1000 or less.

The reactive emulsifier emulsifies the organosilicon component in water and can bind to various materials, especially inorganic materials. In particular, when the aqueous composition of the present invention containing a reactive emulsifier is used as a water-absorbing agent for civil engineering building materials, the permeability to civil engineering building materials is reduced by the conventionally disclosed organosilicon compounds and organosilicon resins. Compared to the aqueous emulsion of the above, the degree of reduction in water absorption prevention and water repellency with time is small, and the durability is excellent.

The amount of the organosilicon component is 1 to 60% by weight, preferably 5 to 50% by weight, based on the whole aqueous composition.
t%, and more preferably 10 to 40% by weight. If the amount of the organosilicon component is too small, it is necessary to apply 1
The number of times of application may be insufficient in one application, and the number of application must be increased. On the other hand, if it is too large, the viscosity tends to be high and the permeability to the material tends to be poor, or the emulsified state may be a water-in-oil type.

The reactive emulsifier is used in an amount of 0.01 to 20% by weight, preferably 0.02% by weight, based on the organosilicon component.
1 to 10% by weight, more preferably 0.03 to 5%.
wt%, most preferably 0.05 wt% or more,
The range is less than 0.5 wt%. When the amount of the reactive emulsifier in the aqueous composition of the present invention is too small, the emulsification of the organosilicon component becomes insufficient, and the emulsion stability or stability over time may be reduced. May decrease or durability may be poor.

Although the aqueous composition of the present invention does not contain a usual emulsifier and the like, the emulsion stability and the stability with time are sufficiently satisfactory. May be increased. As a normal emulsifier, any of a nonionic emulsifier, an anionic emulsifier, and a cationic emulsifier can be used, but a nonionic emulsifier is preferable because emulsification stability and temporal stability can be particularly improved.

The nonionic emulsifier is not particularly limited, and a conventionally known nonionic emulsifier can be used. Specific examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene Fatty acid esters, dimethylsiloxane copolymers in which the side chains and terminals of dimethylsiloxane are organized with polyalkylene oxide, and celluloses are exemplified. One or more of these nonionic emulsifiers may be used.
The compounding amount of these ordinary emulsifiers is 40% by weight or less, and preferably 30% by weight or less based on the reactive emulsifier.

When the pH of the aqueous composition of the present invention is from 3 to 12, the stability over time is excellent. Preferably it is 4-10, More preferably, it is 5-9. Further, in the aqueous composition of the present invention, a conventionally known emulsifier, a thickener, a pH buffer, a silica sol, an alumina sol, ceria sol, an ultraviolet absorber, a water-soluble polymer, and an organic emulsion polymer may be added. It is not limited to these. In the aqueous composition of the present invention, additives such as a fungicide, an antialgal agent, and a termite may be mixed, but the invention is not limited thereto.

The method of emulsifying the organosilicon component in water using a reactive emulsifier in order to obtain the aqueous composition of the present invention is not particularly limited, and a general mixing or emulsifying method is used. For example, while stirring at high speed with a stirrer, a homomixer, an ultra disperser, a high-pressure homogenizer, or the like, a liquid obtained by separately or mixing an organic silicon component and a reactive emulsifier is added little by little to water, or a mixture of a reactive emulsifier and water is added. An aqueous composition can be obtained by adding the organosilicon component to the liquid little by little, or vice versa.

The aqueous composition of the present invention is suitably used as a water absorption inhibitor for civil engineering and building materials. Although it is not particularly limited as a civil engineering building material, exposed concrete, precast concrete, lightweight cellular concrete (ALC), lightweight concrete, cement board, extruded cement board, asbestos cement board, pulp cement board, wood wool cement board, glass fiber cement Board, cement board with carbon fiber,
Mortar, joint mortar, gypsum board, gypsum plaster, dolomite plaster, hardboard, calcium silicate board, plaster, block, brick, tile, tile, tile, slate, natural stone, artificial stone, glass wool, rock wool, ceramic fiber, wood, plywood Is mentioned.

The method used for the civil engineering building material is not particularly limited, but a preferred method used is, for example, application to the above-mentioned material using a roller, brush, spray, etc., or impregnation or immersion of the above-mentioned material in some cases. It is mentioned. At this time, in the aqueous composition of the present invention, the amount of the organosilicon component is preferably 3 to the entire aqueous composition.
It is used after being diluted with water to a range of -50 wt%, more preferably 10-40 wt%. If the amount of the organosilicon component is too small, it is necessary to increase the number of times of application, impregnation, immersion, etc., and if it is too large, the permeability to the material is deteriorated. Further, as another preferable example used for the civil engineering building material, for example, addition at the time of producing the above-mentioned material can be mentioned. For example, in mortar, cement, sand, water and the like are mixed and prepared after adding the aqueous composition of the present invention, or in concrete, cement, fine aggregate, water reducing material, water and the like are kneaded. Molding is performed after adding the aqueous composition of the invention, and other materials may be added before molding or during molding in the same manner.

The aqueous composition of the present invention further comprises
Form a strong and excellent water absorption and water repellent layer on the surface and inside of the material by polycondensation reaction, deteriorate the material by rainwater, sewage, acid rain, infiltrate dirt, damage by sea (salt) water, cold area It is useful for solving cracks caused by freezing and thawing action, and efflorescence due to elution of salt from the material. Since it also has a function of releasing water vapor, it is excellent in neutralization by carbon dioxide gas, prevention of alkali-aggregate reaction by silica and alkali contained in the aggregate, and the like. Further, since the water absorption preventing layer and the water repellent layer are thick and have good permeability of the aqueous composition of the present invention, the durability can be improved. Further, it is useful as a waterproof primer for various paints, coating agents and finishing materials.

[0073]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. However, the present invention is not limited to the following Examples. "%"
Represents "wt%" unless otherwise specified. Example 1 30 g of polyoxyethylene allyl glycidyl nonyl phenyl ether having oxyethylene having 10 repeating units, 9.5 g of trimethoxysilane, 0.1 g
5 wt% chloroplatinic acid in isopropyl alcohol solution
2 g were mixed and heated at 80 ° C. for 10 hours to perform a hydrosilylation reaction. Next, unreacted trimethoxysilane and isopropyl alcohol were removed by distillation under reduced pressure with heating to produce polyoxyethylene trimethoxysilylpropyl glycidyl nonyl phenyl ether (A-1) having 10 oxyethylene repeating units. .

When the product after distillation was analyzed by gas chromatography, only trace amounts of trimethoxysilane and isopropyl alcohol were detected. Also, (A
The results of H-NMR analysis (internal standard: TMS, solvent: CDCl ₃ ), IR analysis and elemental analysis of -1) are shown below. From the 1 H-NMR analysis, the spectrum of the proton assigned to the allyl group of polyoxyethylene allyl glycidyl nonyl phenyl ether (5.1 to 5.3 in δ value)
ppm, 5.8 to 6.0 ppm) was confirmed to have disappeared.

H-NMR analysis results

[0076]

Embedded image

0.4 to 1.8 ppm 23H 6.7 to 7.3 ppm 4H 3.6 to 4.0 ppm 48H 3.55 to 3.6 ppm 9H (above δ
Value) IR analysis result -CH ₃ , -CH _2- : 2800 to 3000 cm ^{-1 -OH: 3200~3600cm -1 -Si-O-:} 1000~1100cm -1 -C-O-C-: 1100~1150cm -1 elemental analysis C: 58.8% (theoretical 58.9%) H : 9.3% (theoretical value: 9.4%) 0: 28.5% (theoretical value: 28.6%) Si: 3.4% (theoretical value: 3.1%) [Example 2] In Example 1, , Polyoxyethylene allyl glycidyl nonyl phenyl ether having 10 oxyethylene repeating units (hereinafter referred to as "X component")
Polyoxyethylene allyl glycidyl nonyl phenyl ether and triethoxy silane having an average number of repeating units of oxyethylene of 7.5 instead of trimethoxysilane (hereinafter abbreviated as “component Y”) and trimethoxysilane. A polyoxyethylene triethoxysilylpropyl glycidyl nonyl phenyl ether (A-2) having an average number of repeating units of oxyethylene of 7.5 was produced in the same manner as in Example 1 except for using the same. When the product after distillation was analyzed by gas chromatography, only traces of triethoxysilane and isopropyl alcohol were detected. Also, H-NMR of (A-2)
The results of analysis, IR analysis and elemental analysis are shown below. H
From the NMR analysis, it was confirmed that the allyl group of the raw material had disappeared in the same manner as in Example 1.

H-NMR analysis results

[0079]

Embedded image

0.4 to 1.8 ppm 32H 6.7 to 7.3 ppm 4H 3.6 to 4.0 ppm 44H (above δ
Value) IR analysis result -CH ₃ , -CH _2- : 2800 to 3000 cm ^{-1 -OH: 3200~3600cm -1 -Si-O-:} 1000~1100cm -1 -C-O-C-: 1100~1150cm -1 elemental analysis C: 60.7% (theoretical 60.9%) H : 9.9% (theoretical value: 9.7%) 0: 25.9% (theoretical value: 26.0%) Si: 3.5% (theoretical value: 3.4%) [Example 3] In Example 1, In the same manner as in Example 1 except that, instead of the X component, a polyoxyethylene allyl glycidyl nonyl phenyl ether in which the number of repeating units of oxyethylene is 5, and diethoxymethylsilane was used instead of the Y component, Polyoxyethylene diethoxymethylsilylpropyl glycidyl nonyl phenyl ether (A-3) having 5 oxyethylene repeating units was produced. When the product after distillation was analyzed by gas chromatography, only traces of diethoxymethylsilane and isopropyl alcohol were detected. The results of H-NMR analysis, IR analysis, and elemental analysis of (A-3) are shown below. From H-NMR analysis,
It was confirmed in the same manner as in Example 1 that the allyl group of the raw material had disappeared.

H-NMR analysis results

[0082]

Embedded image

0.4 to 1.8 ppm 29H 6.7 to 7.3 ppm 4H 3.6 to 4.0 ppm 32H 0 to 0.2 ppm 3H (above δ
Value) IR analysis result -CH ₃ , -CH _2- : 2800 to 3000 cm ^{-1 -OH: 3200~3600cm -1 -Si-O-:} 1000~1100cm -1 -C-O-C-: 1100~1150cm -1 Si-CH 3: 1200~1300cm -1 elemental analysis C: 63.0 % (Theoretical value 62.8%) H: 9.8% (theoretical value 9.9%) 0: 22.9% (theoretical value 23.2%) Si: 4.3% (theoretical value 4.1%) Example 4 Example 1 was repeated except that the X component was replaced by a polyoxyethylene allyl glycidyl nonyl phenyl ether having 20 oxyethylene repeating units and the Y component was replaced by dimethoxymethylsilane. In the same manner as in Example 1, polyoxyethylene dimethoxymethylsilylpropyl glycidyl nonylphenyl ether having 20 oxyethylene repeating units (A-4) It was prepared. When the product after distillation was analyzed by gas chromatography, only traces of dimethoxymethylsilane and isopropyl alcohol were detected. The results of H-NMR analysis, IR analysis, and elemental analysis of (A-4) are shown below. From H-NMR analysis, it was confirmed that the allyl group of the raw material had disappeared in the same manner as in Example 1.

H-NMR analysis results

[0085]

Embedded image

0.4 to 1.8 ppm 23H 6.7 to 7.3 ppm 4H 3.6 to 4.0 ppm 88H 0 to 0.2 ppm 3H 3.55 to 3.6 ppm 6H (δ
Value) IR analysis result -CH ₃ , -CH _2- : 2800 to 3000 cm ^{-1 -OH: 3200~3600cm -1 -Si-O-:} 1000~1100cm -1 -C-O-C-: 1100~1150cm -1 Si-CH 3: 1200~1300cm -1 elemental analysis C: 57.9 % (Theoretical value 58.2%) H: 9.6% (theoretical value 9.4%) 0: 30.5% (theoretical value 30.3%) Si: 2.3% (theoretical value 2.1%) [Examples 5 to 10] Alkoxysilane compounds (A-5) to (A-5) to (A-5) in the same manner as in Example 1 except that the X component and the Y component in Example 1 were respectively replaced with olefins and hydrosilanes shown in Table 1. A-10) was produced. For the alkoxysilane compounds (A-5) to (A-10), gas chromatography analysis, H-NMR analysis, IR analysis, and elemental analysis were performed in the same manner as in Example 1. In the gas chromatography analysis of the product after distillation, only traces of the starting materials hydrosilane and isopropyl alcohol were detected in any of the examples. From H-NMR analysis, it was confirmed that the allyl group of the raw material had disappeared in the same manner as in Example 1. Further, in each of the examples, it was confirmed from the H-NMR analysis, IR analysis and elemental analysis of the product that the alkoxysilane compounds shown in Table 1 were obtained.

Further, in Example 10, the quantitative determination of sulfur was confirmed by performing ion chromatography analysis.

[0088]

[Table 1]

The chemical formulas of the alkoxysilane compounds (A-5) to (A-10) obtained in Examples 5 to 10 are shown below.

[0090]

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[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

Example 11 10 g of the polyoxyethylene trimethoxysilylpropyl glycidyl nonyl phenyl ether (A-1) having 10 repeating units of oxyethylene obtained in Example 1 was mixed with 85 g of isopropyl alcohol and 2 g of water. The resulting mixture was heated and refluxed for 10 hours to carry out hydrolysis and polycondensation of (A-1). After cooling, isopropyl alcohol and water were distilled off under reduced pressure by heating under reduced pressure, and the hydrolysis-polycondensate (A-1) of (A-1) was removed.
1) was manufactured. When (A-11) was analyzed by gel permeation chromatography (GPC analysis), its number average molecular weight was 1,800. Example 12 A mixture of 0.80 g of (A-1) obtained in Example 1 as a reactive emulsifier and 80 g of isobutyltrimethoxysilane as a silane compound (S) was stirred at high speed using a homogenizer. While water 119.
20 g was gradually dropped and mixed to emulsify. The aqueous composition (1) (milky white emulsion) was produced by continuing high-speed stirring for 1 hour.

The aqueous composition (1) was heated at 50 ° C. for 24 hours.
Even after storage for a long time, no thickening gelation or the like occurred. Table 3 shows the results of evaluating the water absorption preventing property, the permeability, the emulsion stability, and the durability of the aqueous composition (1). The evaluation method is as follows. (Preparation of mortar sample) Coating solution obtained by diluting the aqueous composition with pure water so that the concentration of silane compound (S) becomes 30 wt% based on the total amount of silane compound (S), reactive emulsifier, and water And Mortar (5cm × 5cm × 1.5
cm) was applied at 300 g / m ^2, and then cured at 23 ° C. and 60% RH for 1 week to prepare a mortar sample, which was subjected to the following various tests. (Water absorption prevention property) A mortar sample was immersed in 200 g of water, taken out after 7 hours, and excess water was wiped off with a dry cloth, then weighed, and the water absorption was calculated by the following equation.

Water absorption (wt%) = [(weight after immersion−weight before immersion) / weight before immersion] × 100 The evaluation criteria are as follows. ◎: Water absorption rate of less than 0.5 wt% ：: Water absorption rate of 0.5 wt% to less than 1.0 wt% Δ: Water absorption rate of 1.0 wt% to less than 2.0 wt% ×: Water absorption rate of 2.0 wt% or more In addition, when the water absorption of the untreated mortar was measured similarly, it was 7.5 wt%. (Permeability) A mortar sample was cut, water was sprayed on its cross section, and the penetration depth was measured based on the thickness of the water-repellent layer. The evaluation criteria are as follows.

◎: 3 mm or more ２: 2 mm or more and less than 3 mm Δ: 1 mm or more and less than 2 mm ×: less than 1 mm (emulsion stability) The obtained composition was allowed to stand at room temperature, and the presence or absence of two-layer separation was observed. The evaluation criteria are as follows.

◎: No separation of two layers for 24 hours or more ○: No separation of two layers for more than 7 hours, but separation of two layers by 24 hours △: No separation of two layers for more than 1 hour, but two layers by 7 hours Separation ×: Separation into two layers in less than 1 hour (Durability) The mortar sample was irradiated with ultraviolet rays for 1000 hours using a sunshine weather meter type accelerated weathering tester to evaluate the water absorption preventing property. The evaluation criterion is the same as (water absorption prevention). [Examples 13 to 18] The procedure of Example 12 was repeated except that the type and amount of the alkoxysilane compound (A), the type and amount of the silane compound (S), and the amount of water were shown in Table 2. Thus, aqueous compositions (2) to (7) (milky white emulsion) were produced. Aqueous composition (2)-
About (7), similarly to the aqueous composition (1), anti-water absorption property, permeability, emulsion stability, and durability were evaluated. Table 3 shows the evaluation results.

The aqueous compositions (2) to (7) were mixed with 50
Even after storage at 24 ° C. for 24 hours, no thickening gelation or the like occurred.

[0102]

[Table 2]

Example 19 248 g (1.0 mol) of hexyltriethoxysilane, 200 g of ethanol, 1 part of water
2.6 g (0.7 mol) and hydrochloric acid cation exchange resin, Amberlyst 15 (manufactured by Rohm & Haas)
8 g were mixed and heated under reflux for 2 hours to carry out polycondensation of hexyltriethoxysilane. Next, ethanol was distilled off under reduced pressure while heating. After cooling, Amberlyst 15 was removed by filtration to obtain a hydrolysis / polycondensate of hexyltriethoxysilane. The number average molecular weight of this hydrolysis / polycondensate was 800.

Next, 60 g of the hydrolysis / polycondensate, 0.20 g of (A-3) obtained in Example 3 and Example 1
While stirring a liquid obtained by mixing 0.40 g of (A-10) obtained in Example 1 with an ultra disperser, water 1
39.40 g was gradually added and mixed to emulsify. The high-speed stirring was continued for 1 hour to produce an aqueous composition (8) (milky white emulsion). As for the aqueous composition (8), as in the case of the aqueous composition (1), water absorption prevention, permeability,
Emulsion stability and durability were evaluated. Table 3 shows the evaluation results.

The aqueous composition (8) was heated at 50 ° C. for 24 hours.
Even after storage for a long time, no thickening gelation or the like occurred.

[0106]

[Table 3]

[Comparative Example 1] In Example 15, (A-
A comparative aqueous composition (1) was prepared in the same manner as in Example 15 except that sorbitan monolaurate was used instead of 1).
1) (milky white emulsion) was obtained. For the comparative aqueous composition (11), similarly to the aqueous composition (1), the water absorption preventing property, the permeability, the emulsion stability and the durability were evaluated. Table 4 shows the evaluation results. Comparative Example 2 A comparative aqueous composition (12) was prepared in the same manner as in Example 15 except that 1.2 g of sorbitan monolaurate was used instead of (A-1).
(Milky white emulsion) was obtained. Comparative aqueous composition (1
About 2), similarly to the aqueous composition (1), the water absorption prevention property, the permeability, the emulsion stability, and the durability were evaluated. Table 4 shows the evaluation results. [Comparative Example 3] Comparative aqueous composition (13) (milky white emulsion) in the same manner as in Example 1 except that the following compound (T) was used instead of (A-1).
I got About the comparative aqueous composition (13), similarly to the aqueous composition (1), the water absorption prevention property, the permeability, the emulsion stability, and the durability were evaluated. Table 4 shows the evaluation results.

[0108]

Embedded image

This comparative aqueous composition (13) was treated with 5
When stored at 0 ° C. for 24 hours, two layers were separated, and the upper layer was gelled.

[0110]

[Table 4]

[0111]

As described above, the reactive emulsifier of the present invention contains at least one selected from the group consisting of an alkoxysilane compound (A), a hydrolyzate thereof and a polycondensate thereof. When is used as an inorganic material, water resistance is improved. In addition, when a reactive emulsifier is used in an aqueous composition containing an organosilicon compound or an organosilicon resin, durability is improved while maintaining high emulsification stability, stability over time, water repellency and water absorption prevention properties. .

The alkoxysilane compound (A) contained in the reactive emulsifier of the present invention is represented by the formula (1), wherein R ^{1 is} H or an alkyl group having 6 to 18 carbon atoms, and R ^{2 is} 1 to 6 carbon atoms.
R ³ : an alkyl group having 1 to 6 carbon atoms, A:
An alkylene group having 2 to 4 carbon atoms, B: H, SO ₃ NH ₄ or SO ₃ Na, and m: an integer of 1 to 100 increases the hydrophobicity and hydrolyzability of the alkoxysilane compound (A). When the reactive emulsifier of the present invention is used for an inorganic material, the water resistance is further improved. Further, when used in an aqueous composition containing an organosilicon compound or an organosilicon resin, durability is further improved while maintaining all of emulsification stability, aging stability, water repellency and water absorption prevention properties higher.

The aqueous composition of the present invention exhibits high performance in all of emulsion stability, stability over time, water repellency and water absorption prevention, and has high durability. The amount of the organosilicon component is 1 to 60% by weight based on the whole aqueous composition, and the amount of the reactive emulsifier is 0.01 to
When the content is 20% by weight, the permeability to the material is good, the emulsion stability, the stability over time, the water repellency and the water absorption preventing property are improved, and the durability is further increased.

In the silane compound (S) represented by the general formula (2), R ⁴ is at least one selected from the group consisting of a saturated alkyl group having 4 to 18 carbon atoms, an aryl group and an aralkyl group, and R ⁵ is methyl. When the group or the ethyl group, l, is 1, the aqueous composition also has excellent salt barrier properties, alkali resistance and weather resistance. The alkoxysilane compound (A) of the present invention is a novel compound having surface activity. For example, by using this alkoxysilane compound, in an aqueous composition containing an organosilicon compound or an organosilicon resin, durability is improved while maintaining high emulsification stability, stability over time, water repellency and water absorption prevention properties. can do.

[0115] Aqueous compositions comprising A alkoxysilane compound (A), improves the bonding between the inorganic material, with both the emulsion stability and temporal stability and water repellency and water absorption preventing property increases, durability Also improve.

According to the method for producing an alkoxysilane compound (A) of the present invention, an alkoxysilane compound (A) which is a novel compound having surface activity can be produced easily and with good reproducibility.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B01F 17/54 B01F 17/54 C08G 77/14 C08G 77/14 77/46 77/46 // C09K 3/18 104 C09K 3 / 18 104

Claims (8)

(57) [Claims] 1. A reactive emulsifier comprising at least one selected from the group consisting of an alkoxysilane compound (A) represented by the following general formula (1), a hydrolyzate thereof and a polycondensate thereof. Embedded image R ¹ : H, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms R ² : a hydrocarbon group having 1 to 10 carbon atoms R ³ : an alkyl group having 1 to 10 carbon atoms which may be substituted A: carbon atom An alkylene group which may be substituted in the formulas 2 to 4 B: H, SO ₃ NH ₄ , SO ₃ Na, CO ₂ NH ₄ or CO ₂ Nam: an integer of 1 to 200 n: an integer of 0 to 2 2. In the above general formula (1), R ¹ : H or an alkyl group having 6 to 18 carbon atoms R ² : an alkyl group having 1 to 6 carbon atoms R ³ : an alkyl group having 1 to 6 carbon atoms A: alkylene group having 2 to 4 carbon atoms B: H, SO ₃ NH ₄ or SO ₃ Na m: an integer of 1 to 100, the reactive emulsifier according to claim 1. 3. An aqueous composition comprising the following (a), (b) and (c). (A) An organosilicon component comprising at least one selected from a silane compound (S) represented by the general formula (2), a hydrolyzate thereof and a polycondensate thereof. Embedded image (However, R ⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵
Is an alkyl group having 1 to 6 carbon atoms, and 1 is 1 or 2. (B) The reactive emulsifier according to claim 1 or 2. (C) water. 4. The composition according to claim 3, wherein the content of the organosilicon component is 1 to 60% by weight based on the whole aqueous composition, and the content of the reactive emulsifier is 0.01 to 20% by weight based on the weight of the organosilicon component. An aqueous composition as described. 5. The method according to claim 1, wherein R ⁴ is at least one selected from the group consisting of a saturated alkyl group having 4 to 18 carbon atoms, an aryl group, and an aralkyl group, wherein R ⁵ is a methyl group or an ethyl group,
The aqueous composition according to claim 3, wherein 1 is 1. 6. An alkoxysilane compound (A) represented by the following general formula (1). Embedded image However, R ^1: H or an alkyl group R ² having 6 to 18 carbon atoms: alkyl groups R ³ carbon atoms 1-6: alkyl group having a carbon number 1 to 6 A: C2-4 A alkylene group B: _{H, SO 3 NH 4, SO} 3 Na, CO 2 NH 4 or CO ₂ Na m: 1~200 integer n: 0 to 2 integer 7. The alkoxysilane compound (A) according to claim 6, wherein in the general formula (1) , B : H, SO ₃ NH ₄ or SO ₃ Nam: an integer of 1 to 100. 8. A compound (B) represented by the following general formula (3) and a compound (C) represented by the following general formula (4)
A method for producing an alkoxysilane compound (A), wherein the compound is subjected to a humanosilylation reaction using Embedded image (However, R ^{1 is} H, a halogen atom or a carbon number of 1 to 20)
A: an alkylene group having 2 to 4 carbon atoms which may be substituted, B: H, SO ₃ NH ₄ , SO ₃ Na, CO ₂
NH ₄ or CO ₂ Na, m: an integer of 1 to 200. ) (However, R ² : a hydrocarbon group having 1 to 10 carbon atoms, R ³ : an alkyl group having 1 to 10 carbon atoms which may be substituted, n: 0 to 2
Is an integer. )