JP4336974B2 - Water-based water repellent treatment agent and water repellent treatment method - Google Patents

Description

  The present invention improves the prevention of dimensional changes due to water (ink, etc.) and the printing characteristics of paper and the like by processing on materials such as materials derived from lignocellulose such as paper, fibers, bricks, and wood. Further, the present invention relates to a water-based water-repellent treatment method and a water-repellent treatment method capable of imparting high water repellency to lignocellulose-derived materials such as fibers and wood.

  Conventionally, as a method for imparting dimensional stability and water repellency to base materials, particularly paper products or textile products, and building materials such as wood and bricks, silicone-based, acrylic-based, urethane-based, ester-based, and oil-based A method is known in which a resin or monomer dissolved is applied and impregnated into a material and dried. Of these, silicone-based materials are often used, and solvent-diluted silicone-based water repellents dominate.

  However, the solvent-diluted type generally has a greater negative impact on the environment than the water-diluted type, and the development of a water repellent that does not use a solvent is also desired from the viewpoint of protecting the global environment and utilizing resources. In particular, development of a high-performance water-based water repellent is strongly desired.

  Recently, as water-based water repellents, long-term emulsification of alkyltrialkoxysilane in water in JP-A-1-2902089, JP-A-5-156164, and JP-A-5-221748 (Patent Documents 1 to 3). A stable emulsion is disclosed. However, because this emulsion uses alkoxysilane, which has a very slow hydrolysis reaction, when applied to the material, the impregnation is good, but silane volatilization occurs on the surface of the material, and the surface water repellency is lost. There are problems such as wetness, adhesion of dirt, pop-up due to frost damage, and other disadvantages in terms of durability and a milky white appearance.

  On the other hand, those of the uniform aqueous solution type other than the emulsion type as described above are disclosed in JP-A Nos. 61-162553, 4-249588, and 10-81752 (Patent Documents 4 to 6). It is disclosed.

  However, the composition of the above-mentioned Japanese Patent Application Laid-Open No. 61-162553 (Patent Document 4), when diluted with water, the polymerization reaction proceeds rapidly, so that the storage stability is poor and must be used within 1 day after dilution. It cannot withstand actual use. Furthermore, since the polymerization reaction is fast, the molecular weight becomes large and the impregnation property into the material is deteriorated. As a result, there is a drawback that wetting spots are generated on the surface of the material.

  Further, the composition of JP-A-4-249588 (Patent Document 5) is composed of a water-soluble amino group-containing coupling agent and a short alkyltrialkoxysilane having a carbon chain, and is excellent in storage stability. The water repellent component has a disadvantage that it is poor in water repellency because it has only a lower alkyl group. Furthermore, since the amino group-containing coupling agent component is more than the alkylalkoxysilane component (alkylalkoxysilane component / amino group-containing coupling agent component = 0.5 to 3/10 to 1 molar ratio), the wet color of the material There are also problems such as remaining, and yellowing of paper, textiles or wood.

  Furthermore, in Japanese Patent Application Laid-Open No. 2000-95868 (Patent Document 7), a short carbon chain alkyltri or dialkoxysilane and an amino group-containing alkoxysilane are first partially hydrolyzed, and further hydrolyzed by adding hydrolyzed water and acid. Finally, although a method for producing a composition in which a neutralizing agent is added is disclosed, the process is complicated in this method, and in the first step, an alkylalkoxysilane and an amino group-containing alkoxysilane are mixed, When performing the hydrolysis reaction, the hydrolysis speed of the amino group-containing alkoxysilane is generally faster than that of the alkylalkoxysilane, so that it is difficult to perform the cohydrolysis and the cohydrolyzate cannot be produced successfully. However, when this was processed into a neutral substrate or the like, there were problems such as poor water repellency.

  Japanese Patent Application Laid-Open No. 7-150131 (Patent Document 8) discloses a method of treating wood with a composition containing a salt of an organic or inorganic acid and a basic nitrogen-containing organopolysiloxane, a water repellent agent, and water. Although described, this composition has problems of insufficient water repellency and poor storage stability.

  JP-A-55-133466 and JP-A-55-133467 (Patent Documents 9 and 10) disclose alkyl alkoxysilanes, amino group-containing alkoxysilanes, epoxy group-containing alkoxysilanes, and metal / metalloid salts. A composition obtained by hydrolyzing water with water is disclosed. However, in this composition, the amino group is blocked by the reaction of the amino group and the epoxy group, so when treated on the base material, yellowing is reduced, but the water-solubility deteriorates, resulting in an aqueous treatment agent. There is a problem that can not be used as. Furthermore, since the adsorptivity to the substrate and the like is also deteriorated, there is a problem that this composition cannot be used as a treating agent for a substrate.

  In order to solve the above problems, the present inventors disclosed in JP-A-9-77780 (Patent Document 11) an alkylalkoxysilane having 7 to 18 carbon atoms, an alkoxy group-containing siloxane, an amino group-containing alkoxysilane, Although it has been proposed to be composed of a co-hydrolyzed product, water repellency may not be sufficient in spite of the use of a long-chain alkylsilane, and it may be treated on paper, textiles or wood. In some cases, yellowing may occur.

  Japanese Patent Laid-Open No. 10-81752 (Patent Document 6) proposes a binder composition that is stable in an alkaline region. However, since this proposal uses many amino group-containing alkoxysilanes, a group other than alkaline is proposed. As a treatment agent for the material, water repellency is still insufficient, and a wet color may remain in the material or yellowing may occur.

  Furthermore, in order to solve the above problems, in Japanese Patent Application Laid-Open Nos. 2002-241744 and 2002-348567 (Patent Documents 12 and 13), a siloxane oligomer and a small amount of an amino group-containing alkoxysilane were hydrolyzed. A water repellent treatment agent is proposed. This water-repellent treatment agent can absorb less water than untreated products when treated with highly water-absorbing wood (such as cedar sapwood or early-release radiata pine wood), but the annual rings are clogged. In some cases, the performance is not as good as that of low water absorption wood such as conifers (Russian red pine, Russian larch, etc.).

  Therefore, a water-based water repellent agent having further satisfactory performance has been desired.

Japanese Patent Laid-Open No. 1-292089 JP-A-5-156164 JP-A-5-221748 JP 61-162553 A JP-A-4-249588 Japanese Patent Laid-Open No. 10-81752 JP 2000-95868 A JP-A-7-150131 JP-A-55-133466 JP-A-55-133467 Japanese Patent Laid-Open No. 9-77780 JP 2002-241744 A JP 2002-348567 A

  The present invention has been made in view of the above circumstances, has excellent water solubility and storage stability, good impregnation into a substrate, and excellent dimensional stability, water repellency, and water repellency durability imparting effect. Another object of the present invention is to provide a water-based water repellent treatment agent and a water repellent treatment method that can be produced at low cost.

As a result of intensive studies to achieve the above object, the present inventors have
(A) The following average composition formula (1)
(R ¹ ) _a (OR ² ) _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, a is 0.75 to 1.5, and b is 0.2 to 3) And a positive number satisfying 0.9 <a + b < 4.)
100 parts by mass of a siloxane oligomer having 2 to 10 silicon atoms represented by : (B) the following general formula (2)
R ³ R ⁴ NR ⁵ —SiR ⁶ _c (OR ² ) _3-c (2)
(In the formula, R ² is the same as above, R ³ and R ⁴ are the same or different hydrogen atoms, or an alkyl group or aminoalkyl group having 1 to 15 carbon atoms, and R ⁵ is the number of carbon atoms. 1 to 18 divalent hydrocarbon groups, R ⁶ is an alkyl group having 1 to 4 carbon atoms, and c is 0 or 1.)
An amino group-containing alkoxysilane or its partial hydrolyzate 0.5 to 49 parts by mass shown in, (D) the following general formula (3)
(R ¹ ) _3-n (OR ² ) _n Si—Y—Si (R ¹ ) _3-n (OR ² ) _n (3)
[In the formula, R ¹ and R ² are the same as above, Y is an alkylene group having 1 to 20 carbon atoms, or — (CH ₂ ) _a (CF ₂ ) _b (CH ₂ ) _c — (a is 1 to 6, b is 1 to 10, c is a fluorine atom-containing alkylene group represented by 1 to 6), also _{^{-R- (Si (R 7) 2}} O) m -Si (R 7) 2 -R- groups (Where R ⁷ is an alkyl group having 1 to 6 carbon atoms, R is a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is 1 to 30), and n is 1, 2 or 3. ]
A bis (alkoxysilyl) group-containing compound represented by the formula (1) or 0.1 to 20 parts by mass of a partial hydrolyzate thereof, and (C) 0.1 to 10 parts by mass of inorganic oxide fine particles as necessary . What was co-hydrolyzed and condensed in the presence, especially the organosilicon compound obtained by removing alcohol from the system and making it alcohol-free, has been surprisingly improved in water repellency and processed into wood with high water absorption It was found that even in this case, the water absorption rate can be kept low.

  That is, by adding a small amount of colloidal silica, fine irregularities can be formed on the treated surface, improving water repellency, and by adding a bis (alkoxysilyl) group-containing compound, both ends are reactive. Water repellency is improved because the organic group of the linking chain part gives more water repellency, and even if such additives are added, the uniformity when dissolved in water is not bad, just diluting with water at the time of use In addition, it has good storage stability after dilution with water, has good permeability to the base material, can improve water repellency and dimensional stability, and is an organic material such as paper, textiles, or wood Even when treated, the yellowing is kept low because of the small number of aminosilane-containing alkoxysilane components, that is, the substrate has good impregnation properties and excellent dimensional stability, water repellency and water repellency durability. Can be manufactured at low cost And finding that there were able to complete the present invention.

Therefore, the present invention
(A) The following formula (1)
(R ¹ ) _a (OR ² ) _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, a is 0.75 to 1.5, and b is 0.2 to 3) And a positive number satisfying 0.9 <a + b < 4.)
100 parts by mass of a siloxane oligomer having 2 to 10 silicon atoms represented by
(B) The following general formula (2)
R ³ R ⁴ NR ⁵ —SiR ⁶ _c (OR ² ) _3-c (2)
(In the formula, R ² is the same as above, R ³ and R ⁴ are the same or different hydrogen atoms, or an alkyl group or aminoalkyl group having 1 to 15 carbon atoms, and R ⁵ is the number of carbon atoms. 1 to 18 divalent hydrocarbon groups, R ⁶ is an alkyl group having 1 to 4 carbon atoms, and c is 0 or 1.)
0.5 to 49 parts by mass of an amino group-containing alkoxysilane or a partial hydrolyzate thereof represented by
(D) The following general formula (3)
(R ¹ ) _3-n (OR ² ) _n Si—Y—Si (R ¹ ) _3-n (OR ² ) _n (3)
[In the formula, R ¹ and R ² are the same as above, Y is an alkylene group having 1 to 20 carbon atoms, or — (CH ₂ ) _a (CF ₂ ) _b (CH ₂ ) _c — (a is 1 to 6, b is 1 to 10, c is a fluorine atom-containing alkylene group represented by 1 to 6), also _{^{-R- (Si (R 7) 2}} O) m -Si (R 7) 2 -R- groups (Where R ⁷ is an alkyl group having 1 to 6 carbon atoms, R is a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is 1 to 30), and n is 1, 2 or 3. ]
0.1 to 20 parts by mass of a bis (alkoxysilyl) group-containing compound or a partial hydrolyzate thereof represented by
A water-based repellent characterized by containing (C) 0.1 to 10 parts by mass of inorganic oxide fine particles co-hydrolyzed and condensed in the presence of an organic acid or an inorganic acid as an effective component for water repellent treatment. Provided is a water repellent treatment method comprising coating the water-based water repellent agent on the surface of a substrate containing therein a water treatment agent and a compound (F) containing boron.

  The water-based water repellent treatment agent of the present invention has excellent water solubility and storage stability, and can be used as a water repellent agent for wood, etc. by simply diluting in water, and has excellent water repellency and dimensional stability when applied or impregnated. Give sexual effects. In particular, even when treated with wood having a high water absorption rate, the water absorption rate can be kept low, which is particularly useful as a building material.

Hereinafter, the present invention will be described in more detail.
The component (A) for obtaining the water-based water repellent agent of the present invention is the following average composition formula (1)
(R ¹ ) _a (OR ² ) _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, a is 0.75 to 1.5, and b is 0.2 to 3) And a positive number satisfying 0.9 <a + b < 4.)
Is a siloxane oligomer having 2 to 10 silicon atoms .

R ¹ in the above formula (1) is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, and an n-hexyl group, and a methyl group is particularly preferable.

R ² is an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group, and a methyl group and an ethyl group are preferable.

  a and b are the positive numbers described above. When a + b = 4, the organosilicon compound of the formula (1) is silane.

Specific examples of such silanes include the following compounds.
CH ₃ Si (OCH ₃ ) ₃ , CH ₃ Si (OC ₂ H ₅ ) ₃ ,
CH ₃ Si (OCH (CH ₃ ) ₂ ) ₃ , CH ₃ CH ₂ Si (OCH ₃ ) ₃ ,
CH ₃ CH ₂ Si (OC ₂ H ₅ ) ₃ , CH ₃ CH ₂ Si (OCH (CH ₃ ) ₂ ) ₃ ,
C ₃ H ₇ Si (OCH ₃ ) ₃ , C ₃ H ₇ Si (OC ₂ H ₅ ) ₃ ,
C ₃ H ₇ Si (OCH (CH ₃ ) ₂ ) ₃ , C ₄ H ₉ Si (OCH ₃ ) ₃ ,
C ₄ H ₉ Si (OC ₂ H ₅ ) ₃ , C ₄ H ₉ Si (OCH (CH ₃ ) ₂ ) ₃ ,
C ₅ H ₁₁ Si (OCH ₃ ) ₃ , C ₅ H ₁₁ Si (OC ₂ H ₅ ) ₃ ,
C ₅ H ₁₁ Si (OCH (CH ₃ ) ₂ ) ₃ , C ₆ H ₁₃ Si (OCH ₃ ) ₃ ,
C ₆ H ₁₃ Si (OC ₂ H ₅ ) ₃ , C ₆ H ₁₃ Si (OCH (CH ₃ ) ₂ ) ₃

  The said silane may be used independently, 2 or more types of mixtures may be used, and the partial hydrolyzate of mixed silane may be used.

In this case, as the component (A), Ru with the silane alkoxy group-containing siloxanes (mixed silane mixture over the silane alone or two kinds) partial hydrolytic condensation. The number of silicon atoms in this partial hydrolyzate (siloxane oligomer) is preferably 2 to 10, particularly 2 to 4.

Furthermore, the siloxane, in formula (1), a is 0.75 to 1.5, b is 0.2 to 3, a + b is 0.9 <a + b <4, particularly 0.95 ≦ a + b <4 Particularly preferably, a is 0.8 to 1.2, b is 0.5 to 2.5, and a + b is 1.3 to 3.7.

  In addition, as (A) component, what is obtained by reaction of a C1-C6 alkyltrichlorosilane and methanol or ethanol in water may be used. Also in this case, the number of silicon atoms in the siloxane oligomer is preferably 2 to 6, particularly 2 to 4.

As the siloxane oligomer, a siloxane dimer represented by [CH ₃ (OR ² ) ₂ Si] ₂ O is particularly preferable. In this case, siloxane trimer or siloxane tetramer may be included.

Moreover, what has a viscosity of 300 mm < ² > / s or less at 25 degreeC is preferable, and what has a viscosity of 1-100 mm < ² > / s is especially suitable.

The component (B) of the present invention has the following general formula (2)
R ³ R ⁴ NR ⁵ —SiR ⁶ _c (OR ² ) _3-c (2)
(However, in the formula, R ² is the same as above, and R ³ and R ⁴ are the same or different from each other, or each having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. An alkyl group or an aminoalkyl group, R ⁵ is a divalent hydrocarbon group having 1 to 18, preferably 1 to 8, more preferably 3 carbon atoms, R ⁶ is an alkyl group having 1 to 4 carbon atoms, and c Is 0 or 1.)
Or an amino group-containing alkoxysilane or a partial hydrolyzate thereof.

Examples of R ³ and R ⁴ in the above formula (2) include a methyl group, an ethyl group, a propyl group, a butyl group, an aminomethyl group, an aminoethyl group, an aminopropyl group, and an aminobutyl group. Examples of R ⁵ include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of R ⁶ include a methyl group, an ethyl group, a propyl group, and a butyl group.

As a specific example of such an amino group-containing alkoxysilane of the above formula (2),
H ₂ N (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,
H ₂ N (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
H ₂ N (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ,
CH ₃ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
CH ₃ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ,
CH ₃ NH (CH ₂ ) ₅ Si (OCH ₃ ) ₃ ,
CH ₃ NH (CH ₂ ) ₅ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ,
CH ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
CH ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ,
C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ N (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ N (CH ₂ ) ₂ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
H ₂ N (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ N (CH ₂ ) ₃ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
CH ₃ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ ,
_{CH 3 NH (CH 2) 3} SiCH 3 (OCH 2 CH 3) 2,
CH ₃ NH (CH ₂ ) ₅ SiCH ₃ (OCH ₃ ) ₂ ,
CH ₃ NH (CH ₂ ) ₅ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ ,
_{H 2 N (CH 2) 2} NH (CH 2) 3 SiCH 3 (OCH 2 CH 3) 2,
CH ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ ,
_{CH 3 NH (CH 2) 2} NH (CH 2) 3 SiCH 3 (OCH 2 CH 3) 2,
C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ ,
_{C 4 H 9 NH (CH 2} ) 2 NH (CH 2) 3 SiCH 3 (OCH 2 CH 3) 2
Etc.

  Among these, in particular, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane or the like is preferably used.

  Component (C) of the present invention is inorganic oxide fine particles, and examples thereof include silicon oxide, titanium oxide, zinc oxide, aluminum oxide, and cerium oxide. When these inorganic oxide fine particles are used, it is preferable to use those dispersed in water or a solvent. From the viewpoint of cost and ease of use, colloidal silica in which silica fine particles are dispersed in water or alcohol. Is particularly preferred.

  Colloidal silica is a colloidal dispersion of fine silica particles in water or an alcohol solvent such as methanol, ethanol, isobutanol, diacetone alcohol, etc., for example, SNOWTEX O, SNOWTEX O-40, Snowtex OXS, Snowtex OS, Snowtex OL, Snowtex OUP, methanol silica sol, IPA-ST (manufactured by Nissan Chemical Industries, Ltd.) and the like.

  The average particle size of the inorganic oxide fine particles is preferably 1 to 200 nm, particularly preferably 5 to 100 nm. When the average particle diameter exceeds 200 nm, the substrate may be white or the water repellency may be deteriorated, and when it is less than 1 nm, the stability of the treatment agent may be deteriorated. The particle shape is not particularly limited, but is preferably spherical. The average particle diameter is a value obtained by a laser scattering diffraction measurement method.

The component (D) of the present invention is a bis (alkoxysilyl) group-containing compound represented by the following general formula (3) or a partial hydrolyzate thereof.
(R ¹ ) _3-n (OR ² ) _n Si—Y—Si (R ¹ ) _3-n (OR ² ) _n (3)
[In the formula, R ¹ and R ² are the same as above, Y is an alkylene group having 1 to 20 carbon atoms, or — (CH ₂ ) _a (CF ₂ ) _b (CH ₂ ) _c — (a is 1 to 6, b is 1 to 10, c is a fluorine atom-containing alkylene group represented by 1 to 6), also _{^{-R- (Si (R 7) 2}} O) m -Si (R 7) 2 -R- groups (Where R ⁷ is an alkyl group having 1 to 6 carbon atoms, R is a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is 1 to 30), and n is 1, 2 or 3. ]

R ^1, R ² in the formula (3) is the same as R ^1, R ² in the formula (1). Y represents an organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms (preferably an alkylene group or — (CH ₂ ) _a (CF ₂ ) _b (CH ₂ ) _c — (a 1 to 6, b is 1 to 10, fluorine atom-containing alkylene group c is represented by 1~6)), - (OSi ( R 7) 2) m O- group or -R- (Si (R ⁷⁾ ₂ O) _m —Si (R ⁷ ) ₂ —R— group (wherein R ⁷ is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Specifically, a methyl group, an ethyl group, Examples include an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, etc. A methyl group is particularly preferable, and R is a carbon atom having 1 to 6 carbon atoms, particularly 2 to 3 carbon atoms. (It is a divalent hydrocarbon group, particularly preferably an alkylene group. M is an integer of 1 to 30, particularly 5 to 20.)
Specifically, the following can be exemplified, but the invention is not limited thereto.

_{-CH 2 -, - CH 2 CH} 2 -, - CH 2 CH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 CH 2} -, - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -,
_{-CH 2 C 4 F 8 CH 2} -, - CH 2 C 6 F 12 CH 2 -,
_{- (OSi (CH 3) 2} ) 2 O -, - (OSi (CH 3) 2) 4 O-,
_{- (OSi (CH 3) 2} ) 6 O -, - (OSi (CH 3) 2) 8 O-,
_{-CH 2 CH 2 Si (CH 3} ) 2 OSi (CH 3) 2 CH 2 CH 2 -,
_{-CH 2 CH 2 (Si (CH} 3) 2 O) 3 Si (CH 3) 2 CH 2 CH 2 -,
_{-CH 2 CH 2 (Si (CH} 3) 2 O) 5 Si (CH 3) 2 CH 2 CH 2 -,
_{-CH 2 CH 2 (Si (CH} 3) 2 O) 7 Si (CH 3) 2 CH 2 CH 2 -,
_{-CH 2 CH 2 (Si (CH} 3) 2 O) 9 Si (CH 3) 2 CH 2 CH 2 -,
_{-CH 2 CH 2 (Si (CH} 3) 2 O) 19 Si (CH 3) 2 CH 2 CH 2 -,
_{-CH 2 CH 2 (Si (CH} 3) 2 O) 39 Si (CH 3) 2 CH 2 CH 2 -

  n is 1, 2 or 3, preferably 2 or 3, and n = 3 is particularly preferable for improving water repellency.

Specific examples of the bis (alkoxysilyl) group-containing compound satisfying these include the following.
(CH ₃ O) ₃ SiCH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₄ F ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₆ F ₁₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₈ F ₁₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₁₀ F ₂₀ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 4 F 8 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 6 F 12 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 8 F 16 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 10 F 20 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₂ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₄ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₆ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₈ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₁₀ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₃ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₅ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₇ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₉ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

Among these, preferably,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₄ F ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₆ F ₁₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₆ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₈ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₁₀ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₅ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₇ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₉ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
Etc.

  The use ratio of the components (A) to (D) is 0.5 to 49 parts, preferably 5 to 30 parts, of the component (B) with respect to 100 parts (parts by mass) of the component (A). When the component (B) is less than 0.5 part, the water solubility becomes weak, and the stability of the aqueous solution becomes poor. On the other hand, when the component (B) exceeds 49 parts, the water repellency and long-term water absorption preventive properties are deteriorated, or yellowing becomes severe when the substrate is processed.

  When (C) component is used, the compounding quantity is 0.1-10 parts with respect to 100 parts of (A) component, Preferably it is 0.5-5 parts. (C) If a component is less than 0.1 part, the expression of a water-repellent effect will become weak. Moreover, when (C) component exceeds 10 parts, it will become disadvantageous in cost or stability of a processing agent will worsen.

  Moreover, when using (D) component, the compounding quantity is 0.1-20 parts with respect to 100 parts of (A) component, Preferably it is 0.5-10 parts. (D) If a component is less than 0.1 part, the expression of a water-repellent effect will become weak. Moreover, when (D) component exceeds 20 parts, it will become disadvantageous in cost or the solubility to water will deteriorate.

  In terms of mole, (A) + (C) (added only when the (C) component is colloidal silica) + (D) 1 mol of Si atom of the component (B) Si atom of the component (0.01) It is preferable to use so that it may become -0.3 mol, especially 0.05-0.2 mol.

  In the present invention, in addition to the above components (A) and (B), (C) component or (D) component, or both (C) component and (D) component as water repellent treatment effective components Although it can be used, it is preferable to use the component (D), and it is more preferable to use both the component (C) and the component (D). That is, those using the components (A), (B), (C) and (D) are most preferred, and then those using the components (A), (B) and (D) are preferred.

  In order to produce an aqueous water repellent using these (A) component, (B) component, (C) component and / or (D) component, co-hydrolysis is carried out in the presence of an organic acid or an inorganic acid. What is necessary is just to decompose. In this case, the components (A), (C), and (D) are first cohydrolyzed in the presence of an organic acid or an inorganic acid, and the cohydrolyzed product and the component (B) are mixed to obtain an organic acid or an inorganic acid. It is preferable to further cohydrolyze in the presence of an acid.

  First, examples of the organic acid and inorganic acid used when the components (A), (C), and (D) are cohydrolyzed include hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, formic acid, acetic acid, propionic acid, At least one acid selected from citric acid, oxalic acid, maleic acid and the like is used, and particularly preferred are acetic acid and propionic acid. The amount of the acid used is preferably 2 to 40 parts, particularly 3 to 15 parts, per 100 parts of component (A).

  The hydrolysis is preferably carried out in a state of being appropriately diluted with a solvent. As the solvent, alcohol solvents are preferable, and methanol, ethanol, isopropyl alcohol, and tertiary butyl alcohol are particularly preferable. The amount of the solvent used is preferably 50 to 300 parts, particularly 70 to 200 parts with respect to 100 parts in total of the components (A), (C), and (D). If the amount of solvent used is less than 50 parts, condensation may proceed, and if it exceeds 300 parts, cohydrolysis may take time.

  The amount of water added to co-hydrolyze the components (A), (C) and (D) is 0.5 to 4 mol with respect to 1 mol in total of the components (A), (C) and (D). An amount, in particular 1 to 3 molar, is preferred. If the amount of water added is less than 0.5 mol, a large amount of alkoxy groups may remain, and if the amount exceeds 4 mol, condensation may proceed excessively. Moreover, when using the colloidal silica which (C) component has disperse | distributed in water, it is good also as the water used for co-hydrolysis. The reaction conditions for co-hydrolyzing the components (A), (C), and (D) are preferably a reaction temperature of 10 to 40 ° C., particularly 20 to 30 ° C., and a reaction time of 1 to 3 hours for the hydrolysis reaction. It is good.

  The cohydrolyzed product of the component (A) obtained above and the component (C) and / or the component (D) and the component (B) are cohydrolyzed. The reaction conditions for cohydrolysis are preferably a reaction temperature of 60 to 100 ° C. and a reaction time of 1 to 3 hours. After completion of the reaction, the temperature is raised to the boiling point of the solvent or higher, and the alcohol solvent is distilled off. In this case, it is preferable to distill off the total alcohol in the system (alcohol as a reaction solvent, alcohol as a by-product) to 30% by mass or less, particularly 10% by mass or less. When a large amount of alcohol is contained, when diluted with water, it may become cloudy or gel, and storage stability may also be reduced.

The reaction product can be produced by the above method, the viscosity at 25 ° C. in viscometry by capillary viscometer is 5~2,000mm ² / s, it is particularly preferably 50 to 500 mm ² / s. If the viscosity is too high, workability and storage stability may decrease, and water solubility may decrease. The weight average molecular weight is preferably in the range of 500 to 5,000, particularly 800 to 2,000.

  The water-based water repellent agent of the present invention is obtained from a cohydrolysis / condensation reaction product of the component (A), the component (B), the component (C) and / or the component (D) obtained by the above-described method. This is because it is diluted with water and the hydrophilic part (amino group, silanol group) and hydrophobic part (alkylsilyl group) are well oriented in an aqueous solution, so that it becomes dissolved or micellar. Water solubility develops even in small amounts. Moreover, since there are inorganic oxide fine particles, the water repellency is improved, probably because fine irregularities are formed. Furthermore, the water repellency is further improved by the bis (alkoxysilyl) group-containing compound. Moreover, water repellent durability is also improved by these synergistic effects. Therefore, it is possible to easily impart high water repellency and low water absorption by treating a substrate with high water absorption.

  In this case, it is preferable to add (E) an aliphatic quaternary ammonium compound and / or (F) a compound containing boron to the aqueous water-repellent treatment agent of the present invention.

Here, as said aliphatic quaternary ammonium compound (E), following General formula (4)
[(CH ₃ ) ₂ R ⁸ N (CH ₂ ) ₃ —SiR ¹ _k (OR ² ) _3−k ] ⁺ X ⁻ (4)
(In the formula, R ¹ and R ² are the same as described above, and R ⁸ is a monovalent hydrocarbon group having 11 to 22 carbon atoms, particularly an alkyl group, an alkenyl group, etc. X is fluorine, chlorine, bromine. And a halogen atom such as iodine, etc. k is 0 or 1.)
It is preferable that it is a quaternary amino group containing alkoxysilane shown by these, or its partial hydrolyzate, and this is a component which gives antibacterial and antifungal properties to wood, when processed to wood.

R ⁸ in the above formula (4) is —C ₁₁ H ₂₃ group, —C ₁₂ H ₂₅ group, —C ₁₅ H ₃₁ group, —C ₁₆ H ₃₃ group, —C ₁₈ H ₃₇ group, —C ₂₀ H ₄₁ groups, -C ₂₂ H ₄₅ groups, and the like.

As a specific example of such a quaternary amino group-containing alkoxysilane of the above formula (4),
[C ₁₂ H ₂₅ (CH ₃ ) ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ] ⁺ Cl ⁻ ,
[C ₁₄ H ₂₉ (CH ₃ ) ₂ N (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ] ⁺ Cl ⁻ ,
[C ₁₆ H ₃₃ (CH ₃ ) ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ] ⁺ Cl ⁻ ,
[C ₁₆ H ₃₃ (CH ₃ ) ₂ N (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ] ⁺ Cl ⁻ ,
[C ₁₆ H ₃₃ (CH ₃ ) ₂ N (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ ] ⁺ Cl ⁻ ,
[C ₁₆ H ₃₃ (CH ₃ ) ₂ N (CH ₂ ) ₃ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ] ⁺ Cl ⁻ ,
[C ₁₈ H ₃₇ (CH ₃ ) ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ] ⁺ Cl ⁻ ,
[C ₁₈ H ₃₇ (CH ₃ ) ₂ N (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ] ⁺ Cl ⁻ ,
[C ₁₈ H ₃₇ (CH ₃ ) ₂ N (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ ] ⁺ Cl ⁻ ,
[C ₁₈ H ₃₇ (CH ₃ ) ₂ N (CH ₂ ) ₃ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ] ⁺ Cl ⁻
Etc. are preferably used.

  Moreover, didecyl dimethyl ammonium chloride can also be used as the said aliphatic quaternary ammonium compound (E).

  By adding the above component (E), antibacterial and antifungal properties can be imparted, and the blending amounts thereof are water repellent active ingredients (component (A), component (B), and component (C). And / or cohydrolyzed condensate with component (D)) is preferably 0.05 to 10 parts, more preferably 0.1 to 5 parts, per 100 parts. If the amount is too small, the antibacterial and antifungal properties may be insufficient, and if the amount is too large, the storage stability of the water-based water repellent agent may be deteriorated.

On the other hand, the boron-containing compound (F) is preferably a boric acid compound. Specifically, orthoborates such as InBO ₃ and Mg ₃ (BO ₃ ) ₂ ; Mg ₂ B ₂ O ₅ and Co ₂ B ₂ Diborates such as O ₅ ; metaborates such as NaBO ₂ , KBO ₂ , LiBO ₂ and Ca (BO ₂ ) ₂ ; tetraborate such as Na ₂ B ₄ O ₇ ; _five such as KB ₅ O ₈ Examples thereof include borates. Boric acid such as orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ), tetraboric acid (H ₂ B ₄ O ₇ ); borax (Na ₂ B ₄ O ₇ .10H ₂ O); Examples thereof also include disodium borate tetrahydrate (Na ₂ B ₈ O ₁₃ · 4H ₂ O).

  Addition of the above component (F) can provide ant-repellent properties, and the blending amount thereof is the water repellent active component (component (A), component (B), component (C) and / or (D). ) Cohydrolyzed condensate with component) 0.1 to 1,000 parts, particularly 2 to 500 parts, with respect to 100 parts. If the amount is too small, the termite-proofing property may be insufficient. If the amount is too large, the storage stability of the water-based water repellent may be deteriorated.

  The water-based water-repellent treatment agent of the present invention can be used for water-repellent treatment of a substrate, particularly a substrate such as a lignocellulose-derived substance such as paper, fiber, brick, and wood. In this case, examples of the lignocellulose-derived substance include wood materials such as wood, plywood, veneer laminate, wood powder molding material, wood fiber board, cellulose-derived paper, fiber and the like.

  Specifically, the water-based water-repellent treatment agent of the present invention can be applied to paper as a dimensional stabilizer to prevent paper squeezing, wrinkling, and dimensional change due to water-based ink (for example, ink jet printing), and to improve printing characteristics. Therefore, the print quality is also improved. In addition, it can be applied to substrates such as various textile products, bricks, wood, plywood, veneer laminates and wood fibers for wood fiber boards, and is also suitable as a primer for various paints and finishing materials. is there.

  As a processing method in the case of processing the water-based water repellent agent of the present invention on the substrate, the water repellent active ingredient is 0.5 to 50% by mass, preferably 1 to 10% by mass in water. It is preferable to use it diluted. If diluted below 0.5% by weight, not only the original performance will not be exhibited, but also a large amount of coating must be applied, so it may take time to dry, and if the concentration is higher than 50% by weight In some cases, the dilution is not performed sufficiently, the viscosity becomes high, the impregnation property to the base material is deteriorated, and smearing or discoloration occurs.

  Here, when this aqueous water repellent is diluted with water, the pH of the aqueous solution is preferably 7 to 3, more preferably 6 to 4. When the pH exceeds 7 and becomes alkaline, there is a risk of breaking the cellulosic substrate when applied to a cellulosic substrate such as paper or wood. In addition, there may be a problem that the substrate is damaged or the treated substrate is corroded even under strong acidity with a pH of less than 3. If it synthesize | combines with the method of this invention, what is in said range can be performed. Therefore, it is most preferable when a treatment liquid having a neutral to weakly acidic level is treated as in the present invention.

When the water-based water repellent treatment agent of the present invention is diluted with water, an antiseptic, an antifungal agent, an antifungal agent, a fragrance, a colorant, carboxymethylcellulose, polyvinyl alcohol (PVA), a water-soluble acrylic resin, SBR latex, etc. May be added as a secondary agent. In addition, the addition amount of these arbitrary components can be made into a normal amount in the range which does not inhibit the effect of this invention.

  In addition, when it is desired to penetrate the water-based water repellent agent deeper into the substrate, a surfactant may be added in order to further increase the permeability of the water-based water repellent agent.

  The surfactant to be used is not particularly limited, and various conventionally known nonionic, cationic and anionic surfactants are applicable. Specifically, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene carboxylic acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyether-modified silicone, alkyltrimethyl Cationic surfactants such as ammonium chloride and alkylbenzylammonium chloride, anionic surfactants such as alkyl or alkylallyl sulfate, alkyl or alkylallyl sulfonate, dialkylsulfosuccinate, amino acid type, betaine type, etc. These zwitterionic surfactants can be mentioned. Among these, polyether-modified silicone surfactants are particularly preferable.

  The addition amount of the surfactant is preferably 0.01 to 5% by mass, more preferably 0.2 to 2.5% by mass with respect to the water repellent active ingredient. If the amount is less than 0.01% by mass, there is almost no change from the water-based water repellent treatment alone, and the effect of addition may not be obtained. Further, when an amount exceeding 5% by mass is added, water absorption prevention and water repellency may be weakened.

  In addition, the surfactant is not added to the water-based water repellent treatment agent in advance, but before the water-based water repellent treatment agent is processed, the base material is pretreated with the surfactant diluted solution, and then the water-based water repellent treatment agent is used. It may be processed. In that case, for example, a solution in which a surfactant is diluted in water or an organic solvent at a concentration of 0.01 to 5% by mass, particularly 0.1 to 2% by mass is prepared, and a roller, a brush, a spray, or the like is used. Can be deeply infiltrated into the substrate by pre-treating the substrate by an immersion method and then treating with a water-based water repellent.

The Mizuki dilution liquid of the aqueous water repellent of the present invention to be applied to the substrate, a roller, brush, using a spray or the like, may be by dipping method in some cases, atmospheric pressure, under reduced pressure or under pressure An injection process may be performed. Further, at this time, the treatment liquid may be heated (30 to 100 ° C.) for treatment. As a drying method, it may be left at room temperature, or may be sun drying or heat drying.

  In other countries, as a preservative and ant-preventive treatment, wood in which the above boron-containing compound (F) has been pre-injected into the interior is used for building materials. Since the compound (F) to be contained is eluted, there is a problem that it cannot be used as an exterior material. However, by applying the water-based water repellent treatment agent of the present invention to the surface of the treated wood that has been pre-injected with such a compound (F) containing boron, the surface is provided with excellent water repellent performance. The elution of the compound (F) containing boron inside can be suppressed, and it can be used for exterior materials. The concentration of the treatment liquid in this case is as described above, and it is preferable that the application method is applied to the surface using a roller, a brush, a spray, or the like. As a drying method, it may be left at room temperature, or may be sun drying or heat drying.

  The water-based water repellent treatment agent of the present invention impregnated into the substrate in this way forms a strong and excellent water repellent layer by hydrolysis reaction and condensation reaction. Therefore, when applied to paper, a dimensional stability effect appears. Also, when applied to textile products, it has a good water repellency, and when applied to building materials such as bricks, general wood, plywood, and veneer laminates, various problems caused by water such as swelling, corrosion, and wrinkles In addition to helping to solve the problem, it is also excellent as a base waterproof primer for various paints and finishing materials. In addition, if wood is treated with extremely high water absorption, high water repellency and low water absorption can be easily provided.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part. In the following examples, the average particle diameter indicates a value measured by a laser scattering particle size distribution measuring device, the viscosity indicates a value at 25 ° C. measured by a capillary viscometer, and the weight average molecular weight is measured by a GPC measuring device. The converted polystyrene value is shown.

[ Reference Example 1 ]
In a 500 ml four-necked flask equipped with a condenser, thermometer and dropping funnel, 199 g of methyltrimethoxysilane oligomer (0.88 mol in terms of dimer), 120 g of methanol and 11.8 g of acetic acid are being stirred. 19.8 g (0.88 mol of water) of Snowtex O (SiO ₂ content 20% aqueous solution, average particle size 10-20 nm) manufactured by Nissan Chemical Industries, Ltd. was added and stirred at 25 ° C. for 2 hours. There, 38.9 g (0.18 mol) of 3-aminopropyltriethoxysilane was added dropwise. Then, after heating to the reflux temperature of methanol and reacting for 1 hour, the alcohol was distilled off with an ester adapter until the internal temperature reached 110 ° C. to obtain 209 g of a pale yellow transparent solution having a viscosity of 460 mm ² / s (weight). Average molecular weight 1,000). The residual amount of alcohol (methanol + ethanol) in this system was 2% by mass (water repellent 1).

[ Reference Example 2 ]
In a 500 ml four-necked flask equipped with a condenser, thermometer and dropping funnel, 199 g of methyltrimethoxysilane oligomer (0.88 mol in terms of dimer), methanol silica sol manufactured by Nissan Chemical Industries, Ltd. (SiO ₂ content 30) % Methanol solution, average particle size 10-20 nm) 13.2 g, 120 g of methanol and 11.8 g of acetic acid are added, and 15.8 g (0.88 mol) of water is added to the stirring place, and at 25 ° C. for 2 hours. Stir. There, 38.9 g (0.18 mol) of 3-aminopropyltriethoxysilane was added dropwise. Then, after heating to the reflux temperature of methanol and reacting for 1 hour, the alcohol was distilled off with an ester adapter until the internal temperature reached 110 ° C. to obtain 200 g of a pale yellow transparent solution having a viscosity of 280 mm ² / s (weight). Average molecular weight 800). The residual amount of alcohol (methanol + ethanol) in this system was 2% by mass (water repellent 2).

[ Reference Example 3 ]
The reaction was carried out in the same manner as in Reference Example 2 except that methanol silica sol (SiO ₂ content 30% methanol solution, average particle size 10 to 20 nm) manufactured by Nissan Chemical Industries, Ltd. was changed to 39.5 g, and the viscosity was 290 mm ² / s. 210 g of a pale yellow transparent solution was obtained (weight average molecular weight 1,100). The residual amount of alcohol (methanol + ethanol) of this product was 3% by mass (water repellent 3).

[Example 1 ]
In a 500 ml four-necked flask equipped with a condenser, a thermometer and a dropping funnel, 199 g of methyltrimethoxysilane oligomer (0.88 mol in terms of dimer), (CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₉ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ 7.5 g (0.008 mol), 120 g of methanol and 11.8 g of acetic acid were added and water (0 .88 mol) was added and stirred at 25 ° C. for 2 hours. There, 38.9 g (0.18 mol) of 3-aminopropyltriethoxysilane was added dropwise. Then, after heating to the reflux temperature of the alcohol and reacting for 1 hour, the alcohol was distilled off with an ester adapter until the internal temperature reached 110 ° C. to obtain 206 g of a pale yellow transparent solution having a viscosity of 180 mm ² / s (weight). Average molecular weight 800). The residual amount of alcohol (methanol + ethanol) in this system was 3% by mass (water repellent 4).

[Example 2 ]
_{(CH 3 O) 3 SiCH 2} CH 2 (Si (CH 3) 2 O) 9 Si (CH 3) 2 CH 2 CH 2 Si (OCH 3) 3 and _{7.5g (CH 3 O) 3 Si} -C 6 The reaction was conducted in the same manner as in Example 1 except that 5.0 g (0.015 mol) of H ₁₂ -Si (OCH ₃ ) ₃ was obtained to obtain 201 g of a pale yellow transparent solution having a viscosity of 170 mm ² / s (weight average molecular weight). 700). The residual amount of alcohol (methanol + ethanol) of this product was 3% by mass (water repellent 5).

[Example 3 ]
_{(CH 3 O) 3 SiCH 2} CH 2 (Si (CH 3) 2 O) 9 Si (CH 3) 2 CH 2 CH 2 Si (OCH 3) the _{3 7.5g (CH 3 O) 3} SiCH 2 The reaction was carried out in the same manner as in Example 1 except that 8.9 g (0.015 mol) of CH ₂ —C ₆ F ₁₂ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ was used, and a pale yellow having a viscosity of 195 mm ² / s. 213 g of a clear solution was obtained (weight average molecular weight 1,000). The residual amount of alcohol (methanol + ethanol) of this product was 2% by mass (water repellent 6).

[Example 4 ]
In a 500 ml four-necked flask equipped with a condenser, a thermometer and a dropping funnel, 199 g of methyltrimethoxysilane oligomer (0.88 mol in terms of dimer), (CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₉ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ 7.5 g (0.008 mol), 120 g of methanol and 11.8 g of acetic acid are added and stirred. Ltd. Snowtex O (SiO ₂ content of 20% aqueous solution, average particle size: 10 to 20 nm) was charged 19.8 g (0.88 mol of water) and stirred for 2 hours at 25 ° C.. There, 38.9 g (0.18 mol) of 3-aminopropyltriethoxysilane was added dropwise. Then, after heating to the reflux temperature of the alcohol and reacting for 1 hour, the alcohol was distilled off with an ester adapter until the internal temperature reached 110 ° C. to obtain 210 g of a pale yellow transparent solution having a viscosity of 160 mm ² / s (weight). Average molecular weight 700). The residual amount of alcohol (methanol + ethanol) in this system was 2% by mass (water repellent 7).

[Example 5 ]
_{(CH 3 O) 3 SiCH 2} CH 2 (Si (CH 3) 2 O) 9 Si (CH 3) 2 CH 2 CH 2 Si (OCH 3) 3 and _{7.5g (CH 3 O) 3 Si} -C 6 The reaction was conducted in the same manner as in Example 4 except that 5.0 g (0.015 mol) of H ₁₂ -Si (OCH ₃ ) ₃ was obtained to obtain 203 g of a pale yellow transparent solution having a viscosity of 200 mm ² / s (weight average molecular weight). 700). The residual amount of alcohol (methanol + ethanol) of this product was 3% by mass (water repellent 8).

[Example 6 ]
_{(CH 3 O) 3 SiCH 2} CH 2 (Si (CH 3) 2 O) 9 Si (CH 3) 2 CH 2 CH 2 Si (OCH 3) the _{3 7.5g (CH 3 O) 3} SiCH 2 The reaction was carried out in the same manner as in Example 4 except that 8.9 g (0.015 mol) of CH ₂ —C ₆ F ₁₂ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ was used, and a pale yellow having a viscosity of 250 mm ² / s. 215 g of a clear solution was obtained (weight average molecular weight 900). The residual amount of alcohol (methanol + ethanol) of this product was 2% by mass (water repellent 9).

[Comparative Example 1]
In a 500 ml four-necked flask equipped with an aspirator and a thermometer, 136 g (1.0 mol) of methyltrimethoxysilane and 222.0 g (1.0 mol) of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane ) And 43.2 g (2.4 mol) of water and stripped with an aspirator while heating and stirring to 60 ° C. to obtain a pale yellow transparent solution (weight average molecular weight 900). The amount of methanol remaining in this product was 1% by mass (water repellent 10).

[Comparative Example 2]
10.5 g (0.04 mol) of decyltrimethoxysilane, 8.8 g of methanol, 0.8 g of acetic acid and 2.2 g (0.12 mol) of water are mixed and stirred at 25 ° C. for 1 hour to obtain a transparent solution. It was.
A 500 ml four-necked flask equipped with a condenser, thermometer and dropping funnel was charged with 85 g of methyltrimethoxysilane oligomer (0.37 mol in terms of dimer) and 170 g of methanol, and the above decyltrimethoxy was stirred. The silane hydrolyzate was added dropwise and stirred at 25 ° C. for 1 hour. Thereafter, 5.1 g of acetic acid and 6.7 g (0.37 mol) of water were added, and the mixture was further stirred at 25 ° C. for 1 hour. Thereto, 17.8 g (0.08 mol) of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added dropwise. Then, after heating to the reflux temperature of methanol and reacting for 1 hour, methanol was distilled off with an ester adapter until the internal temperature reached 110 ° C. to obtain a pale yellow transparent solution (weight average molecular weight 1,300). The residual amount of methanol in this product was 8% by mass (water repellent 11).

[Comparative Example 3]
A 500 ml four-necked flask equipped with a condenser, a thermometer and a dropping funnel is charged with 85 g of methyltrimethoxysilane oligomer (0.37 mol in terms of dimer), 154 g of methanol and 5.1 g of acetic acid. Was charged with 6.8 g (0.37 mol) of water and stirred at 25 ° C. for 2 hours. Thereto, 8.9 g (0.04 mol) of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added dropwise. Then, after heating to the reflux temperature of methanol and reacting for 1 hour, the methanol was distilled off with an ester adapter until the internal temperature reached 110 ° C. to obtain 81 g of a pale yellow transparent solution having a viscosity of 71 mm ² / s (weight). Average molecular weight 1,100). The amount of methanol remaining in this system was 5% by mass (water repellent 12).

[Comparative Example 4]
In a 500 ml four-necked flask equipped with a condenser, a thermometer and a dropping funnel, 85 g of methyltrimethoxysilane oligomer (0.37 mol in terms of dimer), N- (2-aminoethyl) -3-aminopropyltrimethoxy 8.9 g (0.04 mol) of silane was added, and 5.1 g of acetic acid was added to the mixture and stirred, and stirred at 25 ° C. for 1 hour to obtain 98 g of a pale yellow transparent solution. However, an attempt was made to dilute 10 parts of this composition into 90 parts of water, but it gelled as soon as it was diluted.

[Comparative Example 5]
In a 500 ml four-necked flask equipped with a condenser, thermometer and dropping funnel, 85 g of methyltrimethoxysilane oligomer (0.37 mol in terms of dimer) and N- (2-aminoethyl) -3-aminopropyltrimethoxy 8.9 g (0.04 mol) of silane was added, and 6.8 g (0.37 mol) of water was added to the stirring place, and the reaction was stirred at 60 ° C. for 3 hours. The reaction solution gelled.

[Comparative Example 6]
In a 1 L four-necked flask equipped with a condenser, thermometer and dropping funnel, 150 g (1.1 mol) of methyltrimethoxysilane, 100 g (0.41 mol) of 3,4-epoxycyclohexylethyltrimethoxysilane and N 20 g (0.09 mol) of-(2-aminoethyl) -3-aminopropyltrimethoxysilane was added, and a mixture of 100 g of water (5.55 mol) and 200 g of methanol was added dropwise over 30 minutes while stirring. did. The reaction was further stirred at 60 ° C. for 1 hour to obtain 567 g of a pale yellow transparent solution. However, an attempt was made to dilute 10 parts of this composition into 90 parts of water, but it gelled as soon as it was diluted.

[Example 7 ]
10 parts of the water repellent 7 synthesized in Example 4 , 0.5 part of 3- (trimethoxysilyl) propyloctadecyldimethylammonium, 1.5 parts of boric acid and 88 parts of water were mixed and dissolved. The solution 13 was obtained.

[Example 8 ]
10 parts of the water repellent 7 synthesized in Example 4 , 2 parts of boric acid, and 88 parts of water were mixed and dissolved to make the water repellent 14.

[Example 9 ]
10 parts of the water repellent 7 synthesized in Example 4 , 0.5 part of didecyldimethylammonium chloride, 1.5 parts of boric acid, and 88 parts of water were mixed and dissolved to make the water repellent 15.

[Example 10 ]
The water repellent 16 synthesized was 1.1 parts of the water repellent 7 synthesized in Example 4 , 2.9 parts of boric acid, and 96 parts of water.

Storage stability evaluation
Reference Examples 1-3, Examples 1-6 , 10 parts of the water repellents 1-12 synthesized in Comparative Examples 1-3, diluted with 90 parts of water, and the water repellents obtained in Examples 7-10 Agents 13 to 16 were placed in a plastic container, and the storage stability at room temperature and 40 ° C. was evaluated. The results are shown in Table 1.

[Usage example 1]
The treatment liquid which diluted 5 parts of the water repellents 1-12 obtained in Reference Examples 1-3, Examples 1-6 , and Comparative Examples 1-3 with 95 parts of water, and obtained in Examples 7-9 . A treatment solution was prepared by diluting 50 parts of the water repellents 13 to 15 with 50 parts of water. Each performance test was performed by the following method about the surface discoloration, water repellency, and water absorption prevention property about this sample. The results are shown in Table 2.

Surface discoloration, water repellency, water absorption prevention performance Solid cedar cedar (45 x 100 x 100 mm), solid radiata pine (45 x 100 x 100 mm), and laminated lamella pine (45 x 100 x 100 mm) ) Was immersed on the entire surface at room temperature and normal pressure for 5 minutes, then cured at room temperature for 7 days, and surface discoloration (yellowing) was observed visually. The water repellency was evaluated by measuring the contact angle of water on the wood surface. In addition, water repellency was similarly evaluated about the untreated cedar solid sapwood, solid radiata pine timber, and radiata pine laminated timber. Subsequently, the entire specimen was immersed in tap water, and after 48 hours, the mass, thickness, and width of the specimen were measured, and the water absorption, the width expansion coefficient, and the thickness expansion coefficient were calculated. At the same time, Russian larch material (45 × 100 × 100 mm) was also measured as an untreated comparative sample.

The surface discoloration was visually evaluated according to the following evaluation criteria. The results are shown in Table 2.
○: No color change △: Some color change ×: Color change

Water repellency (measurement of water contact angle)
Using a contact angle meter (CA-X150 type, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of water was measured by the sessile drop method. Five points were measured per sample, and the average value was taken as the value of the contact angle. The results are shown in Table 2.

Water absorption prevention performance The water absorption rate, width expansion rate and thickness expansion rate were calculated according to the following formula. These results are shown in Tables 3-5.

Water absorption (mass%) = [(Wt−Wo) / Wo] × 100
Wt: Weight of test piece at time t (g)
Wo: Weight of test piece before starting test (g)

Width expansion coefficient (%) = [(WIt−WIo) / WIo] × 100
WIt: Width of test piece at time t (mm)
WIo: Specimen width before test start (mm)

Thickness expansion rate (%) = [(Tt−To) / To] × 100
Tt: Thickness of the test piece after elapse of time (mm)
To: Thickness (mm) of the test piece before the start of the test

[Usage example 2]
What was obtained by diluting 25 parts of the water repellents 13, 14 and 15 obtained in Examples 7, 8 and 9 with 75 parts of water in cedar and lauan materials, air-dried at room temperature for 1 week, and for evaluation Samples were prepared, and tests for wood decay test and termite mortality test were conducted by the following methods. The results are shown in Table 6.

(A) Wood decay test with white and brown rot fungi In accordance with Japan Wood Conservation Association (JWPA) Standard No. 3-1992 “Durability Test Method for Woody Materials” for evaluation of antibacterial and antifungal performance The decay test of inorganic composite wood was conducted. After drying at 60 ° C. for 48 hours and sterilization, place the test piece prepared on the flora of white rot fungus Kawaratake (Trametes versicolor) and brown rot fungus Prunus periwinkle (Fomitopsis palustris) that has been fully grown in an incubator in a glass bottle. It was. After culturing in a constant humidity room at room temperature of 26 ° C. and relative humidity of 55 to 65% for 8 weeks, the test piece was taken out, bacteria on the surface of the test piece were removed, and the absolute dry weight of the test piece was determined. The weight reduction rate (%) due to the rot fungus was determined from the absolute dry weight before the treatment measured in advance.

(B) Corrosion test by burial test 9 months in unsterilized soil (17 cm above the ground) for untreated wood test pieces and water repellent treated wood specimens each soxhlet extracted with acetone and water for 24 hours. The burial test was performed, and the weight reduction rate was calculated from the absolute dry weight before the test and the absolute dry weight after the test, and the progress of the degree of decay was estimated.

(C) Test of termite mortality 200 200 termites were placed in a container containing untreated wood pieces and water repellent treated wood pieces, and the mortality rate of the termites after standing for 20 days was measured.

[Usage example 3]
A solution obtained by diluting 25 parts of the water repellent 16 obtained in Example 10 with 75 parts of water was injected into cedar wood (2 × 2 × 1 cm) at a reduced pressure of 700 kg / m ³ (the silicone component was wood). 2kg / m ^{3 in the} inside and boric acid in the wood at a rate of 5kg / m ³ ). Thereafter, curing was performed at 60 ° C. for 16 hours to prepare a sample for evaluation. Based on JIS K 1571 “Performance Standards and Test Methods for Wood Preservatives”, tests for wood decay test and termite mortality test were conducted by the following methods. The results are shown in Table 7.
However, the following biological tests (d) and (e) shall be performed after the weather resistance operation is performed on the specimen. In this method, a leaching operation is performed by immersing in stirring water for 8 hours, followed by drying in a high-temperature vessel at a temperature of 60 ° C. This operation was repeated 10 times.

(D) Wood decay test using white rot fungus and brown rot fungus Brown rot fungus Fomitopsis palustris and white rot fungus Kawaratake (Trametes versicolor) were used as test bacteria. The mycelium obtained by shaking culture of stock strains (Ozuuratake FFPRI-0507, Kawaratake FFPRI-1030) in a liquid medium was placed in a mayonnaise bottle with quartz sand and a culture solution (composition of glucose, peptone, malt extract) Static culture was sprinkled on the medium.
When the bacterial flora spread sufficiently, a gas-sterilized test specimen (20 × 20 mm × test specimen thickness) was placed in a culture bottle and decayed in a 26 ° C. culture chamber for 3 months. The number of test specimens was nine, and constant weights (W1, W2) were determined by drying at 60 ° C. before and after the decay operation. The mass reduction rate of the test body was calculated by [(W1-W2) / W1] × 100.

(E) Termite mortality test The treated specimens were subjected to weathering operations in advance. As in JIS K 1571, the weathering operation was repeated 10 times by leaching for 8 hours by immersion in stirring water and drying in a 60 ° C. incubator.
One specimen was placed in a plastic container (diameter 80 mm, length 60 mm), 150 termite ants and 15 soldier ants were added, and a damage test was conducted in the dark at 28 ° C. for 3 weeks. . The plastic container was set in a container preliminarily spread with absorbent cotton after the bottom was hardened with plaster, and appropriate moisture was given to the absorbent cotton. The mass loss rate due to the damage of termites after standing for 3 weeks and the death rate of termites were measured.

[Usage example 4]
Borate compounds _{(Na 2 B 8 O 13 ·} 4H 2 O) cedar sapwood containing 6 kg / m ³ in the wood (2 × 2 × 1cm), water repellent obtained in Example 1 A sample obtained by diluting 10 parts of No. 4 with 90 parts of water was applied to the surface with a brush and then cured at 25 ° C. for 7 days to prepare a sample for evaluation. In accordance with JIS K 1571 “Performance Standards and Test Methods for Wood Preservatives”, tests for wood decay test and termite mortality test were carried out on those subjected to leaching operation in the same manner as in Use Example 3. The results are shown in Table 8.
Moreover, the quantitative determination of boric acid in the wood pieces after this leaching operation was measured by the following method. The results are also shown in Table 8.

(F) Boric acid determination method A piece of wood was placed in a Teflon beaker, 50 ml of 3% nitric acid was added, and the mixture was heated at 200 ° C. for 2 hours. After cooling, 50 ml of water was added and quantified. This operation was repeated 5 times, and the amount of boron in each aqueous solution was measured with an ICP analyzer, and the total amount of boron was converted to boric acid for quantification.

Claims (19)

(A) The following formula (1)
(R ¹ ) _a (OR ² ) _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, a is 0.75 to 1.5, and b is 0.2 to 3) And a positive number satisfying 0.9 <a + b <4.)
100 parts by mass of a siloxane oligomer having 2 to 10 silicon atoms represented by
(B) The following general formula (2)
R ³ R ⁴ NR ⁵ —SiR ⁶ _c (OR ² ) _3-c (2)
(In the formula, R ² is the same as above, R ³ and R ⁴ are the same or different hydrogen atoms, or an alkyl group or aminoalkyl group having 1 to 15 carbon atoms, and R ⁵ is the number of carbon atoms. 1 to 18 divalent hydrocarbon groups, R ⁶ is an alkyl group having 1 to 4 carbon atoms, and c is 0 or 1.)
0.5 to 49 parts by mass of an amino group-containing alkoxysilane or a partial hydrolyzate thereof represented by
(D) The following general formula (3)
(R ¹ ) _3-n (OR ² ) _n Si—Y—Si (R ¹ ) _3-n (OR ² ) _n (3)
[In the formula, R ¹ and R ² are the same as above, Y is an alkylene group having 1 to 20 carbon atoms, or — (CH ₂ ) _a (CF ₂ ) _b (CH ₂ ) _c — (a is 1 to 6, b is 1 to 10, c is a fluorine atom-containing alkylene group represented by 1 to 6), or _{^{-R- (Si (R 7) 2}} O) m -Si (R 7) 2 -R- group ( Here, R ⁷ is an alkyl group having 1 to 6 carbon atoms, R is a divalent hydrocarbon group having 1 to 6 carbon atoms, m is 1 to 30), and n is 1, 2 or 3 It is. ]
As a water-repellent treatment active ingredient, a product obtained by cohydrolyzing and condensing 0.1 to 20 parts by mass of a bis (alkoxysilyl) group-containing compound represented by the above or a partial hydrolyzate thereof in the presence of an organic acid or an inorganic acid A water-based water repellent treatment agent characterized by   The water repellent active ingredient cohydrolyzes the component (A) and the component (D) in the presence of an organic acid or inorganic acid and alcohol, and then cohydrolyzes the cohydrolyzate and the component (B). The water-based water repellent treatment agent according to claim 1, which is obtained by decomposing and then removing the alcohol from outside the system. (A) The following formula (1)
(R ¹ ) _a (OR ² ) _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, a is 0.75 to 1.5, and b is 0.2 to 3) And a positive number satisfying 0.9 <a + b <4.)
100 parts by mass of a siloxane oligomer having 2 to 10 silicon atoms represented by
(B) The following general formula (2)
R ³ R ⁴ NR ⁵ —SiR ⁶ _c (OR ² ) _3-c (2)
(In the formula, R ² is the same as above, R ³ and R ⁴ are the same or different hydrogen atoms, or an alkyl group or aminoalkyl group having 1 to 15 carbon atoms, and R ⁵ is the number of carbon atoms. 1 to 18 divalent hydrocarbon groups, R ⁶ is an alkyl group having 1 to 4 carbon atoms, and c is 0 or 1.)
0.5 to 49 parts by mass of an amino group-containing alkoxysilane or a partial hydrolyzate thereof represented by
(C) 0.1 to 10 parts by mass of inorganic oxide fine particles and (D) the following general formula (3)
(R ¹ ) _3-n (OR ² ) _n Si—Y—Si (R ¹ ) _3-n (OR ² ) _n (3)
[In the formula, R ¹ and R ² are the same as above, Y is an alkylene group having 1 to 20 carbon atoms, or — (CH ₂ ) _a (CF ₂ ) _b (CH ₂ ) _c — (a is 1 to 6, b is 1 to 10, c is a fluorine atom-containing alkylene group represented by 1 to 6), or _{^{-R- (Si (R 7) 2}} O) m -Si (R 7) 2 -R- group ( Here, R ⁷ is an alkyl group having 1 to 6 carbon atoms, R is a divalent hydrocarbon group having 1 to 6 carbon atoms, m is 1 to 30), and n is 1, 2 or 3 It is. ]
As a water-repellent treatment active ingredient, a product obtained by cohydrolyzing and condensing 0.1 to 20 parts by mass of a bis (alkoxysilyl) group-containing compound represented by the above or a partial hydrolyzate thereof in the presence of an organic acid or an inorganic acid A water-based water repellent treatment agent characterized by   The water repellent active ingredient cohydrolyzes the component (A), the component (C) and the component (D) in the presence of an organic acid or an inorganic acid and an alcohol, and then the cohydrolyzate (B) The water-based water-repellent treatment agent according to claim 3, wherein the water-based water repellent is obtained by cohydrolyzing the component (1) and then removing the alcohol from outside the system. The water-based water repellent agent according to any one of claims 1 to 4, wherein R ^{1 of the} component (A) is a methyl group. The aqueous repellent according to any one of claims 1 to 5, wherein the component (A) is a siloxane dimer represented by [CH ₃ (OR ² ) ₂ Si] ₂ O (wherein R ² is the same as above). Water treatment agent. The (B) component amino group-containing alkoxysilane is

The water-based water-repellent treatment agent according to claim 1, wherein The water-based water repellent treatment agent according to any one of claims 3 to 7, wherein the inorganic oxide fine particles of component (C) are colloidal silica. (D) component bis (alkoxysilyl) group-containing compound,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₅ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₇ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₉ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) _{3
(CH 3 O) 3 SiCH 2} CH 2 C 4 F 8 CH 2 CH 2 Si (OCH 3) 3 or _{(CH 3 O) 3 SiCH 2} CH 2 C 6 F 12 CH 2 CH 2 Si (OCH 3) 3
The water-based water repellent agent according to any one of claims 1 to 8, wherein   Furthermore, 0.05-10 mass parts of aliphatic quaternary ammonium compounds (E) are contained with respect to 100 mass parts of water-repellent treatment active ingredients, The water-based water-repellent treatment agent of any one of Claims 1 thru | or 9 . The aliphatic quaternary ammonium compound (E) is represented by the following general formula (4)
[(CH ₃ ) ₂ R ⁸ N (CH ₂ ) ₃ —SiR ¹ _k (OR ² ) _3−k ] ⁺ X ⁻ (4)
(In the formula, R ¹ and R ² are the same as above, R ⁸ is a monovalent hydrocarbon group having 11 to 22 carbon atoms, X is a halogen atom, and k is 0 or 1). )
The water-based water-repellent treatment agent according to claim 10, which is a quaternary amino group-containing alkoxysilane represented by the formula (1) or a partial hydrolyzate thereof. The water-based water-repellent treatment agent according to claim 10, wherein the aliphatic quaternary ammonium compound (E) is didecyldimethylammonium chloride.   The water-based water repellent agent according to any one of claims 1 to 12, further comprising 0.1 to 1,000 parts by mass of the boron-containing compound (F) with respect to 100 parts by mass of the water repellent active ingredient.   The water-based water repellent treatment agent according to claim 13, wherein the compound (F) containing boron is a boric acid compound.   15. The aqueous water repellent agent aqueous solution has a pH in the range of 7 to 3 when the aqueous water repellent agent is diluted with water and treated on a substrate. The water-based water repellent treatment agent described.   The water-based water-repellent treatment agent according to any one of claims 1 to 15, wherein the substrate to be treated is selected from a lignocellulose-derived substance such as paper, fiber, brick, and wood.   The water-based water-repellent treatment agent according to claim 16, wherein the substrate contains a compound (F) containing boron therein.   The water-based water-repellent treatment agent according to any one of claims 1 to 17, wherein the water-repellent treatment active ingredient is diluted with water so as to be 0.5 to 50% by mass.   A water repellent treatment method comprising applying the water-based water repellent treatment agent according to any one of claims 1 to 12 to the surface of a substrate containing therein a boron-containing compound (F).