JP2002121285A - New organopolysiloxane and waterproofing agent containing the same and waterproofing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new organopolysiloxane imparting a wide range of members with both high waterproofness and durability, thus useful as a waterproofing agent for building members, organic members, and the like, a waterproofing agent comprising the organopolysiloxane, and to provide a waterproofing method using the agent. SOLUTION: This organopolysiloxane with a new chemical structure is represented by formula (1) (R is H or any group selected from 1-15C univalent hydrocarbon groups; R1 is a 16-30C alkyl; Q is an alkoxysilyl; A is a group selected from R, R1 and Q; (x) is an integer of 0-500; (y) is an integer of 0-20; (z) is an integer of 0-100; wherein, when (y) is 0, at least one of As is Q; when (z) is 0, at least one of As is R1; when (y) and (z) are each 0, either one of As is Q, the others being each R1). The waterproofing agent for building members or organic members comprises the organopolysiloxane. The waterproofing method using the agent is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organopolysiloxane, a waterproofing agent containing the same, and a waterproofing method thereof, and more particularly, it shows excellent waterproofness and durability to a wide range of members. Accordingly, the present invention relates to a novel organic polysiloxane useful as a waterproofing agent for building members and organic members, a waterproofing agent containing the same, and a waterproofing method using the same.

[0002]

2. Description of the Related Art In recent years, porous materials for construction materials or industrial materials such as concrete, lightweight concrete, precast concrete, lightweight foam concrete (ALC), mortar, etc .; asbestos cement boards, pulp cement boards, wood grain cement boards, glass fibers Containing cement board (GRC),
Various types of building materials, industrial or household materials, such as cement boards containing carbon fibers, glass wool, rock wool, ceramic fibers, natural fibers, man-made fibers, paper, woven fabrics, and non-woven fabrics are used for roads, railways, bridges, and buildings. It is used in large quantities in a wide range of fields such as objects, gardens, parks, harbors, rivers, stadiums, airports, factories, etc. If moisture enters these materials, salt damage, frost damage, alkali-aggregate reaction, decay, etc. This causes the various materials to deteriorate and become unusable, so that it is necessary to perform a waterproof treatment with a waterproof treatment agent to prevent moisture from entering the inside of the various materials.

Conventionally, as a waterproofing agent, wax, paraffin, metal soap, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic resin, styrene resin, styrene butadiene rubber, emulsion such as asphalt, vinyl chloride, Polyurethane-based, amino-resin-based, fluorine-based resin and other paints, silanes having hydrolyzable groups and alkyl groups, silicon macromonomers, polysiloxanes, silicone resins, silicone rubbers, hydroxy-containing polysiloxanes, alkoxy-containing poly Silicone compounds such as siloxane are used, but the waterproofing effect, the durability of the waterproofing effect, the difficulty of the waterproofing method, the impact resistance, the scratch resistance, the chemical resistance,
Acid resistance, alkali resistance, icing resistance, heat resistance, cold resistance,
Because of differences in air permeability, weather resistance, cracking of the film, peeling resistance, environmental protection, safety, price, etc., different waterproofing agents were used depending on the purpose of waterproofing.

[0004] Among these waterproofing agents, those having a silicone compound as a main component are those having waterproofness, water repellency and water repellency.
It is used in many fields because of its excellent permeability, weather resistance, waterproofing property, etc., and appropriate cost performance. Silicone waterproofing agents include silanes with alkyl and alkoxy groups, Siloxanes are known and they have been used alone or in combination. Unfortunately, these silicone compounds are unfortunately waterproof, have a long lasting waterproof effect (durability).
However, it was not satisfactory in terms of quality, and further improvement was required.

Various proposals have been made to solve the problems of the conventional organic polysiloxane. For example, Japanese Patent Publication No. Sho 62-37049 discloses that one molecule contains 1 to 4 carbon atoms. Further, Japanese Patent Application Laid-Open No. 3-47841 (Japanese Patent No. 2722103) discloses that an organic group containing an alkyl group and an alkoxysilyl group has an alkyl group having 6 to 15 carbon atoms in one molecule. And organopolysiloxanes containing alkoxysilyl groups. However, although these organic polysiloxanes are effective as water repellents for fibers and hydraulic inorganic substances, they are useful for waterproofing a wide range of members aimed at by the present invention, particularly organic building materials and inorganic building materials, and also daily necessities or clothing fibers. The treating agent was not particularly satisfactory in terms of durability.

Therefore, there is a strong demand for the development of a novel organic polysiloxane which solves the problems of the conventional organic polysiloxane and which has a sufficiently excellent property, especially in terms of durability, as a waterproofing agent for a wide range of members. Had been.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent waterproofing and durability property for a wide range of members in view of the above-mentioned problems of the conventional organic polysiloxane waterproofing agent. It is an object of the present invention to provide a novel organic polysiloxane useful as a waterproofing agent for members and organic members, and to provide a waterproofing agent containing the same or a waterproofing method using the same.

[0008]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, an organic polysiloxane having a specific chemical structure has solved the above-mentioned disadvantages of the prior art. The present invention was found to be excellent for building materials such as organic building materials and inorganic building materials, and also for waterproofing agents for industrial and domestic fibers or paper, and completed the present invention.

That is, according to the first aspect of the present invention,
An organic polysiloxane represented by the following general formula (1) is provided.

General formula (1):

Embedded image[Wherein, R is independently a hydrogen group or a carbon atom 1
Any group selected from monovalent hydrocarbon groups of
¹Is an alkyl group having 16 to 30 carbon atoms, and Q is a general formula: -R²-Si (R³)_3-a(X)_a  (Where R²Is an alkylene group having 2 to 5 carbon atoms, R³
Is a monovalent hydrocarbon group having 1 to 15 carbon atoms, and X is a carbon atom.
An alkoxy group having 1 to 5 children, a is an integer of 2 or 3
You. A represents R, R¹Or Q
Group, x is an integer of 0 to 500, y is an integer of 0 to 20, z
Represents an integer of 0 to 100. However, when y is 0, A
When at least one is a Q group and z is 0,
At least one is R¹And if y = z = 0, no A
This is a Q group, and the other A is R¹Group. ]

According to the second aspect of the present invention, the first aspect is provided.
In the invention, an organic polysiloxane wherein R is a methyl group is provided.

According to a third aspect of the present invention, there is provided a waterproofing agent comprising the organopolysiloxane according to the first or second aspect of the present invention.

Further, according to a fourth aspect of the present invention, in the third aspect of the present invention, there is provided a method for measuring a water absorption rate in the third aspect of the invention.
A waterproofing agent characterized in that the water absorption after 00 hours is 12% or less. In addition, the water absorption rate measurement test
Mortar board according to JIS A-1404 (50 × 50 × 20m
m) using a test method according to the water absorption measurement method of JIS R-2205 5.2.

Further, according to a fifth aspect of the present invention, there is provided a waterproofing method comprising using the waterproofing agent according to the third or fourth aspect of the present invention for a building member or an organic member. A processing method is provided.

Further, according to a sixth aspect of the present invention, there is provided the waterproofing method according to the fifth aspect of the present invention, wherein the building member is an inorganic building material.

Further, according to a seventh aspect of the present invention, there is provided the waterproofing method according to the sixth aspect of the present invention, wherein the inorganic building material is concrete, mortar, wall soil, or roof soil. You.

According to an eighth aspect of the present invention, in the fifth aspect of the present invention, the organic member is a fiber or paper for building materials, industrial use or home use, and is provided with a waterproof treatment. A method is provided.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

1. Organopolysiloxane The novel organopolysiloxane of the present invention has at least one Q group (alkoxysilylalkyl group) and at least one R ¹ group (carbon atom number) in one molecule represented by the general formula (1). Organic polysiloxane having 16 to 30 long-chain alkyl groups).

General formula (1):

Embedded image[Wherein, R is independently a hydrogen group or a group having 1 to carbon atoms.
Any group selected from 15 monovalent hydrocarbon groups, R¹
Is a long-chain alkyl group having 16 to 30 carbon atoms, and Q is
Formula: -R²-Si (R³)_3-a(X)_a  (Where R²Is an alkylene group having 2 to 5 carbon atoms, R³
Is a monovalent hydrocarbon group having 1 to 15 carbon atoms, and X is a carbon atom.
An alkoxy group having 1 to 5 children, a is an integer of 2 or 3
You. A) is an alkoxysilylalkyl group represented by
R, R¹And a group selected from Q, x is 0 to 500
An integer, y is an integer of 0 to 20 and z is an integer of 0 to 100
You. However, when y is 0, at least one of A is a Q group
And if z is 0, at least one of A is R¹In the base
When y = z = 0, one of A is a Q group, and the other is
A is R¹Group. ]

Examples of R in the above formula include a hydrogen group,
An alkyl group having 1 to 15 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc., acyl group (eg, acetyl group), aryl group (eg, phenyl group, naphthyl group, etc.), aralkyl group ( Examples thereof include a benzyl group and a phenylethyl group), a tolyl group, a xylyl group, a cyclohexyl group, and a halogenated alkyl group (a trifluoropropyl group, a chloropropyl group and the like), and a methyl group is particularly preferable.

Examples of R ^{1 in} the above formula include an alkyl group having 16 to 30 carbon atoms, for example, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henycosyl group, docosyl group, tricosyl group, tetracosyl group, Examples include a pentacosyl group, a hexacosyl group, a heptacosyl group, an octakosyl group, a nonacosyl group, a triacontyl group, and the like, and a mixture thereof.

Examples of R ² of the Q group in the above formula include:
It is an ethylene group, a propylene group, a butene group, a heptene group or the like, and preferably an ethylene group. R ³ is the same as R except for removing a hydrogen group, X is a methoxy group,
It is an alkoxy group having 1 to 5 carbon atoms exemplified by an ethoxy group, a propoxy group and a methoxyethoxy group. a is an integer of 2 or 3, but preferably 3.

Specific examples of the Q group include —CH₂CH₂S
i (OCH₃)₃, -CH₂CH₂SiCH₃(OCH
₃)₂, -CH₂CH₂Si (OCH₂CH₃)₃, −
CH ₂CH₂Si ｛OCH (CH₃)₂｝₃,-(CH
₂)₃Si (OCH₃)₃,-(CH₂)₅SiC2H
₅(OCH₂CH₃)₂Is mentioned. Especially limited
But -CH₂CH₂Si (OCH₃)₃Or -CH
₂CH₂Si (OCH ₂CH₃)₃Is preferred.

A is a group selected from R, R ¹ and Q;
x is an integer of 0 to 500, y is an integer of 0 to 20, z is 0 to
Indicates an integer of 100. However, when y is 0, at least one of A is a Q group, when z is 0, at least one of A is an R ¹ group, and when y = z = 0, one of A is a Q group. And the other A is an R ¹ group. Preferably, x is an integer of 5-100, y is an integer of 1-10, z is 1-20
Is an integer.

The organic polysiloxane having a long-chain alkyl group having 16 to 30 carbon atoms and an alkoxysilylalkyl group according to the present invention is, for example, a corresponding polymethyl compound represented by the following general formula (2): For example, an alkene having a corresponding unsaturated group represented by the following general formula (3) and an alkoxysilane having a corresponding unsaturated alkyl group represented by the following general formula (4) are hydrosilyl, for example. It is obtained by carrying out an addition reaction in the presence of a conversion catalyst.

General formula (2):

Embedded image [Wherein, R is an arbitrary group selected from monovalent hydrocarbon groups having 1 to 15 carbon atoms, A is a group selected from R, R ¹ and H, x is 0 to 500 Integer, y is an integer of 0 to 20, z is an integer of 0 to 100. However,
y + z is a numerical range of 1 ≦ (y + z) ≦ 120. ]

General formula (3):

Embedded image Wherein R ⁴ is an alkyl group having 14 to 28 carbon atoms. Examples of the alkene having 16 to 30 carbon atoms and having an unsaturated group represented by the general formula (3) include the following. 1-hexadecene, 1-heptadecene, 1-
Octadecene, 1-nonadecene, 1-icosene, 1-hemicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacocene, 1-
Heptacocene, 1-octacocene, 1-nonacocene, 1
-Toria content.

General formula (4):

Embedded image Wherein Q ¹ is a general formula: —Si (R ³ ) 3 -a (X) a (wherein, R ³ is a monovalent hydrocarbon group having 1 to 15 carbon atoms, and X is 1 carbon atom. And a is an integer of 2 or 3, and n is an integer selected from 0, 1, 2, or 3. ]

Examples of the alkoxysilane having an unsaturated alkyl group represented by the general formula (4) include the following. Trimethoxyvinylsilane, dimethoxymethylvinylsilane, methoxydimethylvinylsilane, triethoxyvinylsilane, diethoxymethylvinylsilane, ethoxydimethylvinylsilane, tris (n
-Propoxy) vinylsilane, tris (n-butoxy)
Vinylsilane, tris (n-pentoxy) vinylsilane, allyltrimethoxyvinylsilane, allylmethyldimethoxysilane, allyldimethylmethoxysilane, allyltriethoxysilane, allylmethyldiethoxysilane, allyldimethylethoxysilane, allyl-tris (n-propoxy) silane Allyl-tris (n-butoxy) silane, allyl-tris (n-pentoxy) silane, 3-butenyltrimethoxysilane, 3-butenylmethyldimethoxysilane, 3-butenyldimethylmethoxysilane, 3-butenyltrisilane Ethoxysilane, 3-butenylmethyldiethoxysilane, 3-butenyldimethylethoxysilane, 3-butenyl-tris (n-propoxy)
Silane, 3-butenyl-tris (n-butoxy) silane, 3-butenyl-tris (n-pentoxy) silane,
4-pentenyltrimethoxysilane, 4-pentenylmethyldimethoxysilane, 4-pentenyldimethylmethoxysilane, 4-pentenyltriethoxysilane, 4-pentenylmethyldiethoxysilane, 4-pentenyldimethylethoxysilane, 4-pentenyl-tris (n -Propoxy) silane, 4-pentenyl-tris (n-butoxy) silane, 4-pentenyl-tris (n-heptoxy) silane, n-butoxydimethylvinylsilane, bis (n-pentoxy) methylvinylsilane, n-butoxydimethylvinylsilane, Dimethyl-n-pentoxyvinylsilane, allyldipentoxydimethylsilane. Among these, trimethoxyvinylsilane, triethoxyvinylsilane, allyltrimethoxysilane, allyltriethoxysilane, 3-butenyltrimethoxysilane, 4-pentenyl-trimethoxysilane, and the like are desirable, and trimethoxyvinylsilane is particularly desirable.

Specific examples of the organic polysiloxane containing a long-chain alkyl group and an alkoxysilylalkyl group having 16 to 30 carbon atoms in the present invention include, for example, the following general formulas (5), (6), (7) and (8) ) And (9).

Formula (5):

Embedded image

Formula (6):

Embedded image

General formula (7):

Embedded image

Formula (8):

Embedded image

General formula (9):

Embedded image

2. Waterproofing agent The waterproofing agent of the present invention contains, as a main component, a long-chain alkyl group organic polysiloxane having 16 to 30 carbon atoms represented by the general formula (1). Therefore, even if the long-chain alkyl organic polysiloxane having 16 to 30 carbon atoms represented by the general formula (1) is used alone, other waterproofing agents such as wax, paraffin, metal soap, ethylene- Emulsions such as vinyl acetate copolymer, polyvinyl alcohol, acrylic resin, styrene resin, styrene butadiene rubber and asphalt, paints such as vinyl chloride, polyurethane, amino resin, and fluorine resin, and hydrolyzable groups Silane having an alkyl group,
It may be used in combination with a silicone compound such as a silicon macromonomer, a polysiloxane, a silicone resin, a silicone rubber, a hydroxy group-containing polysiloxane and an alkoxy group-containing polysiloxane.

The waterproofing agent of the present invention may optionally contain a curing accelerating catalyst. As a curing acceleration catalyst,
Organics such as tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin marker peptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dibutyltin oxide, monobutyltin oxide, dioctyltin thiocarboxylate, dioctyltin marker peptide Tin compounds, organic lead compounds such as lead octenoate, organic mercury compounds such as phenylmercury propionate, organic antimony compounds, potassium, sodium, calcium, iron, magnesium, mercury, nickel,
Carboxylates such as cobalt, zinc, aluminum, tin, vanadium and titanium; amine salts such as dibutyltinamine-2-ethylhexoate; and other acidic catalysts and basic catalysts, and are not particularly limited. But,
Organotin compounds are preferred. These catalysts can be added, for example, in an amount of 0.001 to 5% by weight based on the specific organic polysiloxane.

The waterproofing agent of the present invention (in the present invention, the expression of the waterproofing agent includes a long-chain alkyl group having 16 to 30 carbon atoms and an alkoxysilylalkyl group represented by the above general formula (1)). In the case where the organic polysiloxane is used alone, and / or a water-proofing composition containing the water-proofing agent, a curing accelerator, a solvent, and other additives is further required. If present, organic and / or inorganic fillers, inorganic fillers, pigments and colorants, and / or inorganic fillers, plasticizers, anti-sagging agents, crosslinkers, diluents, antistatic agents, ultraviolet absorbers, light stabilizers, An antioxidant, a flame retardant, a diluent, a rust inhibitor, an antibacterial agent, an antifungal agent, an antialgal agent, an organic wax, and the like may be added. Among the organic and / or inorganic fillers, reinforcing agents include carbon black, finely divided silica, carbon fiber, glass fiber, and other fibers, and inorganic fillers include calcium carbonate, talc, clay, and silica. Examples of pigments and colorants include inorganic pigments such as iron oxide, chromium oxide, and titanium oxide, and organic pigments such as phthalocyanine blue and phthalocyanine green. Examples of plasticizers include non-reactive silicones represented by polydimethylsiloxane, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, chlorinated paraffins, and petroleum-based plasticizers. , Hydrogenated castor oil, aluminum stearate, calcium stearate, zinc stearate, finely divided silica, and the like. Examples of the crosslinking agent include silicates such as tetraethoxysilane, tetramethoxysilane and oligomers thereof, alkoxysilanes, reactive silicones such as amino-modified silicone, hydroxyl-modified silicone, and carbinol-modified silicone.

Examples of the diluent include water, alcohols such as methanol, ethanol and isopropanol, and one or a mixture of two or more solvents such as hexane, heptane, octane, benzene, toluene, xylene, ether and ester. No. As antistatic agents,
Metals, inorganic compounds such as carbon black, polyether compounds such as polyethylene oxide, cationic surfactants, anionic surfactants, amphoteric surfactants,
Examples include surfactants such as nonionic surfactants, and organic compounds such as amino compounds, amide compounds, urethane compounds, polyols, and other alcohol group-containing compounds. Examples of the organic wax include paraffin, crystallin wax, carnauba wax and the like.

The waterproofing agent of the present invention can be produced by mixing the above-mentioned raw materials by a conventional method. In addition, it is optional to use a one-pack type, a two-pack type or more types depending on the packaging form. Methods for adjusting the one-pack type and the two-pack type are well known to those skilled in the art. For example, in the case of the two-pack type, one of the compounding agents such as the organopolysiloxane of the present invention and other diluents, And other compounding agents such as diluents.

3. Waterproofing method A method for waterproofing the waterproofing agent of the present invention to a target substrate will be described below. The waterproofing agent of the present invention is 1
In the case of the liquid type, the treatment is carried out by a method such as kneading, coating, spraying, spraying, impregnating on the target substrate. In the case of the two-liquid type, the two liquids are mixed, and then processed by a method such as kneading, coating, spraying, spraying, or impregnating, as in the one-liquid type. After the treatment, if the treated material is left in an atmosphere of about 0 ° C. to about 50 ° C., waterproof treatment performance is imparted by reaction with moisture in the air and / or the base material and / or by the action of a curing acceleration catalyst. . The use amount of the waterproofing agent of the present invention with respect to the substrate is not particularly limited. For example, when kneading to the substrate, the amount is 0.01 to 5 watts.
t% is preferred. JIS standard mortar 50mm x 50m
when applied to ^m × 25mm, 10~300g / m ² is preferred. Examples of the substrate to be waterproofed by the waterproofing agent of the present invention include the following. concrete,
Lightweight concrete, precast concrete, lightweight foamed concrete (ALC), mortar, joint mortar,
Natural stone, Otani stone, artificial stone, wall soil, roof soil, tile, tile,
Brick, block, plaster, plaster plaster, dolomite plaster, asbestos cement board, pulp cement board,
Wood grain cement board, glass fiber cement board (GR
C), carbon fiber cement board, or glass wool, rock wool, ceramic fiber, natural fiber, artificial fiber or paper, woven fabric, woven fabric, non-woven fabric, knitted fabric, mat, cloth, for building materials, industrial and domestic use band,
Belts etc.

[0043]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(Example 1)-Synthesis of organopolysiloxane-In a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, a polymer represented by the general formula (10) was added. 47 parts by weight of dimethylhydrosiloxane and 16 parts by weight of toluene were charged.

General formula (10):

Embedded image The mixture was stirred while the temperature was maintained at 70 to 80 ° C., and a 10% toluene solution of chloroplatinic acid was added to the mixture at 15 ppm based on the total amount. Then, while maintaining the temperature, 17 parts by weight of triethoxyvinylsilane was added dropwise to carry out an addition reaction. Further, while maintaining the temperature, 20 parts by weight of 1-hexadecene was added dropwise to carry out an addition reaction in the same manner.
The end of this reaction was determined by a negative AgNO ₃ test for SiH. Thereafter, the reaction mixture was neutralized with sodium hydrogen carbonate, solids were removed by filtration, and the solvent was distilled off at 50 ° C./1 mmHg by a rotary distillation apparatus.
A compound of the general formula (11) represented by the following molecular formula was obtained with a yield of 93%.

General formula (11):

Embedded image

(Example 2)-Synthesis of organopolysiloxane-In a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, a polymer represented by the general formula (12) was added. 36 parts by weight of dimethylhydrosiloxane and 17 parts by weight of toluene were charged.

General formula (12):

Embedded image The mixture was stirred while the temperature was maintained at 70 to 80 ° C., and a 10% toluene solution of chloroplatinic acid was added to the mixture at 15 ppm based on the total amount. Subsequently, while maintaining the temperature, 13 parts by weight of trimethoxyvinylsilane was added dropwise to carry out an addition reaction. Further, while maintaining the temperature, 34 parts by weight of 1-tetracosene was added dropwise to carry out an addition reaction in the same manner.
The end of this reaction was determined by a negative AgNO ₃ test for SiH. Thereafter, the reaction mixture was neutralized with sodium hydrogen carbonate, solids were removed by filtration, and the solvent was distilled off at 50 ° C./1 mmHg by a rotary distillation apparatus.
A compound of the general formula (13) represented by the following molecular formula was obtained in a yield of 95%.

General formula (13):

Embedded image

(Example 3)-Synthesis of organopolysiloxane-In a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, a polymer represented by the general formula (14) was added. 75 parts by weight of dimethylhydrosiloxane and 16 parts by weight of toluene were added.

General formula (14):

Embedded image The mixture was stirred while the temperature was maintained at 70 to 80 ° C., and a 10% toluene solution of chloroplatinic acid was added to the mixture at 15 ppm based on the total amount. Then, while maintaining the temperature, 6 parts by weight of trimethoxyvinylsilane was added dropwise to carry out an addition reaction. While maintaining the temperature, 3 parts by weight of 1-icosene was added dropwise to carry out an addition reaction in the same manner. The end of this reaction was determined by a negative AgNO ₃ test for SiH. Thereafter, the reaction mixture was neutralized with sodium hydrogen carbonate, solids were removed by filtration, and the solvent was distilled off at 50 ° C./1 mmHg by a rotary distillation apparatus.
%, A compound of the general formula (15) represented by the following molecular formula was obtained.

Formula (15):

Embedded image

Example 4 Synthesis of Organopolysiloxane A glass represented by the general formula (16) was placed in a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet. 40 parts by weight of dimethylhydrosiloxane and 17 parts by weight of toluene were charged.

General formula (16):

Embedded image The mixture was stirred while the temperature was maintained at 70 to 80 ° C., and a 10% toluene solution of chloroplatinic acid was added to the mixture at 15 ppm based on the total amount. Next, while maintaining the temperature, 16 parts by weight of triethoxyvinylsilane was added dropwise to carry out an addition reaction. Further, while maintaining the temperature, 27 parts by weight of 1-tria content was added dropwise to carry out an addition reaction in the same manner. The end of this reaction was determined by a negative AgNO ₃ test for SiH. Thereafter, the reaction mixture was neutralized with sodium hydrogen carbonate, solids were removed by filtration, and the solvent was distilled off at 50 ° C./1 mmHg by a rotary distillation apparatus. Equation (1
The compound of 7) was obtained.

General formula (17):

Embedded image

(Example 5)-Synthesis of organic polysiloxane-In a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, a polymer represented by the general formula (18) was added. 29 parts by weight of dimethylhydrosiloxane and 17 parts by weight of toluene were added.

General formula (18):

Embedded image The mixture was stirred while the temperature was maintained at 70 to 80 ° C., and a 10% toluene solution of chloroplatinic acid was added to the mixture at 15 ppm based on the total amount. Subsequently, while maintaining the temperature, 53 parts by weight of trimethoxyvinylsilane was added dropwise to carry out an addition reaction. Further, while maintaining the temperature, 17 parts by weight of 1-tetracosene was added dropwise to carry out an addition reaction in the same manner.
The end of this reaction was determined by a negative AgNO ₃ test for SiH. Thereafter, the reaction mixture was neutralized with sodium hydrogen carbonate, solids were removed by filtration, and the solvent was distilled off at 50 ° C./1 mmHg by a rotary distillation apparatus.
A compound of the general formula (19) represented by the following molecular formula was obtained at a yield of 93%.

General formula (19):

Embedded image

(Comparative Example 1)-Synthesis of organopolysiloxane-In a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, a polymer represented by the general formula (20) was added. 58 parts by weight of dimethylhydrosiloxane and 16 parts by weight of toluene were added.

Formula (20):

Embedded image The mixture was stirred while the temperature was maintained at 70 to 80 ° C., and a 10% toluene solution of chloroplatinic acid was added to the mixture at 15 ppm based on the total amount. Next, while maintaining the temperature, 20 parts by weight of triethoxyvinylsilane was added dropwise to carry out an addition reaction. Further, while maintaining the temperature, 6 parts by weight of 1-octene was added dropwise to carry out an addition reaction in the same manner. The end of this reaction was determined by a negative AgNO ₃ test for SiH. Thereafter, the reaction mixture was neutralized with sodium hydrogen carbonate, the solid content was removed by filtration, and the solvent was distilled off at 50 ° C./1 mmHg by a rotary distillation apparatus.
At 1%, a compound of the general formula (21) represented by the following molecular formula was obtained.

General formula (21):

Embedded image

(Comparative Example 2)-Synthesis of organopolysiloxane-A polymer represented by the general formula (22) was placed in a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet. 54 parts by weight of dimethylhydrosiloxane and 17 parts by weight of toluene were added.

Formula (22):

Embedded image The mixture was stirred while the temperature was maintained at 70 to 80 ° C., and a 10% toluene solution of chloroplatinic acid was added to the mixture at 15 ppm based on the total amount. Next, while maintaining the temperature, 6 parts by weight of ethanol was added dropwise to carry out an addition reaction. Further, while maintaining the temperature, 23 parts by weight of 1-hexadecene was added dropwise to carry out an addition reaction in the same manner. The end of this reaction was determined by a negative AgNO ₃ test for SiH. Thereafter, the reaction mixture was neutralized with sodium hydrogen carbonate, the solid content was removed by filtration, and the solid content was removed by a rotary distillation apparatus.
After the solvent was distilled off at 0 ° C./1 mmHg, a compound of the general formula (23) represented by the following molecular formula was obtained in a yield of 92%.

Formula (23):

Embedded image

(Examples 6 and 7, Comparative Examples 3 and 4)-Waterproofing test-Using the organic polysiloxanes obtained in Examples 1 and 2 and Comparative Examples 1 and 2, waterproofing properties were as follows. The test was performed. Each organic polysiloxane (general formula (11) and general formula (1) was added to 100.0 parts by weight of mortar.
3) 0.3 parts by weight of the general formulas (21) and (23) were added and kneaded with a Glen mixer for 15 minutes to obtain a waterproofed mortar. A mortar plate (50 × 50 × 20 mm) according to JIS A-1404 is formed and
It was allowed to stand in a thermostat at ± 5 ° C., and the mass when the mass reached a constant weight was defined as a dry mass W ₁ (g). The organic polysiloxanes used in Examples 6 and 7 and Comparative Examples 3 and 4 are shown in Table 1.

[0066]

[Table 1] A 1 L death cup was filled with 900 mL of tap water, and the dried waterproofed mortar was gently immersed therein. Remove the sample from the water at appropriate intervals, wipe the surface quickly with a compress, remove water droplets, weigh, and weigh
₂ (g). After weighing, it was immersed again gently.
Thereafter, this operation was repeated to determine the water absorption at appropriate time intervals. The water absorption A _W (%) is calculated by the following equation [JIS R
2205 5.2 Based on the method for measuring the water absorption of refractory bricks] and rounded to one decimal place according to JIS Z8401.

The following formula:

(Equation 1) The results are summarized in FIG. As is clear from FIG. 1, the waterproofing agent of the present invention is excellent in waterproofness and excellent in durability.

(Examples 8-9, Comparative Examples 5-6)-Water Repellency Test of Fiber-Water Repellency of Fiber Treated with Organic Polysiloxanes Obtained in Examples 1-2 and Comparative Examples 1-2 The test was performed. A cloth (10 cm × 10 cm, 100% cotton broad weave # 60) is immersed in 500 g of a solution obtained by diluting each of the organic polysiloxanes obtained in Examples 1 and 2 and Comparative Examples 1 and 2 with isopropyl alcohol to 1%. . Subsequently, mangle (VPM-1, 0.8kgf, manufactured by Tsujii Dyeing Machinery Co., Ltd.)
/ Cm ² ) and dried at room temperature for 72 hours or more, and then subjected to a water repellency test [JIS L-1004,5. 2
3.2 Water repellency Depends on method A (spray method)].
The evaluation criteria are as follows. [Water repellency] 100: no adhesion wetness on the surface 90: slight adhesion wetness on the surface 80: wetness like a water droplet on the surface 70: considerable partial wetness on the surface 50: wetness on the entire surface 0: completely wet over the entire surface The results are summarized in Table 2. The results obtained by using the organopolysiloxane of the present invention obtained in Examples 1 and 2 show complete water repellency, Those obtained in Comparative Examples 1 and 2 were inferior in water repellency.

[0069]

[Table 2]

(Examples 10 to 11, Comparative Examples 7 to 8)-Water Repellency Test of Paper-Repellency of paper treated with the organic polysiloxane obtained in Examples 1 and 2 and Comparative Examples 1 and 2 A water test was performed. Each of the organic polysiloxanes obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was diluted to 5% with isopropyl alcohol, and was reduced to 200 g / m ² on a 30 cm × 30 cm paper without creases, wrinkles, or unevenness. And dried at room temperature for 72 hours or more. The test piece was mounted on a test piece mounting base having a 45 ° slope, and the tip of a biuret containing distilled water at a temperature of 20 ± 1 ° C. was vertically separated from the test piece by 10 cm, so that water droplets could flow down on the test piece. The length was adjusted to be about 30 cm [based on the water repellency test method of JIS P-8137 paper and paperboard]. One drop of water was dropped from the biuret, and the state after the flow was observed. The results are summarized in Table 3. The results obtained by using the organopolysiloxane of the present invention obtained in Examples 1 and 2 show excellent water repellency, whereas Comparative Example 1
2 were inferior in water repellency. This allows
It is understood that the polysiloxane containing a long-chain alkyl group has excellent water repellency.

[0071]

[Table 3]

[0072]

The present invention has the effect of providing an organopolysiloxane having a novel chemical structure. Furthermore, the waterproofing agent containing the same and the waterproofing method using the same have excellent waterproofness for a wide range of members. It has the effect of imparting properties and durability. The waterproofing agent of the present invention has excellent permeability, diffusibility, and reactivity with the base material, and is suitably used for building members such as organic building materials and inorganic building materials, and also for industrial and household fibers or paper. There is an effect that can be done.

[Brief description of the drawings]

FIG. 1 is a diagram showing the results of a waterproofing test performed in Examples 6 and 7 and Comparative Examples 3 and 4 of the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Norihisa Kishimoto Inventor 1-17-1-506, Konan-ku, Yokohama-shi, Kanagawa F-term (reference) 4H020 BA32 4J035 BA02 CA07U CA071 LB07 LB20

Claims (8)

[Claims] 1. An organic polymer represented by the following general formula (1):
Siloxane. General formula (1):[Wherein, R is independently a hydrogen group or a carbon atom 1
Any group selected from monovalent hydrocarbon groups of
¹Is an alkyl group having 16 to 30 carbon atoms, and Q is a general formula: -R²-Si (R³)_3-a(X)_a  (Where R²Is an alkylene group having 2 to 5 carbon atoms, R³
Is a monovalent hydrocarbon group having 1 to 15 carbon atoms, and X is a carbon atom.
An alkoxy group having 1 to 5 children, a is an integer of 2 or 3
You. A represents R, R¹Or selected from Q
X is an integer of 0 to 500, y is an integer of 0 to 20,
z shows the integer of 0-100. However, when y is 0, A
At least one is a Q group, and when z is 0,
At least one is R¹Group, and if y = z = 0, A
Is the Q group, and the other A is R¹Group. ] 2. The organopolysiloxane according to claim 1, wherein R is a methyl group. 3. A waterproofing agent comprising the organopolysiloxane according to claim 1 or 2. 4. The waterproofing agent according to claim 3, wherein the water absorption after 100 hours in the water absorption measurement test is 12% or less. 5. A waterproofing method comprising using the waterproofing agent according to claim 3 for a building member or an organic member. 6. The waterproofing method according to claim 5, wherein the building member is an inorganic building material. 7. The waterproofing method according to claim 6, wherein the inorganic building material is concrete, mortar, wall soil or roof soil. 8. The waterproofing method according to claim 5, wherein the organic member is fiber or paper for building materials, industrial use or household use.