JPH0234997B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antifouling agent, and particularly to an antifouling agent that provides an antifouling coating with excellent weather resistance to architectural structures and the like. Various structures, such as ordinary houses and buildings, are constantly contaminated by automobile exhaust gas containing carbon, hydrocarbons, or grease, and by water containing earth and sand. This contamination also makes it difficult to see signs and signals on signal lights and tunnel walls.
Inside a tunnel, there is a disadvantage that the interior becomes dark due to a decrease in the reflectance of the lighting. For this reason, these types of structures require frequent cleaning with a cloth or brush, but sticky contaminants such as exhaust fumes are difficult to remove from the surface, and the surface must be repainted or replaced with new material. Because it is necessary,
A method of applying an antifouling treatment agent to the surface of a building has also been proposed, but no satisfactory treatment agent has yet been found. The present invention relates to an antifouling agent that can solve these disadvantages, and is based on the general formula

[Formula] [Here, R ^a is the formula R _f R ¹ SR ² − (R _f in the formula is a perfluoroalkyl group having 6 to 20 carbon atoms, and R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms. , R ² is a monovalent group represented by a divalent hydrocarbon group having 2 to 8 carbon atoms), R ^b is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, 0<x≦3, 0≦ y≦3, 0<x+
y<4] and has at least one hydroxyl group and/or halogen atom, an alkoxy group having 1 to 10 carbon atoms, and a silazane group in one molecule, and / or general formula (Here, R ^a and R ^b are the same as above, X is a hydroxyl group or a halogen atom, an alkoxy group having 1 to 10 carbon atoms,
a hydrolyzable group selected from silazane groups, c is 1, 2 or 3, d is 0, 1 or 2, e is 1,
2 or 3, c+d+e=4) or a partial hydrolyzate thereof as a main component. To explain this, the present inventors have conducted various studies on antifouling agents for buildings, especially antifouling agents for sticky pollutants such as exhaust gas.
It has been discovered that organosilicon compounds having a group in which a perfluoroalkyl group is bonded to a silicon atom through a sulfur atom (S) and a divalent hydrocarbon group are extremely effective. The present invention was completed by conducting research on the types and manufacturing methods. As mentioned above, the organosilicon compound which is the main material of the antifouling agent of the present invention has the general formula

【formula】 and/or general formula

It is an organosiloxane, an organosilane, or a partial hydrolyzate thereof represented by the formula: R ^a in this formula is a monovalent group represented by the formula R _f R ¹ SR ² -, and this R _f has a low antifouling effect when the number of carbon atoms is 5 or less, so C ₆ F ₁₃ -, C ₈ F ₁₇ −, C ₁₀ F ₂₅ −,
A perfluoroalkyl group having 6 to 20 carbon atoms, such as C ₁₄ F ₂₉ -, which may be linear, branched, or cyclic, and R ¹ has 1 to 20 carbon atoms. 8 divalent hydrocarbon group, R ₂ has 2 or more carbon atoms
8 is a divalent hydrocarbon group, and examples thereof include a methylene group, an ethylene group, a propylene group, an octylene group, and the like. R ^b is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and includes alkyl groups such as methyl group, ethyl group, and tertiary butyl group, and cycloalkyl groups such as cyclopentyl group and cyclohexyl group. alkenyl groups such as vinyl groups and allyl groups, aryl groups such as phenyl groups and tolyl groups, and chloromethyl in which some of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. and 3,3,3-tolylfluoropropyl group. Also, x and y in this formula () are 0<x≦3, 0≦y
≦3 and 0<x+y<4, and the organosiloxane represented by this formula () contains at least one hydroxyl group and/or halogen atom, and an alkoxy group having 1 to 10 carbon atoms in one molecule. ,
It has a hydrolyzable group selected from silazane groups. In addition, X in this formula () is a hydroxyl group or a hydrolyzable group, and this hydrolyzable group may be the same as the hydrolyzable group to be included in the above-mentioned formula (). Examples of the organosilicon compound represented by the above formula () or () include the following compounds, but are not limited thereto. C ₆ F ₁₃ (CH ₂ B) ₆ S (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , Examples include organosiloxanes as shown in the following three types having at least one hydroxyl group and/or a hydrolyzable group selected from a halogen atom, an alkoxy group having 1 to 10 atoms, and a silazane group. (u, v, w are each positive numbers) C ₁₂ F ₂₅ (CH ₂ ) ₂ S (CH ₂ ) ₂ Si (NH) _3/2 This type of organosilicon compound has the formula R _f , R ₁ SH ......() (R _f and R ₁ are the same as above) to the mercapto group-containing compound, (Here, R ^b is the same as above, n is 0 to 6, p and q are 0<p<4, 0≦q<3, and only 0<p+
q<4, and at least 1 in the molecule
siloxane with hydroxyl or hydrolyzable groups, or with the formula (Here, R ^b , X, n are the same as above, k is 1, 2
or 3, l is 0, 1 or 2, m is 1, 2 or 3, k+l+m=4) can be easily obtained by addition reaction. Mercaptoxy-containing compounds represented by the above formula () include C ₆ F ₁₃ (CH ₂ ) ₂ SH,

[Formula], C ₁₀ F ₂₁ CH ₂ SH, C ₁₄ F ₂₉ (CH ₂ ) ₄ SH, etc. are exemplified, and the above (),
The organosilicon compound represented by the formula () is

[Formula] CH ₂ = CHCH ₂ SiO _3/2 , _CH2 =CH( _CH2 ) _{6SiO3 /2} ,

[Formula] (CH ₂ = CH) ₂ SiO,

Organopolysiloxane containing one or more siloxane units such as [Formula] and having at least one hydroxyl group and/or hydrolyzable group in one molecule, or vinyltrichlorosilane,
Examples include silanes such as vinylvinyldimethoxysilane and allylmethyldiethoxysilane. Since this reaction is an addition reaction, the proportion of the mercapto group-containing compound represented by formula () and the organic silicon compound represented by formulas () and () is as follows: formula(),()
It is preferable that the number of moles of unsaturated groups therein be approximately equal moles. This reaction may be carried out in an organic solvent or in an emulsion system, but in an organic solvent, benzoyl peroxide, t
- It is preferably carried out in the presence of an organic peroxide such as butyl hydroperoxide, cumene hydroperoxide, or t-butyl peroxide, or an azo compound such as azobisisobutyronitrile, or carried out in an emulsion system. This may be carried out in the presence of ammonium persulfate, potassium persulfate, etc., but it may also be carried out by ultraviolet irradiation in the presence of a photosensitive compound such as benzoin or benzophenone. The antifouling coating material of the present invention is mainly composed of an organosilicon compound represented by the above-mentioned general formula () and/or (). It may also be used as a copolymer obtained by reacting with cyclic siloxanes such as octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane in the presence of reactive silanes and/or siloxanes, as well as zinc A tin-based, titanium-based condensation catalyst, or a platinum-based addition reaction catalyst may be added. Also,
This organosilicon compound may be appropriately added with various additives that are added to this type of antifouling agent, such as antistatic agents, water repellents, oil repellents, pigments, etc., as long as they do not impede the purpose of the present invention. May be blended. In the treatment of buildings with the antifouling treatment agent of the present invention, the composition of the present invention can be used to treat aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, fluorinated hydrocarbons, ketones, ethers, alcohols, etc. It can be diluted with an appropriate organic solvent or water, or dispersed in the solvent, and then applied to the object by spraying, brushing, etc., followed by drying or heat treatment if necessary. good. Buildings treated in this way have a transparent film containing perfluoroalkyl groups and siloxane skeletons formed on the treated surfaces, so they exhibit excellent weather resistance, water and oil repellency, and are resistant to water and oil stains. Although it exerts a staining effect, this film is also highly durable, and has excellent resistance to various deterioration conditions due to the condensation reaction caused by the functional groups in the molecule, so it has the advantage that this effect lasts forever. give sex.
As mentioned above, the composition of the present invention exhibits excellent antifouling properties for buildings, but this is also useful for surface treatments of various devices and electronic materials where oil stains are a problem, as well as for urethane, epoxy, etc. It is also said to be useful as a mold release agent for various adhesive resins, such as, and for surface treatment of paints. Next, examples of the present invention will be described. In the examples, the degree of contamination as a result of an antifouling test shows the results observed with the naked eye, and this color difference was measured using a colorimeter model 100DP [Nippon Denshoku Kogyo Co., Ltd. ) made by product name], and the brightness is 0 (black) to 100 (white).
It is shown as a numerical value. The chemical structural formulas of the organosiloxanes and organosilanes obtained in the table were determined from the results of infrared spectroscopy, nuclear magnetic resonance analysis, elemental analysis, etc. of the organosilane. Example 1 Internal volume 1 with stirrer, thermometer and reflux condenser
Add vinyltrimethoxysilane 74 to the flask.
g, _C8F17 ( _CH2 ) _SH240g , methyl ethyl ketone
When 314 g and 3.1 g of azobisisobutyronitrile were charged and an addition reaction was carried out at 60°C for 5 hours under nitrogen gas reflux, a pale yellow transparent liquid was obtained, which was analyzed to have the formula C ₈ F ₁₇ CH ₂ S(CH ₂ ) ₂ Si(OCH ₃ ) ₃
(referred to as sample A). Next, this was diluted to 5% with 1,1,1-trichloroethane, and this was used to cure a silicone rubber composition, Sealant 70 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), which is used as a building sealant. After brushing the surface of the silicone rubber and letting it dry, apply this product along a national highway with a lot of traffic.
After exposure for several months, the results regarding the surface condition as shown in Table 1 below were obtained. Example 2 200 g of sample A obtained in Example 1 and 50.5 g of methyltrimethoxysilane were placed in the same flask as in Example 1.
Add 50g of acetone and 30% while stirring.
After dropping 1.0 g of HCl, the temperature was gradually raised under a nitrogen gas stream and the reaction was carried out for 2 hours under refluxing acetone to complete the cohydrolysis condensation reaction. After cooling, the mixture was neutralized with propylene oxide and filtered. A pale yellow transparent solution (sample B) was obtained, which was analyzed by the following formula: It was confirmed that it contained 4.5% by weight of hydroxyl groups. Next, this sample B was diluted to 5% with 1,1,1-trichloroethane and tested as an antifouling agent in the same manner as in Example 1.
This showed the results as shown in Table 1 below. Example 3 In the same flask as in Example 1, the following formula was added. 78g organopolysiloxane, C ₁₀ F ₁₂
(CH ₂ ) ₂ SH 1.74g, isopropyl alcohol 222
When the mixture was charged with 2.2 g of azobisisobutyronitrile and 2.2 g of azobisisobutyronitrile and allowed to react at 60°C for 8 hours under a nitrogen gas flow, a slightly cloudy liquid was obtained, and upon cooling, a white solid precipitate (sample C) became. As a result of analysis, this sample C has the following formula: It was confirmed that it was an organosiloxane represented by 1,1,2-trifluoro-
When diluted with 1,2,2-trifluoroethane to 5% and examined its physical properties as an antifouling agent in the same manner as in Example 1, the results shown in Table 1 below were obtained. . Example 4 The following formula was added to the same flask as in Example 1. 76g organopolysiloxane, C ₈ F ₁₇
( _CH2 ) _2SH96g , 1,1,1-trichloroethane
When 172 g and 1.7 g of azobisisobutyronitrile were charged and the mixture was heated at 60°C for 8 hours under a nitrogen gas stream, a slightly yellow and transparent solution was obtained. It was confirmed that it was an organosiloxane shown by Next, a sample (sample D) was prepared by adding 0.7 g of methyltrimethoxysilane and 0.1 g of dibutyltin dilaurate to 344 g of this solution.
When diluted to 5% with 1,1-trichloroethane and examined for its physical properties as an antifouling agent in the same manner as in Example 1, the results shown in Table 1 below were obtained. Example 5 In the same flask as in Example 1, add 250 g of water and toluene.
Add 70g and 108g of isopropyl alcohol, and add vinyltrichlorosilane while stirring.
32.3g, methyltrichlorosilane 119.2g and toluene 280g were added dropwise to carry out a cohydrolysis reaction, and when aged for 1 hour, (CH ₂ =
CH) SiO _3/2 units 20 mol% CH ₃ SiO _3/2 units 80 mol%
A resin composition was obtained. Next, 69.4 g of this resin composition, 96.0 g of C ₈ F ₁₇ (CH ₂ ) ₂ SH, 165.4 g of methyl ethyl ketone, and 1.7 g of azobisisobutyronitrile were placed in a flask with an internal volume of 500 ml, and the mixture was heated at 60°C under a nitrogen gas flow. After reacting for 8 hours, a pale yellow transparent liquid (sample E) was obtained, which was analyzed by the following formula: It was an organosiloxane containing 2.8% by weight of hydroxyl groups. Next, this sample E was diluted to 5% with 1,1,1-trichloroethane, and its physical properties as an antifouling agent were examined in the same manner as in Example 1. The results were obtained. Example 6 In the cohydrolysis reaction in Example 5, vinylmethyldichlorosilane 24.5 was used as the raw material.
g, treated in the same manner except that 33.6 g of dimethyldichlorosilane and 91.9 g of phenyltrichlorosilane were used ( _CH2 =CH) _CH3SiO units 20 mol%,
A resin composition consisting of 30 mol % of (CH ₃ ) ₂ SiO units and mol % of C ₆ H ₅ SiO _3/2 units was prepared, and the internal volume was
52.0g of this and C ₈ F ₁₇ in a 500ml flask
When 48.0 g of (CH ₂ ) ₂ SH, 100 g of methyl ethyl ketone and 1.0 g of azobisisobutyronitrile were charged and reacted at 60°C for 8 hours under a nitrogen gas stream, a pale yellow transparent liquid (sample F) was produced. is obtained, which is the result of analysis and is expressed by the following formula It was confirmed that it was an organosiloxane containing 2.2% by weight of hydroxyl groups. Next, this sample F was diluted to 5% with 1,1,1-trichloroethane and its properties as an antifouling agent were examined in the same manner as in Example 1. The results were shown. Example 7 Into the same flask as in Example 1, 57.6 g of vinyltrichlorosilane, 242.4 g of C ₁₂ F ₂₅ (CH ₂ ) ₂ SH 2, 300 g of dehydrated methyl ethyl ketone and 3.0 g of azobisisobutyronitrile were charged, and the flask was heated for 60 g under a nitrogen gas stream. ℃
When the addition reaction was carried out for 5 hours, a yellow transparent liquid was obtained, which was analyzed to have the formula C ₁₂ F ₂₅ (CH ₂ ) ₂ S(CH ₂ ) ₂ SiCl ₃ . Confirmed (sample G). Next, this product was diluted to 5% with 1,1,2-tricfluoro-1,2,2-trichloroethane and tested as an antifouling agent in the same manner as in Example 1. The results shown in Table 1 below were obtained. Example 8 300 g of the sample G obtained in Example 7 was placed in the same flask as in Example 1, and after cooling to 10°C, ammonia gas was blown into this liquid at a flow rate of 6 per hour for 6 hours to cause a reaction. After confirming that excess ammonia gas was discharged from the exhaust port, the reaction was stopped and the by-produced NH ₄ Cl was removed by filtration. A yellow transparent liquid was obtained, which was analyzed as [C ₁₂ It was confirmed that the sample was _F25 ( _CH2 ) _2S ( _CH2 ) _2Si (NH) _3/2 ] _n (Sample H). This material was then converted into 1,1,2-trifluoro-
diluted to 5% with 1,2,2-trichloroethane,
When it was tested as an antifouling agent in the same manner as in Example 1, the results shown in Table 1 below were obtained. Comparative Examples 1 to 3 ( _CH2 =CH)SiO3 _/2 obtained in Example 5 described above
69.4 g of a resin composition consisting of 20 mol% units and mol% CH ₃ SiO _3/2 units, 56.0 g of C ₄ F ₉ (CH ₂ ) ₂ SH, 125.4 g of methyl ethyl ketone and 1.3 g of azobisisobutyronitrile were used. When treated in the same manner as in Example 5, a pale yellow transparent liquid (Sample I) was obtained, which was analyzed by the following formula: It contained 3.7% by weight of hydroxyl groups. Next, this was diluted to 5% with 1,1,1-trichloroethane and its physical properties as _{an antifouling} agent were investigated in the same manner as in Example ₁ . ₂ Si(OCH ₃ ) ₃ (Sample J)
When this material was treated in the same manner and its physical properties were investigated, the results shown in Table 1 below were obtained. Note that Comparative Example 3 in the table shows data for an untreated product.

【table】

【table】

Claims (1)

[Claims] 1. General formula [Here, R ^a is the formula R _f R ¹ SR ² − (where R _f is the number of carbon atoms from 6 to
20 perfluoroalkyl groups, R ¹ has 1 or more carbon atoms
8 divalent hydrocarbon group, R ² is a monovalent group represented by a divalent hydrocarbon group having 2 to 8 carbon atoms), R ^b is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, 0 <x
≦3, 0≦y≦3, 0<x+y<4],
and an organosiloxane having in one molecule at least one hydroxyl group and/or a hydrolyzable group selected from a halogen atom, an alkoxy group having 1 to 10 carbon atoms, and a silazane group, and/or the general formula (Here, R ^a and R ^b are the same as above, X is a hydrolyzable group selected from a hydroxyl group and/or a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a silazane group, d is 0, 1 or 2,
An antifouling agent characterized in that the main material is an organosilane represented by (e is 1, 2 or 3, c+d+e=4) or a partially hydrolyzed product thereof.