JPH022894B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silicone rubber tent curtain material, particularly to a silicone rubber tent curtain material having excellent weather resistance and stain resistance. (Prior art) Conventionally, tent curtain materials have been commonly made of fibers reinforced with polyvinyl chloride, polyethylene, polyester, acrylic resin, fluorocarbon resin, etc., but these are resistant to automobile exhaust gas and It is constantly contaminated by factory waste gas, as well as dust containing carbon, hydrocarbons, oxides, sulfides, etc. floating in the air generated by natural phenomena such as yellow sand and volcanic eruptions. The surface has the disadvantage that dust adhesion and accumulation occur, which reduces light absorption and also deteriorates light resistance and weather resistance, so materials treated with fluorine-based resin, which has excellent light resistance and weather resistance, are also used. However, this method has the disadvantages of poor light transmittance and flexibility, the tendency for wrinkles and cracks to form when the tent curtain is folded during use or storage, high specific gravity, and high cost. For this reason, tent curtains made of silicone rubber materials, which have excellent light resistance, weather resistance, and flexibility, have been developed and have various characteristics not found in other resins. They have the drawbacks of being easily contaminated, having poor lighting performance, and poor appearance. (Structure of the Invention) The present invention relates to a silicone rubber tent curtain that solves the above-mentioned disadvantages. , general formula

[Formula] [Here, R ^a is the formula R _f R ¹ SiR ² − (R _f in the formula is a perfluoroalkyl group having 6 to 20 carbon atoms, and R ¹ is 2 having 1 to 8 carbon atoms.
valent 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, R ^c is a hydroxyl group and/or hydrolyzable group, 0<x≦3, 0≦
An organosiloxane represented by y≦3, 0<z≦3, 0<x+y+z<4] and having at least one hydroxyl group and/or hydrolyzable group in one molecule, and/or a general formula

^{Organosilane or _} It is characterized by being coated with an antifouling agent containing the partial hydrolyzate as a main component. To explain this, the present inventors have particularly shown that weather resistance,
As a result of various studies on the development of a silicone rubber tent curtain with excellent stain resistance, it was found that at least one surface of the silicone rubber tent curtain had a sulfur atom (S) and a divalent hydrocarbon group interposed in the molecule. We discovered that coating with an organosilicon compound having a perfluoroalkyl group bonded to a silicon atom is extremely effective, and we conducted research on the types of compounds and manufacturing methods of this type of compound, and developed the present invention. completed. As mentioned above, the organosilicon compound which is the main material of the antifouling agent used to obtain the silicone rubber tent curtain of the present invention has a hydroxyl group and/or a hydrolyzable group in one molecule. and/or general formula These are organosiloxanes, organosilanes, or hydrolysates thereof. 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 −,
It is a perfluoroalkyl group having 6 to 20 carbon atoms such as C ₁₄ F ₂₉ -, but this R ¹ is a perfluoroalkyl group having 1 to 20 carbon atoms.
The divalent hydrocarbon group 8, ^R2, is a divalent hydrocarbon group having 2 to 8 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and an octylene group. In addition, this R ^b is a hydrogen atom or has 1 to 1 carbon atoms.
20 monovalent hydrocarbon groups, including alkyl groups such as methyl, ethyl, and tertiary butyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, alkenyl groups such as vinyl and allyl groups, and phenyl groups. aryl groups such as tolyl groups, as well as chloromethyl groups and 3,3,3-trifluoropropyl groups in which some of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. is exemplified. Note that R ^c in this formula
is a hydroxyl group or a hydrolyzable group, and examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, an amide group, an alkenyloxy group, and a silazane group. Examples of the organosilicon compound represented by the above formula () or () include the following compounds, but are not limited thereto. _C6F13 ( _CH2 ) _6S ( _CH2 ) _{3Si ( OCH3} ) ₃ , This type of organosilicon compound is, for example, a mercapto group-containing organic compound represented by the formula R _f R ¹ SH () (R _f and R ¹ are the same as above). (Here, R ^b and R ^c are the same as above, n is 0 to 6, l,
m and k are 0<l<4, 0≦m<3, 0<k<
3. Siloxane having at least one hydroxyl group or hydrolyzable group in its molecule, or having the formula: 0<l+m+k<4) (Here, R ^b , R ^c , n are the same as above, e, g are 1
or 2, f is 0, 1 or 2, then e+f+
The silane represented by g=4) can be easily obtained by carrying out an addition reaction. The mercaptoxy-containing organic 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 organosilicon compounds represented by the above formulas () and () are

[Formula] CH ₂ = CHCH ₂ SiO _3/2 ,

[Formula] CH ₂ = CH (CH ₂ ) ₆ SiO _23/2 ,

[Formula] (CH ₂ = CH) ₂ SiO,

[Degree of pollution]

The surface of the solar cell is covered with the silicone rubber tent curtain material of the present invention, and the amount of power generated by sunlight passing through this tent material (mA) and the amount of power generated by direct sunlight without this covering (mA) ) to measure the change in contamination due to outdoor exposure over time, and this was taken as the degree of contamination. [Color difference] Measured using a colorimeter, model 100DP [product name manufactured by Nippon Denshoku Industries Co., Ltd.], and the brightness was set to 0 (black).
Indicated by a numerical value of ~100 (white). 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 a thermosetting silicone rubber containing 10 mol% of diphenylsiloxane units and having a refractive index of n _25D = 1.45 was mixed with glass cloth WL110B28.
[Product name manufactured by Nittobo Co., Ltd.] was applied and cured by heating, and the above antifouling treatment agent was brushed onto the surface of a 0.6 mm thick silicone rubber base material with a light transmittance of 65%. When exposed along a national highway with heavy traffic, results were obtained regarding the surface condition as shown in Table 1 below. Example 2 The following formula was added to the same flask as in Example 1. 76g organopolysiloxane, C ₈ F ₁₇
( _CH2 ) _2SH 96g, 1,1,1-trichloroethane 172g and azobisisobutyronitrile 1.7g
When the mixture was prepared and incubated at 60°C for 8 hours under a nitrogen gas stream, a pale yellow transparent solution was obtained, which was analyzed using the following formula: It was confirmed that it was an organosiloxane shown by Next, a sample (sample B) was prepared by adding 0.7 g of methyltrimethoxysilane and 0.1 g of dibutyltin dilaurate to 344 g of this solution.
This antifouling treatment agent was diluted to 5% with 1,1-trichloroethane and applied to the surface of a silicone rubber base material in the same manner as in Example 1, and its effects were examined, as shown in Table 1 below. The results were obtained. Example 3 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.
24.5g, dimethyldichlorosilane 33.6g and phenyltrichlorosilane 91.9g and toluene
After dropping 280g to perform a cohydrolysis reaction and aging for 1 hour, (CH ₂ = CH)SiO _3/2
20 mol% units, 30 mol% ( _CH3 ) _2SiO units and
A resin composition consisting of 50 mol % of _1.5 units of C ₆ H ₅ SiO was obtained. Next, 52.0 g of this resin composition, 48.0 g of C ₈ F ₁₇ (CH ₂ ) ₂ SH, 100 g of methyl ethyl ketone, and 1.0 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 stream. 8
After reacting for a period of time, a pale yellow transparent liquid (sample C) was obtained, which was analyzed by the following formula: It was confirmed that it was an organosiloxane shown by Next, add methyltrimethoxysilane to this solution.
After adding 2.0 g and 0.1 g of dibutyltin dilaurate, the antifouling agent was diluted to 20% with 1,1,1-trichloroethane. Next, addition vulcanization type silicone rubber containing 30 mol% of diphenylsiloxane units and having a refractive index of n ²⁵ _D = 1.51 was applied to the glass cloth WE10G104 [trade name manufactured by Nittobo Co., Ltd.], and then heat cured. film thickness
A 0.4 mm base material with a light transmittance of 95% was made, the above antifouling agent was applied to this base material using Bancoat, and the temperature was heated at 150°C.
A surface-treated curtain material was obtained by heat treatment for 1 hour and hardened, and its effects were examined in the same manner as in Example 1, and the results shown in Table 1 below were obtained.

【table】

Claims (1)

[Claims] 1. On at least one side of a base material made of silicone rubber or a mixture of silicone rubber and other synthetic rubber, the general formula [Formula] [where R ^a is the formula R _f R ¹ SR ² − (in the formula, R _f has 6 to 6 carbon atoms)
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, R ^c is a hydroxyl group and/or a hydrolyzable group, 0<x≦
3, 0≦y≦3, 0<z≦3, 0<x+y+z<
4] and having at least one hydroxyl group and/or hydrolyzable group in one molecule, and/or an organosiloxane having the general formula [Formula] (where R ^a , R ^b , and R ^c are as defined above). Same, p and r are 1
or 2, q is 0, 1 or 2, p+q
1. A silicone rubber tent curtain material coated with an antifouling agent containing organosilane represented by +r=4) or a partially hydrolyzed product thereof as a main component.