JPS6051103A - Antifouling treatment - Google Patents

Abstract

PURPOSE:An antifouling treatment useful as an antifouling agent for buildings, especially having weather resistance to exhaust gas, comprising an organic silicon compound containing perfluoroalkyl group linked through S and bifunctional hydrocarbon group to silicon atom in the molecule. CONSTITUTION:An antifouling treatment comprising an organosiloxane shown by the formula I [R<2> is monofunctional group shown by the formula RfR<1>SR<2> (Rf is 6-20C perfluoroalkyl; R<1> is C1-8 bifunctional hydrocarbon; R<2> is C2-8 bifunctional hydrocarbon); R<b> is H, C1-20 monofunctional hydrocarbon; x and y are in 0<x, y<=3; 0<x+y<4], having at least one OH and/or hydrolyzable group in one molecule and/or an organosiloxane shown by the formula II (X is OH, or hydrolyzable group; 0<z<=3, 0<x+y+z<=4), its partial hydrolyzate as a main component. Useful for buildings, surface treatment of various devices having problem of oil pollution, surface treatment of electronic materials, surface treatment of coating compound, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an antifouling treatment agent, particularly for building materials that have weather resistance σ.
] The present invention relates to an antifouling treatment agent that provides an excellent antifouling coating.

Various buildings, such as ordinary houses and buildings, are constantly contaminated by carbon, automobile exhaust gas containing expanded hydrogen or grease, and water containing earth and sand; Due to this contamination, road signs, signal lights, tunnel walls, etc. are also disadvantageous in that signs and signals become difficult to see, and the interior of tunnels becomes dark due to a decrease in the reflectance of lighting. For this reason,
This type of structure requires frequent cleaning with a cloth or brush, but sticky contaminants such as exhaust gases can slough off the surface.

σ) Since it is necessary to regrade the surface and replace it with a new material, a method of applying an antifouling treatment agent to the building surface has been proposed, but it seems unlikely. Not served.

The present invention is an antifouling treatment agent (with respect to σ) that can solve these disadvantages - it has the general formula SiR-(
In the formula, Rf is a perfluoroalkyl group having 6 to 2 carbon atoms, R1 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and R2 is a divalent hydrocarbon group having 2 to 8 carbon atoms. Group -Rb
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) -
organosylochitin having at least one hydroxyl group and/or hydrolyzable group in one molecule, and R
b, x=y is the above (two same, X is a hydroxyl group and/or a hydrolyzable group, organosilane or its σ shown by 0<z≦:1O(x+y+2≦4)) with the main component as a partial hydrolyzate It is a percentage sign that

To explain this, 1. The present inventors have developed an antifouling treatment agent for buildings.
This is the result of a study on two types of antifouling agents, especially for sticky pollutants such as exhaust gas.

It was discovered that organosilicon compounds having a group in which a perfluoroalkyl group is bonded to a silicon atom through a sulfur atom (PJ) and a divalent hydrocarbon group are extremely effective. The present invention was completed by conducting research on the types and manufacturing methods of .

As mentioned above, the organosilicon compound which is the main material of the antifouling treatment agent of the present invention has the general formula Rb +V RSiO... (11X 4-X-V and/or Rb Y the general formula RSiX... ... It is an organosiloxane-organosilane shown by Tatto Z or its partial hydrolyzate.

Ra in this formula is a monovalent group represented by the formula RR"SR"-, and this R1 has a low antifouling effect when the number of carbon atoms is 5 or less. The number of carbon atoms is 10 25
14 29 6 to 20 perfluoroalkyl groups, which may be linear, monobranched, or cyclic, and 4 this R
is a divalent hydrocarbon group having 1 to 8 carbon atoms.

R is a divalent hydrocarbon group having 2 to 8 carbon atoms, and examples thereof include a methylene group, an ethylene group, a globylene group, and an ogtylene group. monovalent hydrocarbon groups, including alkyl groups such as methyl, ethyl, and tertiary butyl; chloroalkyl groups such as cyclopentyl; vinyl groups; alkenyl groups such as allyl; Phenyl group, tolyl group tx, aryl group, and FI of these groups
Examples thereof include a glolomethyl group and a 3,3°3-trifluoroglopyl group in which a part of the hydrogen atom bonded to the Rr''a atom is substituted with a halogen atom -i/anohado.

In addition, in this formula, the hydroxyl group or the hydrolyzable group may be the same as the hydrolyzable group described above (which should be included in Formula 11).

Examples of this include a halogen atom-alkoxy group, an acyloxy group, an aminoxy group, an amide group, an alkenyloxy group, and a V-raden group.

The following compounds are exemplified as the organosilicon compound represented by the above formula (1+ or (II)).

Of course, this is not limited to these.

c6F13(CH2)6S((3Hρ3Si(OCH3
), -OH 1゜OF (OH) 5(OR) 5i(00B) -8
172222262 0H+ H8 (uv-vr are positive numbers, respectively) This type of organosilicon compound is represented by the formula 1, for example, RR'SH (R, -R are the same as C1 above). The mercapto group-containing tetramerization b to -l-R is the same as above, n is 0 to 6, p and q　0 (p(4-U≦q〈3, Tazoshi 0 < p+q〈4)
and has at least one hydroxyl group or hydrolyzable group in its molecule, and has the formula (O)i = CH((,H2)n)pSiXr ・
・Song (Vl to \ to I (-X-n.p.q is the same as above.
r is 11 ( r ( 3 , Tazoshi 0 ( p + q
+ r≦4) is subjected to an iris addition reaction (2) to obtain 6-52. As a mercaptoxy-containing compound represented by the above Tsukuda formula, OH3 (]6F,3 (OH2)2SH , C8H,, (OH,
)30H8H +C8. F, 10H, SH + 01
, F2,, (OH2)4SR, etc. are exemplified, and the upper Gt
(m- (OH3O as an organic silicate compound represented by the Vl formula)] = CH5iO + OH = OHQH, SiO
3/, -2 OH60)12=OH(IH)SiO+0)],=OR
(OB,)s s"!/2 -0, H, 01 0H=OH810- (cH,=CH), Sin.
-0B.

an organopolysiloxane containing at least one hydroxyl group and/or a hydrolyzable group in one molecule thereof;

Examples include silanes such as vinyltrichlorosilane and vinylvinyldimethoxysilane-allylmethyljethoxysilane. The compounding ratio of this mercapto group-containing compound represented by the formula ff1l+ and the organosilicon compound represented by the formula (IL (Vl) is an advantage since this reaction is an additive reaction) and the mercapto group and 26v It is preferable to adjust f2 so that the number of moles of the unsaturated groups in ) and (i) is approximately equal to each other. This reaction may be carried out in an organic solvent or in an emulsion system, but the reaction in an organic solvent is performed using benzoyl peroxide'.

Organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, i/-1-butyl peroxide, etc. or azopisisobutyroni)
This may be carried out in the presence of an azo compound such as IJL, or in the presence of ammonium persulfate, potassium persulfate, etc. in case of C1 in an emulsifying system, but this may also be carried out in the presence of a photosensitive compound such as benzoin or benzophenone. It may also be carried out by irradiation with ultraviolet rays in the presence of.

The antifouling coating material of the present invention is mainly composed of an organosilicon compound represented by the above-mentioned general formula [1 and/or (Ill). ] In the presence of ogtamethylcycloC7te)rasiloxane, tetramethylcycloa
It may also be used as a copolymer obtained by reacting with a cyclic siloxane such as tetrasiloxane2, which is also reactive σ) silane and/or siloxane, as well as zinc-based, soot-based, titanium-based combination catalysts, A platinum-based addition reaction catalyst may be added. In addition, various additives 1, such as antistatic agents, are added to this type of antifouling treatment agent C2 in this organic silicon compound.

Water repellents, oil repellents, pigments, etc. may be added as appropriate to the extent that they do not impede the object of the present invention.

In the treatment of buildings with the antifouling treatment agent of the present invention, the composition of the present invention is used to treat aliphatic hydrocarbons and aromatic hydrocarbons.

Chlorinated hydrocarbons, fluorinated hydrocarbons, Ghent-based, ether-based, alcohol-based, etc., as appropriate σ) After diluting with an organic medium or water, or dispersing in the relevant solvent, apply this material with gray paint11. - After coating the object to be treated with a brush or the like, it may be dried or heat treated if necessary. When treated in this way, it exhibits excellent weather resistance, water and oil repellency, and has an antifouling effect against water-based and oil-based stains. Due to the double condensation reaction, it has excellent resistance to various degrading conditions - an advantage that this effect is permanent. As mentioned above, the composition of the present invention exhibits excellent antifouling properties for buildings, but this is also useful for surface treatment of various devices and electronic materials where oil stains are a problem, and also for use in surface treatments of urethane.

It is also useful as a mold release agent for various adhesive resins such as epoxy, and for surface treatment of paints.

Next, examples of the present invention will be described. The degree of contamination as the result of the antifouling test in one of the two cases shows the observation result with the naked eye.
(manufactured by Nippon Heavy Industries Co., Ltd., product name).
The brightness is shown as a numerical value from 0 (black) to 100 (white).

Example 1 In a flask with an internal volume of lt equipped with a stirrer, a thermometer, and a reflux condenser, one vinyltrimethoxyl/i/lump 49-08 was added.
F,, (OH2)SH240, 314 g of li'-methyl ethyl ketone and 3.1 g of azobisisobutyminitrile
When 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 as 08F, 0H2S(OH2)2S4 (Q
It was confirmed that the sample was represented by OHs )3 (referred to as sample A).

Next, this was diluted to 5 parts with 1.1.1-trichloroethane, and this was used to cure a silicone rubber composition, Sealant 70 (product name of Shin-Etsu Chemical Co., Ltd.), which is used as a sealant for buildings. The surface of the silicone rubber obtained was brushed twice and dried, and then exposed in the dark for three months along a busy national highway.The surface condition was as shown in Table 1 below. The results were obtained.

Example 2゜Sample A2 obtained in Example 1 was placed in the same flask as in Example 1.
0 (l), 50.5 g of methyltrimethoxysilane and 50 g of acetone, and while stirring, 30% HO11
,0,! / was added dropwise, the temperature was gradually raised under a stream of nitrogen gas, and the reaction was carried out for 2 hours under refluxing acetone to complete the cohydrolytic condensation reaction.After cooling, neutralization was carried out with propylene oxide, and after passing through 1 FI, a pale A yellow, transparent solution (sample B) was obtained, which upon analysis was confirmed to have a linear formula (% formula %).

Next, take this sample B as 1.1.1-)! It was diluted to 5% with Jia loethane and tested as an antifouling agent in the same manner as in Example 1.

This showed the results as shown in Table 1 below.

The following formula was added to the same flask as in Example 1. 78g of organopolysiloxane represented by

0, oF2. (OH2)28H1,741 222 g of inglovil alcohol and 2.2 g of azobisisobutyronitrile were charged and the reaction was carried out at 60°C for 8 hours under a nitrogen gas stream. A slightly cloudy liquid was obtained. When cooled, it became a white solid precipitate (sample 0).

This sample C was confirmed to be organosylochitin expressed by the linear formula Pj of the analysis, and was converted into
) Dilute to 5% with refluoroethane and give 49! l 1
When its physical properties as an antifouling agent were examined in the same manner as above, the results shown in aN IF2 below were obtained.

Example 4 Add the following formula to the same flask as 1 on the power level side. 76g of organopolysiloxane represented by

08 F□7 (OH2,)28R96,9-1,1,
1-) 172 g of dichloroethane and 1.7 g of azobisisobutyronitrile were charged and heated under a nitrogen gas stream (26 g).
When the reaction was carried out at 0°C for 8 hours, a clear yellow solution was obtained, which was confirmed by analysis to be organosylochitin represented by the linear formula.

(2. Make a sample (Sample D) by adding 0.7 g of methyltrimethoxysilane and 1 g of dibutyltin dilaurate O to 344 g of this solution - 1.1.1-)I
Dilute to 5% with JR σ Roetage.

The physical properties of this antifouling agent were examined in the same manner as in Example 1, and the results shown in Table 1 below were obtained.

Example 5゜Same flask I as Example 1: 250 g of water - 70 g of toluene
Add g and isoglobil alcohol losy, stir, then add 32.3 L of vinylt IJ chlorosilane.
Methyltricσrosilane 119.2. ! When i+ and toluene 280I were added dropwise to perform a cohydrolysis reaction and then aged for 1 hour, + (0H2=OH) Si
03/2 unit 20 moles CH3S103/2 unit (S7
A resin composition consisting of 80 moles was obtained.

Next, add this resin composition to a flask with an internal volume of 500 liters 69.4 L 08F, (OH2)2SH96,O
L methyl ethyl ketone 165.4f! When 1.711 l of azobisisobutyanitrile were charged and reacted at 60°C for 8 hours under a mononitrogen gas stream, a pale yellow transparent liquid (sample E) was obtained. %).

Second, this Sandal E was diluted to 5% with 1.1.1-) dichloroethane, and its physical properties as an antifouling agent were examined in the same manner as in Example 1.

The results shown in Table 1 below were obtained.

Example 6 In the cohydrolysis reaction in Example 5, 24.5 I of vinylmethyldiglorosilane, 33.6 g of dimethyldichlorosilane and 91.9 g of phenyltrichlorosilane were used as raw materials, but the same procedure was followed ( O
H2 = (3H)OH3SiO unit 20 molar coefficient + (OH
5) 2SiO units 30molti and 0, HsS
Prepare a resin composition consisting of 50 moles of L O,7, and place 52.0 g of this in a flask with an internal volume of 500 m1.
08F1. (OH2)2SH48,01 100 g of methyl methyl ketone and azobisisobutymini) IJ 1
．． When the reaction was carried out at 60°C for 8 hours under a nitrogen gas stream, a pale yellow transparent liquid (Susiguru F) was obtained, which was analyzed by the linear formula % formula %. It was confirmed that it was the organosiloxane shown in the figure.

Next, this sandal F was diluted to 5 parts with l,i,1-trichloroethane and its properties as an antifouling agent were examined using the same method as in Example 49111.
The results were as shown above.

Comparative Examples 1 to 3 Resin composition consisting of 20 moles of (CH=CH)SiO units obtained in Example 5 described above + 80 moles of 0H3Si037□ units @69.4. ! 7 and OF (OH)SH
When 25.4 g of 4922 56,0JF-methyl ethyl ketone and 1.311 g of azobisisobutyronitrile were treated with C2 in the same manner as in Example 5, a pale yellow transparent liquid (Sandal G) was obtained. is the result of analysis (8” s7
* ) 20 (S' 03/2) 80.

Next - kohwo1. , 1, ]-]4 diluted to 5% with ligroroeta and examined for its physical properties as an antifouling agent in the same manner as in Example 1. (, Su1117
211 13 sample I() was used, and when it was mixed, it was subjected to the same l-treatment and its physical properties were examined, and the results shown in Table 1 C-2 below were obtained.

Note that Comparative Example 3 in the table shows data for untreated products.

Table 1 (Note) Untreated: 111! indicates the surface of the cured product of Sealant 70 which was left untreated and exposed for 30 days. The blank indicates the value of the surface of the cured product before exposure.

Claims (1)

[Claims] L General formula Rb y (KN f-Ra & K RR" 8 R2 (in the formula Rt
tX carbon B perfluoroalkyl group of 6 to 20, R
is a divalent hydrocarbon group having 1 to 8 carbon atoms; R is a monovalent group represented by a divalent hydrocarbon group having 2 to 8 carbon atoms; Group-0 (x≦3-
〇≦y≦3゜o<x+y<4), and 1
Organosyloquitin and/or Rby yt process having at least one hydroxyl group and/or I1 hydrolyzable group in the molecule; -X is the same as above; 0x≦3 -0(x+y+z≦49) An antifouling agent containing as a main component an organosilane or a partially hydrolyzed product thereof.