JPH0347672B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to an oil-repellent film-forming agent for preventing oil adhesion, which is used to prevent oil from adhering to the inner walls or transparent walls of various containers. Prior art and its problems When taking out heavy fuel oil, lubricating oil, slurry fuel oil such as coal oil mixture (COM), liquid hydrocarbons in the form of emulsion, etc. from storage containers or measuring containers, the inner wall of the container It is desirable that the oil adhering to the product be removed quickly. In addition, when using the above oils, be careful not to allow the oil to adhere to the transparent glass, acrylic resin, or vinyl chloride resin used in the transparent glass, liquid level gauge, flow meter, etc. installed in the storage container, etc. In particular, when the oil is colored, cloudy, or emulsified and opaque, it becomes difficult to perform an autopsy, which poses a problem not only in terms of work but also in terms of maintenance management. Conventionally, as a countermeasure to the above-mentioned problem caused by oil adhesion, measures such as coating glass or transparent resin such as the above-mentioned see-through window with fluorine resin or adhering Teflon film have been adopted. However, although these coatings and films exhibit an oil-repellent function for a short period of time immediately after implementation, their oil-repellent function rapidly declines over time, resulting in oil adhesion. It doesn't solve the problem. Incidentally, such a decline in oil repellency over time is thought to be due to oil constantly coming into contact with the coating or film, which causes deterioration, swelling, or elution of these coatings. Note that adhesion of the above-mentioned Teflon film requires a special technique, and furthermore, adhesion may be difficult depending on the shape of the area to which it is applied. Problems to be Solved by the Invention The present invention has been made to solve the above-mentioned problems, and is intended to be applied to the inner surfaces of various containers, liquid level gauges, flowmeters, see-through windows, etc. that are constantly in contact with liquid oil. It is an object of the present invention to provide a film-forming agent for preventing oil adhesion that has excellent oil repellency and exhibits the function of immediately removing oil adhering to an oil-contact surface by simply applying it to the oil-contact surface. The present invention will be explained in detail below. Structure of the Invention The structural features of the present invention are: (a) 100 parts by weight of diorganopolysiloxane whose molecular chain ends are capped with hydroxyl groups; (b) a hydrolyzable group bonded to a silicon atom in the molecule; 0.1 organosilicon compound having at least two
(c) 0 to 400 parts by weight of a filler; and (d) 0 to 5 parts by weight of a curing catalyst. Means for Solving the Problems The film forming agent for preventing oil adhesion according to the present invention has the above-mentioned properties.
It consists of components (a) to (d), and the diorganopolysiloxane used here as component (a) is a well-known substance that has traditionally been used as a main raw material for silicone rubber, and has the following general formula ( ) is a diorganopolysiloxane in which both terminal groups are capped with hydroxyl groups. (In the formula, R ¹ and R ² are alkyl groups such as methyl, ethyl, and propyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl and tolyl groups; or R ¹ and R ² may be the same or different groups; n is an integer of 5 or more). Note that since the viscosity of this diorganopolysiloxane at 25° C. is in the range of 25 to 500,000 cs, preferably in the range of 1,000 to 100,000 cs, n in the above formula is an integer of 5 or more. Next, the organosilicon compound as the above component (b) is
It is an essential component for curing the film formed by the film forming agent according to the present invention, and it is necessary to have at least two hydrolyzable groups bonded to a silicon atom in one molecule. Examples of the hydrolyzable group include acyloxy groups such as acetoxy, octanoyloxy, and benzoyloxy groups, ketoxime groups such as dimethylketoxime, methylethylketoxime, and diethylketoxime, methoxy, and ethoxy groups. , alkoxy groups such as propoxy groups, isopropenyloxy groups, 1-ethyl-2-dimethylamino groups, diethylamino groups, butylamino groups,
Examples include amino groups such as cyclohexylamino groups, aminoxy groups such as dimethylaminoxy groups and diethylaminoxy groups, and amide groups such as N-methylacetamide groups, N-ethylacetamide groups, and N-methylbenzamide groups. The organosilicon compound which is the component (b) above is not particularly limited except that it must have at least two hydrolyzable groups as described above in its molecule, and the silicon atom has no hydrolyzable groups. Even if a group other than the group is bonded, the molecular structure thereof may be either a silane or siloxane structure, and in the case of a siloxane structure, it may be linear, branched, or cyclic. . Groups other than the above-mentioned hydrolyzable groups include alkyl groups such as methyl, ethyl, propyl, and butyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, alkenyl groups such as vinyl and allyl groups, and phenyl groups. tolyl group, aryl group such as naphthyl group, aralkyl group such as 2-phenylethyl group

【formula】

Examples include iminoalkyl groups such as [Formula], and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as chlorine atoms. Note that the use of these is not necessarily limited to only one type, and two or more types may be used in combination. In addition, if the amount of component (b) used is less than 0.1 part by weight per 100 parts by weight of component (a), gelation may occur during production or storage of the film forming agent, resulting in a cure that does not have the desired physical properties. On the other hand, if it exceeds 25 parts by weight, the shrinkage rate during curing will increase, curing will be extremely slow, and the elasticity of the resulting film will decrease.
The amount is preferably in the range of 25 parts by weight. As the filler which is the above component (c) constituting the film forming example according to the present invention, examples include fumed silica, treated silica whose surface is treated with hexamethyldisilazane or cyclic dimethylsiloxane, and precipitated silica. , quartz, diatomaceous earth, titanium oxide, aluminum oxide, lead oxide, carbon black, bentonite, graphite, calcium carbonate, mica, clay, glass beads, glass microballoon, glass balloon, glass fiber, polyvinyl chloride beads, polystyrene Examples include beads, acrylic beads, and the like. The amount of component (c) to be used is 1 to 400 parts by weight, preferably 50 to 150 parts by weight, per 100 parts by weight of component (a). The mechanical strength of the resulting cured film will be poor, and if the amount exceeds 400 parts by weight, the resulting film will not have the desired elasticity. However, if the cured film for preventing oil adhesion formed by the present invention does not require much mechanical strength, the filler of component (c) may not necessarily be used. In addition, as the curing catalyst which is the above component (d),
Conventionally known materials can be used, including lead-2-
Ethyl octoate, dibutyltin octoate, dibutyltin diacetate, dibutyltin dilaurate, butyltin-2-ethylhexoate, iron-2-ethylhexoate, cobalt-2
- Ethylhexoate, manganese-2-ethylhexoate, zinc-2-ethylhexoate, stannous caprylate, tin naphthenate, tin oleate, tin butyrate, titanium naphthenate, zinc naphthenate, Cobalt naphthenate, metal salts of organic carboxylic acids such as zinc stearate, organic titanate esters such as tetrabutyl titanate, tetra-2-ethylhexyl titanate, triethanolamine titanate, tetra(isopropenyloxy) titanate, organosiloxy titanium, β
- Organic titanium compounds such as carbonyl titanium, alkoxyaluminum compounds, aminoalkyl group-substituted alkoxysilanes such as 3-aminopropyltriethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, hexylamine,
Amine compounds and their salts such as dodecylamine phosphate, quaternary ammonium salts such as benzyltriethylammonium acetate, lower fatty acid salts of alkali metal salts such as potassium acetate, sodium acetate, lithium oxalate, dimethylhydroxylamine, diethylhydroxyl Dialkylhydroxyamines such as amines Formula or Examples thereof include guanidine compounds having guanidine groups, and guanidyl group-containing silanes or siloxanes, and when used, these are not limited to one type, but may be used as a mixture of two or more types. Note that component (d) may not be used depending on the type of organosilicon compound that is component (b) above, especially the type of hydrolyzable group bonded to the silicon atom in the compound. However, if its use is required, it may be used in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of component (a). In this case, if the amount used is less than 0.01 part by weight, it will take a long time to cure, and if the film is thick, it will be difficult to cure it uniformly to the deep part, while if it is more than 5 parts by weight, The time required to form a film becomes extremely short, causing various operational inconveniences, and
The resulting cured film also has poor heat resistance or weather resistance. The film-forming agent according to the present invention can be prepared by uniformly mixing each of the components (a) to (d) above in a dry atmosphere, but this mixing can be done using conventionally known mixing means. It's good to do. The resulting mixture is usually packed in a closed container such as a cartridge or tube, and extruded from the container before use. The siloxane component and other components including a curing agent may be filled in separate containers and used as a two-component product by mixing them immediately before use. In addition, in the present invention, coloring agents such as plasticizers and pigments, flame retardant agents, thixotropic agents, antifungal agents, and amino groups, epoxy groups,
There is no problem in adding a predetermined amount of an adhesion improver such as a so-called carbon functional silane having a thiol group or the like as appropriate within a range that does not impede the object of the present invention. The present invention will be specifically explained below using Examples. All "parts" in the examples indicate "parts by weight", and the viscosity indicates the value measured at 25°C. Example 1 Viscosity with both ends of the molecular chain blocked with hydroxyl groups
100 parts of dimethylpolysiloxane with 5200cs,
8 parts of methyltri(methylethylketoxime)silane, γ-aminopropyltrimethoxysilane
A film-forming agent for preventing oil adhesion was obtained by mixing 1.0 parts of fumed silica, 15 parts of fumed silica, and 0.2 parts of dibutyltin dioctoate in an anhydrous state. Example 2 Viscosity with both ends of the molecular chain blocked with hydroxyl groups
100 parts of dimethylpolysiloxane with 19600 cs and 6 parts of vinyltri(isobenobenoxy)silane
part, 10 parts of fumed silica, 7.5 parts of carbon black and formula

A film-forming agent for preventing oil adhesion was obtained by mixing 0.5 part of a guanidyl group-containing compound represented by the formula in an anhydrous state. Example 3 This example shows the oil-repellent effects of the films formed using the oil adhesion prevention film-forming agents obtained in Examples 1 and 2. Formation of cured film: 30 g of each composition obtained in Example 1 and Example 2 was added to 100 g of toluene and mixed to prepare a film forming liquid. Next, a glass plate and an acrylic resin plate each having a size of 50 x 120 x 1.5 (mm) were washed with benzene, dried, immersed in each of the above solutions, and then pulled up and left at room temperature for 1 hour to dry. A cured film was formed. Oil repellency test: Each glass plate and acrylic resin plate with a hardened film formed on the surface as described above was immersed in commercially available gear oil (ISO VG150) containing graphite, and removed every 24 hours to drain the oil. I observed the condition. As a comparative example, a glass plate and an acrylic resin plate treated in the same manner as above were treated with a silicone resin solution (manufactured by Imperial Oil & Greese,
RD6640), then pulled up to room temperature (20~22
℃) for 24 hours to form a dry film, and the state of oil removal was observed according to the same procedure as above. The results are shown in Table 1.

[Table] (Note) In the table, ○ indicates complete oil drain, and × indicates oil and graphite adhesion and poor oil drain.
As shown in Table 1, the film forming agent having the composition of the present invention exhibits an excellent oil repellent effect over a long period of time.

Claims (1)

[Scope of Claims] 1 (a) 100 parts by weight of a diorganopolysiloxane whose molecular chain ends are capped with hydroxyl groups, (b) having at least two hydrolyzable groups bonded to silicon atoms in the molecule Organosilicon compound 0.1
25 parts by weight, (c) 0 to 400 parts by weight of a filler, and (d) 0 to 5 parts by weight of a curing catalyst.