JPH08337757A - Surface treating agent and its use - Google Patents

Abstract

PURPOSE: To obtain a surface treating agent containing an alkoxysilane surfactant, a silanol condensation catalyst and a nonaqueous medium, capable of forming a chemical adsorption protecting film having high durability, extremely thin and excellent in water repellence and oil repellence on the surface of a substrate. CONSTITUTION: This surface treating agent contains (a) 0.1-30wt.% of an alkoxysilane surfactant, (B) 0.0001-20wt.% of a silanol condensation catalyst, (C) 5-99.8999wt.% of a nonaqueous liquid or solid medium and optionally further (D) >0 and <=60wt.% of an abradant based on 100wt.% of the whole surfactant. At least one of the component A and the component B is micro-capsulated. The surface treating agent is preferably used by a method in which the surface treating agent is applied to the well prewashed surface of a substrate, an active hydrogen on the surface of the substrate is reacted with the component A and the component B and the unreacted surface treating gent is removed.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a surface treating agent and a method of using the same. More specifically, it relates to a method for forming a chemical adsorption protective film having excellent durability and extremely thin water and oil repellency on the surface of a substrate.

[0002]

2. Description of the Related Art Conventional surface treatment agents such as polishes are
There are solid type and emulsion type, petroleum solvent,
The mainstream is a mixture of an abrasive with a mixture of silicone, wax, lower alcohol and the like. Further, a surface treatment agent using a fluorine-containing silane compound has also been proposed (for example, Japanese Patent Application Laid-Open No. 3-100060, EP Publication No. 0577951A1).

[0003]

However, the conventional treatment materials are inferior in gloss and water repellency, and the obtained protective film is simply applied to the surface of the base material, resulting in durability and robustness. Was not sufficient, and there was almost nothing that was oil repellent. Further, the methods proposed in Japanese Patent Laid-Open No. 3-100060 and EP Publication No. 0579795A1 also have a problem that the reaction of the alkoxysilane surfactant is slow and a film cannot be easily formed. Although it is possible to use a dealcoholization catalyst, there is a problem that the surfactant is self-crosslinked by water in the air and deactivated by simply adding the dealcoholization catalyst. That is, when the surface treatment agent contains water, the surfactant itself crosslinks before reacting with the surface of the base material, and the reaction at the solid-liquid interface on the surface of the base material is hindered and the chemisorption film is formed. There is a problem that it becomes difficult to do it.

In order to solve the above-mentioned conventional problems, the present invention uses a silanol condensation catalyst to enhance the reactivity of the alkoxysilane surfactant and to prevent the surfactant from being affected by water before the reaction. An object of the present invention is to provide a surface treatment agent which reacts efficiently and rationally with the surface of a substrate and a method for using the same. Further, another object of the present invention is to provide a surface treatment agent capable of forming a fluorocarbon polymer film with good adhesion to a substrate and thinly, and a method for using the surface treatment agent.

[0005]

To achieve the above object, the first surface treating agent of the present invention comprises an alkoxysilane surfactant, a silanol condensation catalyst and a non-aqueous liquid or solid medium. Composed of composition.

In the above composition, the total amount is 100% by weight.
And the alkoxysilane surfactant is 0.1 to 3
0 wt% range, silanol condensation catalyst 0.0001 ~
20% by weight, non-aqueous liquid or solid medium is 5
It is preferably in the range of 99.8999% by weight.
In addition to the three-component system, it is possible to include, for example, a coloring material, a filler such as particles, and an optional additive such as a fragrance.

The second surface-treating agent of the present invention has a composition containing an alkoxysilane surfactant, a silanol condensation catalyst, a non-aqueous liquid or solid medium and an abrasive.

In the above composition, the total amount is 100% by weight.
And the alkoxysilane surfactant is 0.1 to 3
0 wt% range, silanol condensation catalyst 0.0001 ~
20% by weight, non-aqueous liquid or solid medium is 5
~ 99.8999% by weight, abrasive exceeds 0 and 60
It is preferably not more than weight%. In addition to the four-component system, a coloring material, a filler such as particles, and an arbitrary additive such as a fragrance can be included.

In the above, it is preferable that at least one selected from a silanol condensation catalyst and an alkoxysilane surfactant is microencapsulated. In the above, the silanol condensation catalyst is at least one substance selected from carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanic acid esters and titanic acid ester chelates. It is preferable.

In the above, it is preferable that the viscosity of the liquid medium at 25 ° C. is 1000 cps or more. Particularly preferably, it is 1000 to 5000c at 25 ° C.
It is in the ps range.

In the above, the liquid or solid medium comprises a substance having a boiling point of 200 ° C. or higher and a boiling point of 100 to 20.
It is preferably a mixture with substances in the range of 0 ° C. In the above, it is preferable that the alkoxysilane surfactant contains at least a fluorocarbon group.

[0012] In above, the alkoxysilane surface active _{agent, CF 3 - (CF 2)} n - (R) m -SiX p (O
A) _3-p (n is 0 or an integer, R is an alkylene group, a vinylene group, an ethynylene group, an arylene group, a substituent containing a silicon or oxygen atom, m is 0 or 1, X is H, an alkyl group, an alkoxyl Group, a substituent of a fluorine-containing alkyl group or a fluorine-containing alkoxy group, A is an alkyl group, and p is preferably 0, 1 or 2).

In the above, the abrasive has an average particle size of 1
At least one particle selected from alumina, calcium oxide, calcium carbonate, silicon carbide, boron carbide, chromium oxide, iron oxide, artificial diamond and silica fine particles having a size of 0 μm or less is preferable. Especially average particle size 0.2〜
Abrasives consisting of particles in the range of 3 μm are preferred.

Next, the method of using the surface treating agent of the present invention is to thoroughly wash the surface of the base material in advance and then to perform surface treatment containing at least an alkoxysilane surfactant, a silanol condensation catalyst and a non-aqueous liquid or solid medium. Apply the agent,
The method comprises reacting the active hydrogen on the surface of the substrate with the alkoxysilane surfactant and the silanol condensation catalyst to remove the unreacted surface treatment agent.

In the above method, at least one selected from a silanol condensation catalyst and an alkoxysilane surfactant is microencapsulated, and at least a microcapsule of the alkoxysilane surfactant or silanol condensation catalyst is encapsulated in the coating step. It is preferable to apply the treatment agent while destroying.

In the above method, it is preferable that an abrasive is added to the treating agent and the treating agent is applied while polishing at least the surface of the substrate in the applying step. In the above-described surface treatment agent of the present invention and the method of using the same, it is preferable that the water content of the surface treatment agent is 10 ppm or less because the alkoxysilane surfactant can be kept more stable.

As described above, the present invention contains an alkoxysilane surfactant, a silanol condensation catalyst and a non-aqueous liquid or solid medium, or adds an abrasive to the composition. Here, when a non-aqueous liquid or solid medium is used, at the time of application, it prevents the reaction between the moisture in the air, the alkoxysilane surfactant and the silanol condensation catalyst, and prevents the substrate surface from the alkoxysilane surfactant and the silanol condensation. It is convenient for promoting the reaction with the catalyst.

At this time, if either or both of the silanol condensation catalyst and the alkoxysilane surfactant are microencapsulated so as not to come into contact with moisture in the air, the surface treatment agent is further improved in storage stability. convenient. Further, if the viscosity of the liquid medium is set to 1000 cps or more, it is convenient that the liquid does not drip during application. Furthermore, when the liquid or solid medium is a mixture having a boiling point of 200 ° C. or higher and a boiling point of 100 to 200 ° C., solidification due to evaporation of the medium at the time of coating is fast and convenient.

The silanol condensation catalyst is a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal salt polymer, a carboxylic acid metal salt chelate, a titanate ester,
Alternatively, titanate ester chelates are preferable for stable use. In particular, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, dioctanoic acid first
Carboxylic acid metal salts such as tin, lead naphthenate, cobalt naphthenate and iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolic acid ester salts, carboxylic acid ester metal salts such as dioctyltin maleic acid ester salts, dibutyltin malein. Acid salt polymers, carboxylic acid metal salt polymers such as dimethyltin mercaptopropionate polymers,
Carboxylic acid metal salt chelates such as dibutyltin bisacetylacetate and dioctyltin bisacetyllaurate, titanate esters such as tetrabutyl titanate and tetranonyl titanate, or titanate ester chelates such as bis (acetylacetonyl) dipropyl titanate. It is advantageous to use since it can be dissolved in a non-aqueous solvent and does not bring water into the treatment agent.

Further, at least the alkoxysilane surface active
If the agent contains a fluorocarbon group, the treated film will be water and water repellent.
It is convenient because oiliness can be imparted at the same time. Like this
Examples of lucoxysilane surfactants include:
Hydrocarbon-based molecules can be used. CF₃-(CF₂)_n−
(R)_m-SiX_p(OA)_3-p(Where n is 0 or
Integer, R is an alkylene group, a vinylene group, an ethynylene group,
Substitution containing an arylene group, silicon or oxygen atom
Group, m is 0 or 1, X is H, alkyl group, alkoxyl
Group, fluorine-containing alkyl group or fluorine-containing alkoxy group
Substituent, A alkyl group or fluoroalkyl group, p is
0, 1 or 2) or CH₃-(CH₂)_r-Si
X_p(OA)_3-p, CH₃-(CH₂)_s-O- (CH₂)_t
-SiX_p(OA) _3-p, CH₃-(CH₂)_u-Si (C
H₃)₂-(CH₂)_v-SiX_p(OA)_3-p, CF₃COO
-(CH₂)_w-SiX_p(OA)_3-p(Where preferred
As a range, r is 1 to 25, s is 0 to 12, and t is 1 to 2.
0, u is 0 to 12, v is 1 to 20, w is 1 to 25
You X is H, an alkyl group, an alkoxyl group, a fluorine-containing group
A substituent on the alkyl group or fluorine-containing alkoxy group, A is an alkyl group
Kill group, p is 0, 1 or 2).

When alumina, calcium oxide, calcium carbonate, silicon carbide, boron carbide, chromium oxide, iron oxide, artificial diamond or silica fine particles having an average particle diameter of 10 μm or less is used as the polishing agent, the treatment agent is applied while polishing. Therefore, the polishing action is synergistically improved.

To use the surface treating agent, the surface of the substrate is thoroughly washed in advance, and then a surface treating agent containing at least an alkoxysilane surfactant, a silanol condensation catalyst and a non-aqueous liquid or solid medium is applied. After the active hydrogen on the surface of the substrate, the alkoxysilane surfactant and the silanol condensation catalyst are sufficiently brought into contact with each other to cause a reaction, an unreacted unnecessary treating agent is removed. This makes it possible to form a molecular film with a well-ordered molecular orientation.

When either one or both of the alkoxysilane surfactant and the silanol condensation catalyst are microencapsulated, at least the microcapsule of the alkoxysilane surfactant or silanol condensation catalyst in the coating step is used. When the treatment agent is applied while destroying the capsules, even if the treatment is performed in the air, it is possible to smoothly cause the reaction on the surface of the base material without being disturbed by the moisture in the air.

Further, when an abrasive is added to the treating agent, the treating agent is applied while at least polishing the surface of the base material in the coating step so that a reaction is always caused on the clean surface of the base material. It is possible to obtain a coating having higher durability, which is convenient.

[0025]

According to the above composition of the present invention, an alkoxysilane surfactant, a silanol condensation catalyst and a non-aqueous liquid or solid medium are contained, or an abrasive is added to the composition, In addition to increasing the reactivity of the alkoxysilane surfactant, the surfactant can be prevented from being affected by moisture before the reaction, and can be efficiently and reasonably reacted with the surface of the substrate. It can react with the material surface. Further, when the substrate is applied with the surface treatment agent of the present invention, the silanol condensation catalyst and the alkoxysilane surfactant are protected by microcapsules or non-aqueous liquid or solid medium even when used in air. Since the microcapsules come into contact with the water in the air only when they are broken, it is possible to prepare a surface treatment agent with a long shelf life even if an alkoxysilane surfactant and a silanol condensation catalyst are added at the same time. It is possible to use it more easily than when it is divided into two solutions. Further, when the surface treatment agent of the present invention is used, the reaction between the silanol condensation catalyst, the alkoxysilane surfactant and the substrate surface allows the alkoxysilane surfactant to directly react with the substrate surface and be fixed by a covalent bond. It has the effect of extremely easily forming a protective film having excellent water and oil repellency and durability.

By this action, the fluorocarbon polymer film is formed into a thin film with good adhesion to the base material, and is used for weathering electrical appliances, automobiles, industrial equipment, glass, mirrors, eyeglass lenses, interior products, textile products, apparel products, etc. It is possible to improve the antifouling performance of a base material that requires anti-fouling property, abrasion resistance antifouling film and the like.

[0027]

The present invention will be described more specifically with reference to the following examples. The surface treating agent of the present invention comprises at least an alkoxysilane surfactant, a silanol condensation catalyst, and a non-aqueous liquid or solid medium. Alternatively, an abrasive is added to the composition.

The method of use is to thoroughly wash the surface of the base material beforehand, and then apply a surface treatment agent containing at least an alkoxysilane surfactant, a silanol condensation catalyst and a non-aqueous liquid or solid medium, and then apply the base at room temperature. The material surface and the alkoxysilane surfactant are sufficiently reacted in the presence of a silanol condensation catalyst. This reaction is, for example, dealcoholization condensation that occurs between the hydroxyl group (-OH) on the surface of the base material and the alkoxy group (-OR: where R is an alkyl group) at the terminal of the alkoxysilane surfactant molecule. When the reaction time is room temperature (about 25 to 30 ° C.), it is preferably 20 to
30 minutes. At this time, if a silanol condensation catalyst or an alkoxysilane surfactant is microencapsulated and added to the medium, the storage period, that is, the pot life can be extended.

When either one or both of the alkoxysilane surfactant and the silanol condensation catalyst are microencapsulated, at least the microcapsule of the alkoxysilane surfactant or silanol condensation catalyst in the coating step is used. Apply the treatment while breaking the capsule.

The method of microencapsulating a silanol condensation catalyst or an alkoxysilane surfactant is described in "New technology of microencapsulation and application development / application examples thereof, Management Development Center Press, 1978" or "Microcapsule".・ Production method / property / application, Sankyo Publishing, 197
7 years' publication.

Further, when an abrasive is added to the treating agent, the treating agent is applied while at least polishing the surface of the base material in the coating step so that a reaction is always caused on the clean surface of the base material. It is possible to provide a coating with higher durability.

On the other hand, as the substrate usable in the present invention,
Substrates containing active hydrogen on the surface thereof, for example, having hydroxyl groups (-OH), metals such as Al, Cu or stainless, glass, ceramics, paper, natural fibers, leather and other hydrophilic substrates are just a few examples. Therefore, the present invention can be widely applied to the following uses as an example. (A) Example of base material; base material is metal, ceramics, glass,
Alternatively, it can be applied to materials made of plastic, wood and stone. The surface may be painted. (B) Examples of knives: kitchen knife, scissors, knife, cutter, chisel, razor, clipper, saw, planer, chisel, awl, awl, bite, drill blade, mixer blade, juicer blade, milling machine blade , Lawn mower blades, punches, push cutters, stapler blades, can opener blades, or surgical scalpels. (C) Examples of needles: acupuncture needles, sewing needles, sewing needles, tatami needles,
Injection needles, surgical needles, safety pins, etc. (D) Examples of ceramic products: products made of ceramics, glass, ceramics or enamel. For example, sanitary ware (for example, toilet bowl, washbasin, bath, etc.), tableware (for example, bowl, plate, bowl, teacup, cup, bottle, coffee kettle, pot, mortar, cup, etc.), vase (basin, flowerpot,
(A vase, etc.), aquarium (aquarium for aquaculture, aquarium for appreciation, etc.), chemical experiment equipment (beaker, reaction vessel, test tube, flask, etc.)
Petri dish, cooling tube, stirring rod, stirrer, mortar, vat, syringe), roof tile, tile, enamel tableware, enamel basin, enamel pot. (E) Examples of mirrors: hand mirrors, full-length mirrors, bathroom mirrors, washroom mirrors,
Automotive mirrors (rear view mirrors, side mirrors), half mirrors, show window mirrors, department store product section mirrors, etc. (F) Examples of molding members: press molding dies, cast molding dies, injection molding dies, transfer molding dies, vacuum molding dies, blow molding dies, extrusion dies. , Inflation molding die, fiber spinning die, calendering roll, etc. (G) Examples of ornaments: watches, jewels, pearls, sapphires, rubies, emeralds, garnets, cat's eyes, diamonds, topaz, blood stones, aquamarine,
Sardonyx, turquoise, agate, marble, amethyst, cameo, opal, crystal, glass, ring, bracelet, brooch, tie pin, earring, necklace, precious metal decoration product, platinum, gold, silver, copper, aluminum, titanium, tin Or their alloys, stainless steel, eyeglass frames, etc. (H) Examples of food molding molds: cake baking molds, cookie baking molds, bread baking molds, chocolate molding molds, jelly molding molds, ice cream molding molds, oven plates, ice trays and the like. (I) Examples of cookware: pots, kettles, kettles, pots, frying pans, hot plates, grills for cooking grilled foods, oil drainers, octopus grilled plates, etc. (J) Examples of paper: gravure paper, water / oil repellent paper, poster paper,
High-class pamphlet paper, etc. (k) Examples of resins: polyolefins such as polypropylene and polyethylene, polyvinyl chloride, polyvinylidene chloride,
Polyamide, polyimide, polyamideimide, polyester, aramid, polystyrene, polysulfone, polyether sulfone, polyphenylene sulfide, phenol resin, furan resin, urea resin, epoxy resin, polyurethane, silicon resin, ABS resin, methacrylic resin,
Acrylic ester resin, polyacetal, polyphenene oxide, etc. (l) Examples of home appliances: televisions, radios, tape recorders, audios, CDs, refrigerators for freezing-related equipment, refrigerators, air conditioners, juicers, mixers, fan blades. , Lighting fixtures, dials, perm dryers, etc. (M) Examples of sports equipment: skis, fishing rods, pole vaults, boats, yachts, jet skis, surfboards, golf balls, bowling balls, fishing lines, fishnets,
Fishing float etc. (N) Examples applied to vehicle parts: (1) ABS resin: lamp cover, instrument panel, interior parts, motorcycle protector (2) Cellulose plastic: car mark, steering wheel (3) FRP (fiber reinforced resin): Outer bumper, engine cover (4) Phenolic resin: Brake (5) Polyacetal: Wiper gear, gas valve, carburetor parts (6) Polyamide: Radiator fan (7) Polyarylate: Directional lens, instrument panel lens,
Relay housing (8) Polybutylene terephthalate: Rear end, front fender (9) Polyamino bismaleimide: Engine parts, gearbox, wheel, suspension drive system (10) Methacrylic resin is lamp cover lens, instrument panel and cover, center mark (11 ) Polypropylene is bumper (12) Polyphenylene oxide: Radiator grille, wheel cap (13) Polyurethane: Bumper, fender, instrument panel, fan (14) Unsaturated polyester resin: body, fuel tank, heater housing, instrument panel (o) Examples of office supplies: fountain pens, ballpoint pens, sharp pencils, pencil cases, binders, desks, chairs, bookshelves, racks, telephone stands, rulers, drafting tools, etc. (P) Examples of building materials: roofing materials, outer wall materials, interior materials. As roof material, kiln roof tiles, slate roof tiles, galvanized iron (galvanized iron plate), etc.
Outer wall materials include wood (including processed wood), mortar, concrete, ceramic sizing, metal sizing, bricks, stone materials, plastic materials, and metal materials such as aluminum. Interior materials include wood (including processed wood), metal materials such as aluminum, plastic materials, paper, and fibers. (Q) Examples of stone materials: granite, marble, granite, etc. For example, buildings, building materials, art objects, figurines, baths, tombstones, monuments, gateposts, stone walls, sidewalk paving stones, etc. (R) Examples of musical instruments and audio equipment: musical instruments such as percussion instruments, string instruments, keyboard instruments, woodwind instruments, brass instruments, and acoustic equipment such as microphones and speakers. Specifically, percussion instruments such as drums, cymbals, violins, cellos, guitars, koto, pianos, flutes, clarinet, shakuhachi and horns, string instruments, keyboard instruments, woodwind instruments, brass instruments, and microphones, speakers, Audio equipment such as earphones. (S) Others, such as a thermos bottle, a vacuum system device, an insulator for electric power transmission, or a high-voltage insulator having a high water / oil / fouling antifouling effect such as a spark plug.

The present invention will be described in detail below with reference to specific examples and schematic drawings. In the following examples,% means% by weight unless otherwise specified. (Example 1) (A) Preparation of surface treating agent (1) heptadecafluorodecyltrimethoxysilane [fluorine alkoxysilane emissions _{surfactants: CF 3 (CF 2) 7} - (CH 2) 2 -Si ( OCH ₃ ) ₃ ] 10 g (2) n-paraffin (non-aqueous liquid medium: bp 210 ° C.) 20 g (3) Silicone oil (non-aqueous liquid medium: Shin-Etsu Chemical KF-96, 1000 cps) 15 g (4) Paraffin (non-aqueous liquid medium: Kanto Kagaku, mp94-96 ° C) 20 g (5) Alpha alumina (abrasive: average particle size 1 μm micron) 5 g or more are put in an Erlenmeyer flask and mixed, and stirred while heating to 100 ° C. A suspension was obtained. Then, after cooling this liquid to room temperature, (6) 2 g of dibutyltin dilaurate (silanol condensation catalyst: metal salt of carboxylic acid) microencapsulated with a formalin condensation resin was added and stirred to give a solid, soft waxy surface. A treated material was obtained.

At this time, the microencapsulation of dibutyltin dilaurate was carried out according to the method described in the above publication. Incidentally, contrary to Example 1, even if the alkoxysilane surfactant is encapsulated, or both the silanol condensation catalyst and the alkoxysilane surfactant are respectively encapsulated, the same effect can be obtained. Was given. (B) Application of Surface Treatment Agent Next, the surface treatment agent thus obtained was subjected to the following treatments to evaluate water and oil repellency and durability.

A window glass 1 for an automobile was used as a substrate for surface treatment. The surface of the glass substrate 1 contained a large amount of —OH groups 2 containing active hydrogen (FIG. 1 (a)).
Therefore, after thoroughly cleaning the glass substrate in advance, the surface treatment agent prepared as described above was applied to the glass surface by rubbing with a sponge. As a result, the capsule of the formalin condensation resin was broken, and the glass surface was brought into contact with dibutyltin dilaurate and heptadecafluorodecyltrimethoxysilane in a mixed state. Then, if it is left at room temperature (about 25 ° C) for 30 to 40 minutes, n-
The paraffin was evaporated and a white coating was formed. At this time, even if silicon oil or paraffin is present on the coating film and the surface of the base material, there is a certain probability that the methoxysilyl group 3 of the heptadecafluorodecyltrimethoxysilane and the base material will be removed as shown in FIG. Surface -OH groups 2 meet in the presence of the catalyst. At this time, the water content in the air is n
-Parked with paraffin. Therefore, the heptadecafluorodecyltrimethoxysilane surfactant and the water adsorbed on the glass surface or the —OH group on the substrate surface cause the dealcoholation reaction represented by the following formula (Formula 1) to proceed and heptadecafluoro Decyltrisilole molecules are produced.

[0036]

Embedded image

Thereafter, the silanol groups produced by the reaction of the above-mentioned formula (Formula 1) and the active hydrogen of the OH group on the surface of the substrate undergo a dehydration reaction as shown by the following formula (Formula 2) to give heptadeca. Fluorodecyltrimethoxysilole molecule is S
It is chemically adsorbed on the surface of the substrate through the iO bond and is fixed by a covalent bond.

[0038]

Embedded image

After that, when the remaining unreacted surface treatment agent was wiped off with a cloth, a large number of heptadecafluorodecyltrimethoxysilane molecules as shown in FIG. Covalently fixed to. The thickness of the obtained fluorocarbon-based chemical adsorption film 4 is
It was several nm.

At this time, the silanol condensation catalyst or the alkoxysilane surfactant does not necessarily need to be added in the form of microcapsules, but the encapsulation can extend the storage period of the treatment agent.

The contact angle of this film with water is 11
There were 5 times. In addition, no peeling occurred at all even when the goth test was performed. Moreover, even if the salad oil was rubbed, it could be easily removed by wiping with tissue paper. Furthermore, the contact angle was hardly deteriorated even when the cloth was wet with water and rubbed 50,000 times.

The above results are summarized in Table 1 below. In addition, the same experiment was carried out after the treatment agent was stored for 1 year, but no significant difference was observed in the effect. In the method of the present invention, it is clear from the above reaction formulas (Formula 1-2) that water is an important reaction element. That is, when the surface treatment agent contains water, the surfactant cross-links itself before reacting with the substrate surface, and the reaction at the solid-liquid interface of the substrate surface is hindered, and the chemisorption film is formed. It becomes difficult to do it. Therefore, it is necessary to keep the water content in the treatment agent as low as possible. The water content in the composition is preferably 10 pp
m or less is desirable.

If the substrate is a substance such as plastic, synthetic resin, or synthetic fiber that does not have many hydroxyl groups on the surface, the surface is pretreated in a plasma atmosphere containing oxygen, for example, at 100 W for about 20 minutes or by corona treatment. It is preferable to introduce a hydrophilic group by treatment. The hydrophilic group is not limited to the hydroxyl group (-OH), but -COOH having active hydrogen,
Functional groups such as —CHO, ═NH, and —NH ₂ may be used. When the base material is a polyamide resin or a polyurethane resin, an imino group (-NH) is present on the surface, and active hydrogen of this imino group (-NH) and an alkoxysilyl group (-SiOR: R Alkyl group) undergoes a dealcohol reaction to form a siloxane bond (—SiO—), so that surface treatment is not particularly required. For example, when the base material is nylon or polyurethane, a large amount of imino groups (containing active hydrogen) is exposed on the surface, so that the chemisorption film can be formed by the same method as that of the glass plate.

In the above embodiment, the alkoxysilane boundary is used.
CF as a surface-active agent₃(CF₂)₇(CH₂)₂Si (O
CH₃)₃Was used.
Alkoxysilane surfactants containing fluorine are generally
To SiX_p(OA)_4-p(X is H, alkyl group, alkoxy
Syl group, fluorine-containing alkyl group or fluorine-containing alkoxy group
Substituents, A is an alkyl group, p is 0, 1, 2 or 3)
It is possible to use a substance represented by Further example
CF₃-(CF₂)_n-(R)_m-SiX_p(OA)_3-p
(N is 0 or an integer, R is an alkylene group, a vinylene group,
Ethynylene group ,, arylene group, silicon or oxygen
Substituent containing atoms, m is 0 or 1, X is H, alkyl
Group, alkoxyl group, fluorine-containing alkyl group or fluorine-containing
Substituent of alkoxy group, A is alkyl group, p is 0, 1 or
Or the substance represented by 2), the better water repellency
An oil-repellent film can be formed, but is not limited to this.
Not only this but also CH₃-(CH₂)_r-SiX
_p(OA)_3-pAnd CH₃-(CH ₂)_s-O- (CH₂)_t−
SiX_p(OA)_3-p, CH₃-(CH₂) U-Si (CH
₃)₂-(CH₂)_v-SiX_p(OA)_3-p, CF₃COO-
(CH₂)_w-SiX_p(OA)_3-p(Where the preferred range
Enclosed r is 1 to 25, s is 0 to 12, t is 1 to 20, u
Is 0 to 12, v is 1 to 20, and w is 1 to 25. X is
H, alkyl group, alkoxyl group, fluorine-containing alkyl group
Or a substituent of a fluorine-containing alkoxy group, A is an alkyl group,
As p, 0, 1 or 2) or the like can be used. More concrete
Examples of such molecules are as follows. CH₃CH₂O
(CH₂)_FifteenSi (OCH₃)₃, CF₃CH₂O (CH₂)
_FifteenSi (OCH₃)₃, CH₃(CH₂)₂Si (CH₃)₂
(CH₂)_FifteenSi (OCH₃)₃, CH₃(CH₂)₆Si
(CH₃)₂(CH₂)₉Si (OCH₃)₃, CH₃COO
(CH₂)_FifteenSi (OCH₃)₃, CF₃(CF₂)_Five(CH
₂)₂Si (OCH₃)₃, CF₃(CF₂)₇-C₆H₆-S
i (OCH₃)₃, CH₃CH₂O (CH₂)_FifteenSi (OC₂
H_Five)₃, CH₃(CH₂)₂Si (CH₃)₂(CH₂)_FifteenS
i (OC₂H_Five)₃, CH₃(CH₂)₆Si (CH₃)₂(C
H₂)₉Si (OC₂H_Five)₃, CF₃(CH₂)₆Si (CH
₃)₂(CH₂)₉Si (OC₂H_Five)₃, CH₃COO (CH
₂)_FifteenSi (OC₂H_Five)₃, CF₃COO (CH₂)_FifteenSi
(OC₂H_Five)₃, CF₃COO (CH₂)_FifteenSi (OC
H₃)₃, CF₃(CF₂)₉(CH₂)₂Si (OC
₂H_Five)₃, CF₃(CF₂)₇(CH₂)₂Si (OC₂H_Five)
₃, CF₃(CF₂)_Five(CH₂)₂Si (OC₂H_Five)₃, C
F₃(CF₂)₇C₆H₆Si (OC₂H_Five)₃, CF₃(C
F₂)₉(CH₂)₂Si (OCH₃)₃, CF₃(CF₂)_Five
(CH₂)₂Si (OCH₃)₃, CF₃(CF₂)₇(C
H₂)₂SiCH₃(OC₂H_Five)₂, CF₃(CF₂)₇(C
H₂)₂SiCH₃(OCH₃)₂, CF₃(CF₂)₇(CH
₂)₂Si (CH₃)₂OC₂H_Five, CF₃(CF₂)₇(C
H₂)₂Si (CH₃)₂OCH₃ The alkoxysilane interface contained in the treatment agent of the present invention
The preferable content of the activator is 0.1 to 30%. Well
Also, as a silanol condensation catalyst in the method of the present invention
Is a carboxylic acid metal salt, a carboxylic acid ester metal salt,
Rubonic acid metal salt polymer, carboxylic acid metal salt chelate,
Titanate ester or titanate ester chelates
Is available. Especially, as a silanol condensation catalyst, vinegar
Stannous acid, dibutyltin dilaurate, dibutyltin dioc
Tate, dibutyltin diacetate, dioctyltin dilaurate
Dioctyl tin dioctate, dioctyl tin dioctate
Cetate, stannous dioctanoate, lead naphthenate, naphthe
Carboxylic acid such as cobalt acid salt and iron 2-ethylhexenoate
Metal salts, dioctyl tin bis octyl thioglycolic acid
Calcium such as steal salt and dioctyl tin maleate salt
Bonic acid ester metal salt, dibutyltin maleate polymer
, Dimethyltin mercaptopropionate polymer, etc.
Carboxylic acid metal salt polymer, dibutyltin bisacetylacetate
Cetate, dioctyl tin bisacetyl laurate, etc.
Rubonic acid metal salt chelate, tetrabutyl titanate, te
Titanate such as tranonyl titanate, or
Su (acetylacetonyl) dipropyl titanate etc.
It is more preferable to use titanate ester chelates.
Yes. Particularly, carboxylic acid metal salts and carboxylic acid metal salts
A stable chemisorption film can be obtained by using chelates.
It was The preferred amount of silanol condensation catalyst added is
It is 0.1 to 50% with respect to the surface active agent.

Incidentally, if a dealcoholization reaction is simply caused from the alkoxy group, a mineral acid or an organic acid can be used instead of the silanol condensation catalyst. However, as mentioned above, water enters the surface treatment agent. Is not preferable. Therefore, the available catalysts are limited to the silanol condensation catalysts described above.

As the liquid or solid medium, any non-aqueous solvent that does not decompose the surfactant or silanol condensation catalyst can be used, but silicone or petroleum solvents are preferred. Specifically, petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, ligroin, dimethyl silicone, phenyl silicone, alkyl modified silicone, polyether silicone, paraffin wax, microcrystal. Wax, polyethylene wax ester wax, oxidized wax, petroleum wax and the like can be mentioned. These may be used alone or in combination of two or more. The preferred content of the liquid or solid medium in the present invention is 5 to 99.85%.

When the viscosity is 1000 cps or more after the preparation, the flow of the processing liquid is small at the time of application and the handling is convenient, but if it is too hard, it is difficult to use. Furthermore, if the boiling point of the liquid or solid medium is 200 ° C. or higher,
If it is a mixture of 0 to 200 ° C., the low boiling point component evaporates quickly after coating and the coating film hardens, so that removal by wiping becomes extremely easy.

Furthermore, when alumina, calcium oxide, calcium carbonate, silicon carbide boron carbide, chromium oxide, iron oxide, artificial diamond or silica fine particles of about several microns are added as an abrasive, the surface of the base material during coating becomes extremely large. It is convenient because a clean surface that has been cut in a small amount can directly react with a substance having at least one microencapsulated chlorosilyl group. The preferred content of the abrasive in the present invention is 1 to 10%.

Example 2 The surface treating agent as shown below was prepared and evaluated in the same manner as in Example 1. n-paraffin (bp.180 ° C.) 20 g Silicone oil (Shin-Etsu Chemical KF-96, 1000 cps) 10 g Paraffin (Kanto Kagaku mp86 ° C.) 15 g Heptadecafluorodecyltriethoxysilane: (CF ₃ (CF ₂ ) ₇ — (CH ₂ ) _2- Si (OC ₂ H ₅ ) ₃ ) 10 g Calcium carbonate (average particle size 1 μm) 15 g, dibutyltin bisacetylacetate microcapsulated with formalin condensation resin 3 g, stirred and stirred, soft waxy A surface-treated material of

This surface-treating agent had a slightly high fluidity, but was almost the same as Example 1 except that a white coating film was formed by leaving it for 20 to 30 minutes after coating it on a glass substrate. The result was obtained. The results are summarized later in Table 1.

Example 3 The heptadecafluorodecyltrimethoxysilane of Example 2 was converted to tridecafluorooctyltriethoxysilane (CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ —
An experiment was conducted in the same manner as in Example 2 except that Si (OC ₂ H ₅ ) ₃ ) was used. The results are summarized later in Table 1.

Example 4 An experiment was conducted under the same conditions except that the glass of Example 2 was used as a rearview mirror and 2 g of dibutyltin bisacetylacetate was added without being encapsulated. The results are summarized later in Table 1. The pot life of this treating agent was about 3 months.

Example 5 An experiment was conducted under the same conditions except that the mirror of Example 4 was used as a hood of a painted automobile and 5 g of ethanol as an aqueous solvent was further added. The results are summarized later in Table 1. The treating agent could be used for several hours after preparation, but when left for 2 to 3 days, it hardened and became unusable.

Example 6 The same experiment as in Example 2 was conducted using the glass of Example 2 as a urethane bumper. The results are summarized later in Table 1.

Example 7 An experiment was performed in the same manner as in Example 1 except that the alpha alumina of Example 1 was changed to silica (average particle size 5 μm). The results are summarized later in Table 1.

Example 8 An experiment was conducted in the same manner as in Example 1 except that the amount of n-paraffin in Example 1 was 40 g. The obtained treatment liquid became a liquid wax having a viscosity of about 3000 to 4000 cps. The results of the treatment are summarized in Table 1 below.

(Example 9) In Example 4, 5% of water was further added.
A treatment agent was trial-produced under the same conditions except that it was added, and the same experiment was conducted. In this case, when the treating agent was used immediately after preparation, almost the same result as in Example 4 was obtained. The results are summarized later in Table 1. However, it hardened overnight and became unusable.

Comparative Example 1 The same experiment as in Example 1 was carried out except for the microencapsulated dibutyltin dilaurate of Example 1. The results are summarized later in Table 1. When the silanol condensation catalyst is not included as in this comparative example,
The formed film had almost no durability.

Comparative Example 2 An experiment was performed in the same manner as in Example 2 except that the microencapsulated dibutyltin bisacetylacetate of Example 2 was omitted. The results of the treatment are summarized in Table 1 below. Also in this case, the durability of the coating film formed in the same manner as in Comparative Example 1 was almost nonexistent.

[0060]

[Table 1]

As is clear from Table 1, the surface treatment agent of the present invention retained its water and oil repellency even after the surface was repeatedly rubbed with a cloth containing water and washed. In Comparative Examples 1 and 2, the water repellency and oil repellency were rather poor, and almost disappeared after the durability test.

[0062]

As described above, the method of the present invention is
Since a polymer film chemically adsorbed on the surface of a substrate can be formed by using an alkoxysilane surfactant, a silanol condensation catalyst and active hydrogen on the surface of the substrate in a non-aqueous solvent, it can be applied to various materials such as plastics, ceramics, glass, etc. Also, the protective film can be formed efficiently. At this time, when the silanol condensation catalyst and the alkoxysilane surfactant were microencapsulated and added, the pot life could be prolonged by about 3 to 4 times as compared with the case where they were added as they were.

Further, since the treatment method using the treatment material of the present invention is extremely simple, electrical appliances, automobiles, industrial equipment, mirrors,
It has an effect that it can be applied very easily to equipment that requires a heat-resistant, weather-resistant, and wear-resistant antifouling film such as spectacle lenses.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view in which a surface of a base material is enlarged to a molecular level, for explaining a surface treatment step in a first embodiment of the present invention.

[Explanation of symbols]

 1 Glass substrate 2-OH group 3 Methoxysilyl group 4 Fluorocarbon-based chemical adsorption film

Claims (15)

[Claims] 1. A surface treatment agent containing an alkoxysilane surfactant, a silanol condensation catalyst, and a non-aqueous liquid or solid medium. 2. When the total amount is 100% by weight, the alkoxysilane surfactant is in the range of 0.1 to 30% by weight, the silanol condensation catalyst is in the range of 0.0001 to 20% by weight,
The surface treatment agent according to claim 1, wherein the non-aqueous liquid or solid medium is in the range of 5 to 99.8999% by weight. 3. A surface treatment agent containing an alkoxysilane surfactant, a silanol condensation catalyst, a non-aqueous liquid or solid medium, and an abrasive. 4. When the total amount is 100% by weight, the alkoxysilane surfactant is in the range of 0.1 to 30% by weight, and the silanol condensation catalyst is in the range of 0.0001 to 20% by weight.
The surface treatment agent according to claim 3, wherein the non-aqueous liquid or solid medium is in the range of 5 to 99.8999% by weight, and the polishing agent is more than 0 and 60% by weight or less. 5. The surface treating agent according to claim 1, wherein at least one selected from a silanol condensation catalyst and an alkoxysilane surfactant is microencapsulated. 6. The silanol condensation catalyst is at least one substance selected from carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanic acid esters and titanic acid ester chelates. The surface treatment agent according to any one of claims 1 to 5. 7. The viscosity of the liquid medium is 10 at 25 ° C.
The surface treatment agent according to any one of claims 1 to 4, which has a viscosity of 00 cps or more. 8. The liquid or solid medium has a boiling point of 200.
The surface treatment agent according to any one of claims 1 to 4, which is a mixture of a substance having a temperature of not less than 0 ° C and a substance having a boiling point in the range of 100 to 200 ° C. 9. The surface treating agent according to claim 1, wherein the alkoxysilane surfactant contains at least a fluorocarbon group. 10. The alkoxysilane surfactant is CF
_{3 - (CF 2) n -} (R) m -SiX p (OA) 3-p (n is 0
Or an integer, R is an alkylene group, a vinylene group, an ethynylene group, an arylene group, a substituent containing a silicon or oxygen atom, m is 0 or 1, X is H, an alkyl group, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing group. The surface treating agent according to any one of claims 1 to 5, wherein a substituent of an alkoxy group, A is an alkyl group, and p is 0, 1 or 2). 11. The abrasive is at least one particle selected from alumina, calcium oxide, calcium carbonate, silicon carbide, boron carbide, chromium oxide, iron oxide, artificial diamond and silica fine particles having an average particle diameter of 10 μm or less. Item 14. The surface treatment agent according to item 14. 12. A surface treatment agent containing at least an alkoxysilane surfactant, a silanol condensation catalyst and a non-aqueous liquid or solid medium is applied after thoroughly washing the surface of the substrate, and the active hydrogen on the substrate surface is applied. React with an alkoxysilane surfactant and a silanol condensation catalyst,
A method of using a surface treatment agent for removing unreacted surface treatment agent. 13. At least one selected from a silanol condensation catalyst and an alkoxysilane surfactant is microencapsulated, and at least the microcapsule of the alkoxysilane surfactant or silanol condensation catalyst which is microencapsulated is destroyed in the coating step. The method of using the surface treatment agent according to claim 12, wherein the treatment agent is applied while being applied. 14. The method of using a surface treating agent according to claim 12, wherein the treating agent is added to the treating agent and the treating agent is applied while at least polishing the surface of the substrate in the applying step. 15. The surface treatment agent according to any one of claims 1 to 14, and a method of using the surface treatment agent, wherein the water content in the surface treatment agent is 10 ppm or less.