JPH0931449A - Surface treatment agent and method of using the same - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: To provide a protective film having excellent gloss and water repellency, chemically bonded to the surface of a base material and having high durability and fastness, and further having oil repellency, more easily. Obtain the treating agent. SOLUTION: n-paraffin, isopropyl alcohol, silicone oil, paraffin, heptadecafluorodecyltrimethoxysilane and α-alumina are mixed to obtain a suspension, and 3 wt% sulfuric acid as an acid catalyst is microcapsule in a formalin condensation resin. Stir the added product. This surface treatment agent is applied to glass 1 having OH groups 2 containing active hydrogen. The microcapsules are destroyed, and the methoxysilyl groups 3 of the pentadecafluorodecyltrimethoxysilane react with the OH groups 2 on the surface of the base material under sulfuric acid. 30-4
When left for 0 minutes, a fluorocarbon polymer film 4 in which heptadecafluorodecyltrimethoxysilane molecules are covalently fixed to the surface of the base material through the SiO network bond is formed on the surface of the base material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent for forming a highly durable and extremely thin chemical and adsorption protective film having excellent water and oil repellency on a substrate surface and a method for using the same.

[0002]

2. Description of the Related Art Conventional surface treatment agents such as polishes are
There are solid type and emulsion type, and a mixture of a petroleum solvent, silicone, wax, and a lower alcohol mixture with an abrasive is the mainstream (for example, JP-A-2-15).
1676, JP-A-2-170878).

[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. In addition, even when using an alkoxysilane surfactant and an acid catalyst, it was practically difficult to mix them at the same time. Therefore, it is necessary to separately prepare the alkoxysilane surfactant and the acid catalyst to prepare two liquids, which is convenient for use. It was difficult.

In view of the above-mentioned conventional drawbacks, the present invention is not only excellent in gloss and water repellency, but is not only coated with a protective film on the surface of the base material, but also chemically resistant to the surface of the base material. It is an object of the present invention to provide a surface treatment agent for easily forming a protective film which is bonded and has high durability and fastness and further having oil repellency, and a method for using the same. Furthermore, the fluorocarbon polymer film is formed into a thin film with good adhesion to the base material, and heat resistance required for electrical appliances, automobiles, industrial equipment, or glass and mirrors, eyeglass lenses, interior products, apparel products, etc. It is also an object to provide a water / oil repellent / antifouling treatment film having excellent weather resistance and abrasion resistance.

[0005]

To achieve the above object, the surface-treating agent of the present invention comprises an alkoxysilane surfactant, an acid catalyst, and a liquid or solid medium. Either or both of the catalysts are microencapsulated and added. Alternatively, it may contain an abrasive. At this time, it is practically convenient that the viscosity of the liquid medium is 1000 cps or more at 25 ° C. Particularly preferably 1000 to 5000 cps
Range. The liquid or solid medium has a boiling point of 2
It is practically convenient that the mixture is one having a boiling point of 100 ° C. or higher and a boiling point of 100 to 200 ° C.

Further, it is convenient that at least the alkoxysilane surfactant contains a fluorocarbon group, since the treated film can have water and oil repellency. Such alkoxysilane _{surfactant, 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 molecular chain containing a silicon or oxygen atom, and m is 0.
Or an integer of 1, X is a H atom, 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 an integer of 0, 1 or 2) Is big.

Furthermore, as an abrasive, the average particle size is 10 μm.
It is effective to use alumina, silicon carbide, boron carbide, chromium oxide, iron oxide, artificial diamond or silica fine particles of m or less. Further, it may contain calcium carbonate.

On the other hand, in order to use the surface treating agent, after thoroughly washing the surface of the substrate beforehand, the surface treating agent is applied to the surface of the substrate while destroying at least the microcapsules.
After reacting the substrate surface with the alkoxysilane surfactant and the acid catalyst, the excess surface treatment agent is removed, or
After thoroughly cleaning the substrate surface in advance, at least polishing the substrate surface with an abrasive and simultaneously applying a surface treatment agent to the substrate surface while destroying the microcapsules,
A method in which the step of removing the surplus surface treatment agent after the reaction of the cleaned substrate surface, the alkoxysilane surfactant and the acid catalyst is continuously performed is preferable.

At this time, as the substrate, metal, ceramics, glass, plastic, paper, fiber, leather or the like can be used. When the plastic or fiber is water-repellent, it is preferable that the surface is preliminarily treated in a plasma or corona atmosphere containing oxygen to make it hydrophilic, that is, a hydroxyl group is introduced into the surface before use.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION According to the surface treatment agent of the present invention, since the alkoxysilane surfactant and the acid catalyst contact each other only when the microcapsules are broken, the alkoxysilane surfactant and the acid catalyst are simultaneously added. It becomes possible to prepare a surface treatment agent by blending, and it becomes possible to use it more simply than in the case where it is divided into two liquids. Also, due to the reaction on the surface of the substrate with the acid catalyst, the alkoxysilane surfactant,
Since the alkoxysilane surfactant can be directly reacted with the surface of the base material and fixed by a covalent bond, a protective film having extremely thin water and oil repellency and excellent durability can be formed very easily.

The alkoxysilane surfactant is generally represented by the chemical formula of SiB _q (OA) _4-q (wherein B represents a functional group, A represents an alkyl group, and q represents an integer of 1, 2 or 3). Can be used, and more specifically, a hydrocarbon-based or fluorocarbon-based molecule represented by the following chemical formula can be used. _{CH 3 - (CH 2) r} -SiX p (OA) 3-p, CF 3
_{- (CH 2) s -O- (} CH 2) t -SiX p (OA)
_{3-p, CF 3 - (} CF 2) u -Si (CH 3) 2 - (C
_{H 2) v -SiX p (OA} ) 3-p, CF 3 COO- (CH
_{2) w -SiX p (OA)} 3-p ( here, r is 1~25, s is 0~12, t 1-2
It is preferable that 0, u are 0 to 12, v is 1 to 20, and w is an integer of 1 to 25. X represents an H atom, an alkyl group, an alkoxyl group, a fluorine-containing alkyl group or a substituent of a fluorine-containing alkoxy group, A represents an alkyl group, and p represents an integer of 0, 1 or 2. _{) CF 3 - (CF 2)} n - (R) m -SiX p (OA)
_3-p (where n is 0 or an integer, R is an alkylene group, a vinylene group, an ethynylene group, an arylene group, a molecular chain containing a silicon or oxygen atom, m is an integer of 0 or 1, and X is H
(Atom, alkyl group, alkoxyl group, substituent of fluorine-containing alkyl group or fluorine-containing alkoxy group, p is an integer of 0, 1 or 2) Further specific molecules include the following. _{CH 3 CH 2 O (CH 2} ) 15 Si (OCH 3) 3, CH
₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (O
CH ₃ ) ₃ , CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (C
H ₂ ) ₉ Si (OCH ₃ ) ₃ , CH ₃ COO (C
H ₂ ) ₁₅ Si (OCH ₃ ) ₃ , CF ₃ CH ₂ O (C
_{H 2) 15 Si (OCH 3} ) 3, CF 3 (CH 2) 2 Si
(CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃ , CF ₃
(CF ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC
_{H 3) 3, CF 3 COO} (CH 2) 15 Si (OC
_{H 3) 3, CF 3 (} CF 2) 7 (CH 2) 2 Si (OC
H ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC
_{H 3) 3, CF 3 (} CF 2) 7 -C 6 H 6 -Si (OC
_{H 3) 3, CH 3 CH} 2 O (CH 2) 15 Si (OC 2 H
₅ ) ₃ , CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (C
H ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₆ S
_{i (CH 3) 2 (CH} 2) 9 Si (OC 2 H 5) 3,
_{CH 3 COO (CH 2) 15} Si (OC 2 H 5) 3, CF
₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , C
F ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ ,
_{CF 3 (CF 2) 7 -C} 6 H 6 -Si (OC
₂ H ₅ ) ₃ , and the method of microencapsulating alkoxysilane surfactants and acid catalysts is described in “New technology for microencapsulation and its application development and application examples, published by the Management Development Center Publishing Department 1978” or “Microcapsule”.・ It is well known for its manufacturing method, properties, applications, and Sankyo Publishing, 1977. The preferable content of the alkoxysilane surfactant in the surface treatment agent of the present invention is 1 to 30% by weight.

On the other hand, the acid catalyst is preferably an organic acid such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, carboxylic acid or sulfonic acid. Alternatively, an organic amine compound containing no active hydrogen can be used. Moreover, the preferable addition amount is 0.1
15% by weight.

As the liquid or solid medium, any solvent can be used regardless of whether it is aqueous or non-aqueous, as long as it can disperse without breaking the microcapsules, but alcohol or petroleum solvents are preferred. For example, butyl alcohol, isopropyl alcohol, liquid paraffin, silicone, paraffin wax and the like can be used. 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 preferable content of the liquid or solid medium in the present invention is 45 to 98.9% by weight.
It is.

The viscosity of the surface treatment agent is 1000 cp after preparation.
If it is s or more, the flow of the treatment liquid is small at the time of application and handling is convenient, but if it is too hard, it is difficult to use. Furthermore, if the mixture of a liquid or solid medium having a boiling point of 200 ° C. or higher and a boiling point of 100 to 200 ° C.,
After application, the low boiling point components evaporate quickly and the coating film hardens, so removal by wiping becomes extremely easy.

Further, as the polishing agent, alumina, silicon carbide boron carbide, chromium oxide, iron oxide, artificial diamond or silica fine particles having an average particle size of about 10 μm or less are used alone or in combination of two or more kinds. This is convenient because the surface of the substrate is cut in a very small amount during coating, and the clean surface can be directly reacted with a substance having at least one microencapsulated chlorosilyl group. The preferred content of the abrasive in the present invention is 1 to 50% by weight.

Further, when calcium carbonate is added to the surface treating agent of the present invention, when a volatile acid such as hydrochloric acid or nitric acid is used as an acid catalyst, excess volatilization is caused by reacting with the volatile acid. It is possible to prevent the generation of acid odor by trapping the acidic acid.

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 apply the surface-treating agent to the surface of the base material while destroying at least the microcapsules so that the surface of the base material and the alkoxysilane interface are The activator is reacted with the acid catalyst. Alternatively, after the surface of the base material is thoroughly washed in advance, a surface treatment agent is applied to the surface of the base material while at the same time polishing the surface of the base material with an abrasive, while destroying the microcapsules, thereby cleaning the surface of the base material. And an alkoxysilane surfactant and an acid catalyst are preferably 20 to 3
Let react for 0 minutes. At this time, the reaction between the alkoxysilane surfactant, the acid catalyst and the surface of the substrate proceeds as shown in the following chemical formula (Formula 1).

[0018]

Embedded image

Therefore, by this treatment, an ultrathin film in which at least an alkoxysilane surfactant is covalently fixed to the surface of the base material via Si atoms can be formed on the surface of the base material.
As is clear from the above reaction, the base material usable in the present invention is a base material having a hydroxyl group (—OH) on its surface, for example, A
1, hydrophilic metal such as glass, ceramics, paper, fiber, leather and other hydrophilic base materials. If the substance does not have a hydroxyl group on the surface, such as plastic, the surface may be hydrophilized in advance in a plasma atmosphere containing oxygen, for example, by treating with 100 W for 20 minutes or corona treatment. However, in the case of polyamide resin or polyurethane resin, imino group (-N
H) exists, and the hydrogen of this imino group (—NH) and the alkoxysilyl group (—SiOA) of the chemical adsorbent undergo a dehydration reaction to form a siloxane bond (—SiO—). do not need.

The surface treatment agent of the present invention can be widely applied to the following uses, for 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 with paint or the like. (B) Examples of knives: kitchen knives, scissors, knives, cutters, chisels, razors, hair clippers, saws, planes, chisels, cones, awls, bites, drill blades, mixer blades, juicer blades, milling Machine blades, lawnmower blades, punches, push cutters, stapler blades, can opener blades, or surgical scalpels. (C) Examples of needles: needles for acupuncture, sewing needles, sewing needles, tatami needles,
Injection needle, surgical needle, safety pin, etc. (D) Examples of ceramic products: ceramic products, glass products, ceramic products, products containing enamel, and the like. For example, sanitary porcelain (for example, toilet bowl, wash basin, bath, etc.), tableware (for example, bowl, dish, bowl, cup, bottle, coffee kettle, pot, mortar, cup, etc.), vase (basin, flowerpot,
Aquarium, etc.), aquarium (aquaculture aquarium, appreciation aquarium, etc.), chemical laboratory equipment (beaker, reaction vessel, test tube, flask,
Petri dishes, cooling tubes, stirring rods, stirrers, mortars, vats, syringes), tiles, tiles, enamel dishes, enamel washbasins, enamel pots. (E) Examples of mirrors: hand mirror, figure mirror, bathroom mirror, toilet mirror,
Mirrors for automobiles (rearview mirrors, side mirrors), half mirrors, mirrors for show windows, and mirrors for department stores. (F) Examples of molding members: press molding die, cast molding die, injection molding die, transfer molding die, vacuum molding die, blow molding die, extrusion die. , 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, bloodstone, 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 molds for forming food: molds for baking cakes, molds for baking cookies, molds for baking, molds for chocolate molding, molds for jelly molding, molds for ice cream molding, oven dishes, ice trays, and the like. (I) Examples of cooking utensils: pots, kettles, kettles, pots, frying pans, hot plates, grills for cooking, oil drainers, octopus grilling plates, and the like. (J) Examples of paper: gravure paper, water and oil repellent paper, poster paper,
(K) Examples of resins: polyolefins such as polypropylene and polyethylene, polyvinyl chloride, polyvinylidene chloride,
Polyamide, polyimide, polyamideimide, polyester, aramid, polystyrene, polysulfone, polyethersulfone, polyphenylene sulfide, phenolic resin, furan resin, urea resin, epoxy resin, polyurethane, silicon resin, ABS resin, methacrylic resin,
Acrylic ester resin, polyacetal, polyphenylene oxide, etc. (l) Examples of home appliances: televisions, radios, tape recorders, audio, CDs, refrigerators for refrigerators, freezers, air conditioners, juicers, mixers, fans , Lighting equipment, clock face, perm dryer, etc. (M) Examples of sporting goods: skis, fishing rods, poles for pole vaults, boats, yachts, jet skis, surfboards, golf balls, bowling balls, fishing lines, fish nets,
Fishing float. (N) Examples of application to vehicle parts: (1) ABS resin: lamp cover, instrument panel, interior parts, motorcycle protector (2) Cellulose plastic: car mark, handle (3) FRP (fiber reinforced resin): Outer panel bumper, engine cover (4) Phenol 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) Polyaminobismaleimide: engine parts, gearbox, wheel, suspension drive system (10) Methacrylic resin is lamp cover lens, instrument panel and cover, center mark (11) ) Polypropylene is a bumper. (12) Polyphenylene oxide: radiator grill, 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, measuring instruments, drafting tools, etc. (P) Examples of building materials: roof materials, outer wall materials, and interior materials. Roof materials include kiln tiles, slate tiles, and galvanized iron sheets.
Wood (including processed wood), mortar, concrete, ceramic sizing, metal sizing, bricks, stones, plastic materials, metal materials such as aluminum, etc. are used as outer wall materials. 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 and the like. For example, buildings, building materials, art objects, figurines, baths, tombstones, monuments, gateposts, stone walls, sidewalk paving stones, etc. (R) Examples of musical instruments and acoustic instruments: musical instruments such as percussion instruments, string instruments, keyboard instruments, woodwind instruments, brass instruments, and acoustic instruments such as microphones and speakers. Specifically, drums, cymbals, violins, cellos, guitars, kotos, pianos, flutes, clarinets, shakuhachi, horns and other percussion instruments, string instruments, keyboard instruments, woodwind instruments, brass instruments, and microphones, speakers, Sound equipment such as earphones. (S) Others, such as thermos bottles, vacuum equipment, insulators for electric power transmission or spark plugs, etc., which have high water-repellent, oil-repellent and antifouling effects and have a high withstand voltage.

[0021]

EXAMPLES Examples will be described below with reference to FIG. 1, which is a schematic sectional view in which the surface of a base material is enlarged to the molecular level. In the following examples,% means% by weight unless otherwise specified.

(Example 1) Preparation of surface treatment agent n-paraffin (bp 210 ° C.) 20 g isopropyl alcohol 5 g Silicone oil (Shin-Etsu Chemical KF-96, 1000 cps) 5 g Paraffin as a paraffin wax (Kanto Kagaku mp94-96). ° C.) 20 g heptadecafluorodecyltrimethoxysilane _{(CF 3 (CF 2) 7} - (CH 2) 2 -Si (OCH 3) 3) 10g α- alumina (mixture put average particle size 1 [mu] m) 5 g in an Erlenmeyer flask Then, the suspension was obtained by stirring while heating to 100 ° C. After cooling this liquid to room temperature (25 ° C.), 10 g of 3% sulfuric acid microencapsulated with formalin condensation resin as an acid catalyst was added and stirred, and a solid soft waxy viscosity of about 2500 c
It became a ps surface treatment agent. The 3% sulfuric acid was microencapsulated according to the method described in the above publication. The surface treatment agent thus obtained was used to perform the following treatments to evaluate water and oil repellency and durability.

As a surface-treated substrate, automobile window glass 1
Was used. On the surface of this glass 1, OH containing active hydrogen
The group 2 is contained in a large amount (FIG. 1 (a)). Therefore, the surface treatment agent prepared as described above is applied to the glass surface by rubbing with a sponge. At that time, the glass surface is polished and removed very thinly with an abrasive (α-alumina) to be cleaned. Further, the capsules of the formalin condensation resin are destroyed and sulfuric acid and putadecafluorodecyltrimethoxysilane are mixed and brought into contact with the clean glass surface. Then, when left for 30 to 40 minutes, n-paraffin was evaporated and a white coating film was formed. At this time, at the interface between the coating film and the surface of the substrate, even if silicone oil or paraffin is present, there is a certain probability that the methoxysilyl group 3 of heptadecafluorodecyltrimethoxysilane is changed as shown in FIG. 1 (b). The OH group 2 on the surface of the base material reacts in the presence of sulfuric acid. At this time, first, a dealcoholization reaction represented by the following formula (Formula 2) proceeds to produce a heptadecafluorodecyltrisilole molecule.

[0024]

Embedded image

Thereafter, the silanol groups produced in the above reaction and the group-active hydrogen of the OH group on the surface of the substrate undergo a dehydration reaction as shown in the following formula (Formula 3), and the heptadecafluorodecyltrisilole molecule becomes SiO 2. It is chemically adsorbed to the surface of the base material through the bond and fixed by the covalent bond.

[0026]

Embedded image

After that, when the excess surface treatment agent is wiped off with a rag, a large number of heptadecafluorodecyltrimethoxysilane molecules as shown in FIG. 1 (c) are covalently bonded to the surface of the substrate via the network bond of SiO. The fixed fluorocarbon polymer film (ultra-thin film having a film thickness of several nm) 4 could be formed on the surface of the substrate.

It should be noted that this coating did not peel at all even after the goth test. The water repellent angle was 115 degrees. Further, even though it was rubbed with a wet cloth 50,000 times, the water repellency was hardly deteriorated. Moreover, even if the salad oil was rubbed, it could be easily removed by wiping with tissue paper. Table 1 shows the evaluation results.

In this embodiment, the acid catalyst is added in the form of microcapsules to prevent self-reaction of the surface treatment agent and ensure storage stability.
This occurs mainly due to the hydrolysis reaction of water in the acid catalyst and the alkoxysilane surfactant under the acid catalyst. Therefore,
In order to improve the storability, it is sufficient that the acid catalyst and the alkoxysilane surfactant are not mixed in the treatment agent. That is, at least one of the alkoxysilane surfactant and the acid catalyst, or both of them were microencapsulated and added, and the same effect was exhibited. Therefore, it is not necessary to be limited to microencapsulating only the acid catalyst. Furthermore, in this method, at the time of treatment, it is necessary to mix at least the surface of the base material with the acid catalyst and the alkoxysilane surfactant to bring them into contact with each other, that is, it is necessary to react the alkoxysilane surfactant and the acid catalyst on the surface of the base material. The microcapsules prevent the catalyst and surfactant from mixing. This problem could be solved by making the microcapsules pressure-sensitive and applying them to the surface of the substrate while destroying the capsules.

When a volatile acid such as hydrochloric acid or nitric acid is used as the acid catalyst, a substance that reacts with the volatile acid,
For example, by adding calcium carbonate in an amount of 5 to 30%, an excessive volatile acid was trapped and almost no acid odor was generated.

The following example shows the case where calcium carbonate is added. (Example 2) The following surface treatment agent was prepared and evaluated in the same manner as in Example 1. n-paraffin (bp. 180 ° C.) 20 g butyl alcohol 4 g silicone oil (Shin-Etsu Chemical KF-96, 1000 cps) 3 g paraffin (Kanto Kagaku mp86 ° C.) 25 g calcium carbonate (average particle size 1 μm) 15 g in an Erlenmeyer flask and mixed. Then, the suspension was obtained by stirring while heating to 100 ° C. After the liquid was cooled to room temperature, 4% hydrochloric acid 8g and heptadecafluorodecyl triethoxysilane as an acid catalyst _{(CF 3 (CF 2) 7} - (C
H ₂ ) _2- Si (OC ₂ H ₅ ) ₃ ) was microencapsulated with formalin condensation resin, 10 g of which was added and stirred,
Solid soft waxy viscosity about 4500 cps
Became a surface treatment material. The encapsulation of heptadecafluorodecyltriethoxysilane followed the method of the above-mentioned publication.

Using this surface treating agent, the same evaluation as in Example 1 was carried out. It had a slightly high fluidity, but after application it was 20
The same result as in Example 1 was obtained except that a white coating film was formed after standing for about 30 minutes. Table 1 shows the evaluation results. When the glass was treated with this treating agent, almost no odor of hydrochloric acid was felt.

Example 3 The heptadecafluorodecyltrimethoxysilane of Example 1 was converted into tridecafluorooctyltriethoxysilane (CF ₃ (CF ₂ ) ₅ (CH ₂ ).
_2- Si (OC ₂ H ₅ ) ₃ ) was used, and the same experiment as in Example 1 was performed. Table 1 shows the evaluation results. Even when glass was treated with this treating agent, almost no odor of hydrochloric acid was felt.

Example 4 An experiment was conducted under the same conditions except that the window glass of Example 2 was replaced with a rearview mirror and calcium carbonate was removed. The results are shown in Table 1. When the rearview mirror was treated with this treating agent, a slight smell of hydrochloric acid was felt.

Example 5 An experiment was carried out under the same conditions except that the mirror of Example 4 was replaced with the hood of a painted automobile, and 15 g of activated alumina was added instead of calcium carbonate. The results are shown in Table 1. When the bonnet was treated with this treating agent, the smell of hydrochloric acid was slightly felt.

Example 6 An experiment was conducted in the same manner as in Example 2 except that the window glass of Example 2 was replaced with a urethane bumper. The results are shown in Table 1.

Example 7 An experiment was performed in the same manner as in Example 1 except that silica (average particle size: 5 μm) was used in place of the alpha alumina of Example 1. The results are shown 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. Table 1 shows the processing results.

Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that the microcapsulated sulfuric acid of Example 1 was omitted. Table 1 shows the processing results. When only the alkoxysilane-based substance was used as in this comparative example, the durability of the formed coating was almost nonexistent.

Comparative Example 2 An experiment was conducted in the same manner as in Example 2 except that the microencapsulated hydrochloric acid of Example 2 was omitted. Table 1 shows the processing results. In this case, there was no smell of hydrochloric acid,
Similar to Comparative Example 1, the formed film had almost no durability.

[0041]

[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.

[0043]

As described above, according to the surface treating agent of the present invention, the active hydrogen on the surface of the substrate is used to form the polymer film, so that it can be applied to various materials such as plastics, ceramics, glass, etc. The protective film can be formed efficiently. At this time, since either one or both of the alkoxysilane surfactant and the acid catalyst are added in a microencapsulated form, the pot life can be extended by about four times as long as when added as it is. further,
When a volatile acid is used, by adding a substance that reacts with the acid, the odor of the volatile acid can be considerably trapped.

The method of using the surface treatment agent of the present invention is to provide a water-repellent, oil-repellent, and anti-fouling protective film for electronic products, electric appliances, automobiles, industrial equipment, mirrors, spectacle lenses, etc., which has heat resistance, weather resistance, and abrasion resistance. Applicable to required equipment.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view in which a substrate surface of Example 1 of the present invention is enlarged to a molecular level, (a) shows a substrate surface before applying a surface treatment agent, and (b) shows a surface treatment agent. The surface of the base material immediately after coating, (c) shows the surface of the base material on which the reaction has further proceeded and the chemical adsorption film is formed.

[Explanation of symbols]

 1 substrate 2 OH group 3 interface between coating film and substrate 4 fluorocarbon polymer film

Claims (9)

[Claims] 1. An alkoxysilane surfactant, an acid catalyst,
A surface treatment agent containing a liquid or solid medium, to which at least one selected from an alkoxysilane surfactant and an acid catalyst is added by being microencapsulated. 2. The surface treatment agent according to claim 1, which contains an abrasive. 3. The viscosity of the liquid medium at 25 ° C. is 100.
The surface treatment agent according to claim 1 or 2, which has a viscosity of 0 cps or more. 4. The liquid or solid medium has a boiling point of 200.
The surface treatment agent according to claim 1, 2 or 3, which is a mixture of a medium having a temperature of not less than 0 ° C and a medium having a boiling point of 100 to 200 ° C. 5. The surface treatment agent according to claim 1, wherein the alkoxysilane surfactant has a fluorocarbon group. 6. The alkoxysilane surfactant is CF <sub>3
- (CF 2) n - (</sub> R) m -SiX p (OA) 3-p (n
Is 0 or an integer, R is an alkynyl group, a vinylene group, an ethynylene group, an arylene group, a molecular chain containing a silicon or oxygen atom, m is an integer of 0 or 1, X is an H atom, an alkyl group, an alkoxyl group, a fluorine-containing alkyl group. Group or a substituent of a fluorine-containing alkoxy group, A is an alkyl group, p is 0, 1
Or the integer of 2) is used, The surface treatment agent of any one of Claims 1-5. 7. The abrasive is at least one selected from alumina, silicon carbide, boron carbide, chromium oxide, iron oxide, artificial diamond and silica fine particles, and the abrasive is particles having an average particle size of 10 μm or less. The surface treatment agent according to any one of claims 2 to 6. 8. The surface treatment agent according to claim 1, wherein calcium carbonate is added. 9. After thoroughly cleaning the surface of the base material in advance,
The surface treatment agent is applied to the surface of the base material while destroying the microcapsules of the surface treatment agent according to any one of claims 1 to 8, and the surface of the base material and the alkoxysilane surfactant of the surface treatment agent and A method for using a surface treatment agent, which comprises removing an excess surface treatment agent after reacting with an acid catalyst.