JP3126837B2 - Surface treatment composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a so-called wax type surface treatment composition and a method for producing the same. More specifically, the present invention relates to a surface treatment composition for forming a chemically adsorbed protective film having high durability, small thickness, and excellent water / oil repellency on a substrate surface, and a method for producing the same.

[0002]

2. Description of the Related Art Surface treatment agents include, for example, wax agents for cars, wax agents for floors and interior products, polishing agents, polisher agents for fur, lubricants for sliding doors and sliding doors, and lubricants for sliding parts of machine parts. Used in various fields.

Incidentally, these conventional surface treatment agents such as polishing agents are of a solid type or an emulsion type, and the mainstream is a mixture of a petroleum-based solvent, a silicone, a wax, a lower alcohol or the like and an abrasive. .

[0004]

However, the conventional surface treatment material does not have high gloss and water repellency, and the obtained protective film is merely applied to the surface of the base material. Robustness was not enough, and there was almost no oil repellency. In particular, there were problems with durability and robustness. This is simply due to the treatment agent being physically attached to the substrate surface.

[0005] The present invention provides a so-called wax type surface treatment agent for solving the above-mentioned problems of the prior art,
Not only excellent in luster and water repellency, the protective film is chemically bonded to the surface of the base material, and has high durability and robustness. It is intended to provide a manufacturing method.

[0006]

In order to achieve the above object, the surface treatment composition of the present invention comprises SiCl ₄ , SiHC
l ₃ , SiH ₂ Cl ₂ and SiCl ₃ O (SiCl ₂ O) _n S
Si (OH) ₄ , SiH (OH) ₃ , SiH ₂ (O ₂ ) generated by hydrolysis of at least one inorganic chlorosilyl compound selected from iCl ₃ (n is 0 or an integer)
H) ₂ and _{Si (OH) 3 O [Si} (OH) 2 O] n Si
(OH) ₃ (n is 0 or an integer)
Further, it has a configuration including one inorganic siloxane compound, an organic chemisorption compound having at least one halosilyl group, and a non-aqueous viscous liquid or solid medium.

[0007]

In the above structure, the organic chemisorbed compound having at least one halosilyl group is A-Si
X _p Y _3-p (where A is an organic group containing at least one group selected from an alkyl group, a vinyl group, an ethynyl group, an aryl group, a substituent containing a silicon or oxygen atom,
X is H, an alkyl group, an alkoxyl group, a substituent of a fluorine-containing alkyl group or a fluorine-containing alkoxy group, Y is Cl, B
at least one halogen group selected from r, F, and I;
p is preferably 0, 1 or 2).

In the above structure, the viscosity of the non-aqueous viscous liquid or solid medium is preferably 1000 cps or more. Further, in the above configuration, it is preferable that the viscous liquid or solid medium is a mixture of one having a boiling point of 100 ° C or higher and one having a boiling point of 25 ° C to 100 ° C or lower.

In the above composition, the composition preferably contains inorganic particles having an average particle diameter of 10 μm or less. Furthermore, SiCl ₄ , SiHCl ₃ , SiH ₂ C
l ₂ and SiCl ₃ O (SiCl ₂ O) _n SiCl ₃ (n is
0 or an integer).
Rosilyl compound and the inorganic chlorosilyl compound
A siloxane compound formed by decomposition and a halosilyl group
An organic chemisorption compound having at least one
Surface treatment composition comprising a viscous liquid or a solid medium
Contains a tertiary amine containing no active hydrogen or an active hydrogen.
If amide chloride is contained, hydrochloric acid is generated.
Is practically preferable.

Next, the method for producing the surface treatment composition of the present invention comprises the steps of: adding SiC to a non-aqueous viscous liquid or solid medium;
l ₄ , SiHCl ₃ , SiH ₂ Cl ₂ and SiCl ₃ O (S
adding at least one inorganic chlorosilyl compound selected from iCl ₂ O) _n SiCl ₃ (n is 0 or an integer),
By reacting with water contained in the mixture , Si (O
H) ₄ , SiH (OH) ₃ , SiH ₂ (OH) ₂ and Si
(OH) ₃ O [Si (OH) ₂ O] _n Si (OH) ₃ (n is
0 or an integer) and a step of mixing an organic chemisorbed compound having at least one halosilyl group. Another method for producing a surface treatment composition of the present invention does not include active hydrogen before or after the step of adding an inorganic chlorosilyl compound and reacting with water contained in the mixture to generate a siloxane compound. A step of adding and mixing a tertiary amine or an amide containing no active hydrogen.

[0012]

According to the constitution of the surface composition (surface treating agent) of the present invention, the composition comprises an inorganic siloxane compound, a chemisorbed compound having at least one halosilyl group, and a non-aqueous viscous liquid or solid medium. It is a so-called wax type surface treatment agent that not only has excellent luster and water repellency, but also has a protective film chemically bonded to the substrate surface, and has high durability and robustness. A certain protective film can be formed. Further, for example, if a treatment similar to the treatment method of car wax is performed using the surface treatment agent, a chemically adsorbed compound is fixed by a covalent bond to an arbitrary base material surface, so that extremely thin water / oil repellency and durability are obtained. An excellent protective film can be formed very easily. Further, the coating operation is easy and does not require extensive reaction equipment.

Further, the siloxane compound is Si (OH)
_{4, SiH (OH) 3,} SiH 2 (OH) 2, and Si
(OH) ₃ O [Si (OH) ₂ O] _n Si (OH)
_When at least one compound selected from ₃ (n is 0 or an integer), it has an effect of polishing the formed film and an effect of adjusting the viscosity.

Further, the organic chemisorption compound having at least one halosilyl group is A-SiX _p Y _3-p (where A is an alkyl group, a vinyl group, an ethynyl group, an aryl group, a silicon or oxygen-containing substituent). An organic group containing at least one group selected from the group: X is a substituent of H, an alkyl group, an alkoxyl group, a fluorinated alkyl group or a fluorinated alkoxy group, and Y is at least one group selected from Cl, Br, F and I. If one halogen group, p is 0, 1 or 2), a chemical adsorption film can be formed on the surface of the substrate via the Si group. Particularly preferred organic chemisorption compounds are
It is a compound having a chlorosilyl group.

When the viscosity of the non-aqueous viscous liquid or solid medium is 1000 cps or more, the flow of the processing liquid during coating is small, and the handling is convenient. Furthermore, if the viscous liquid or solid medium is a mixture of those having a boiling point of 100 ° C. or more and those having a boiling point of room temperature to 100 ° C. or less, the low-boiling components evaporate quickly after application and the coating film is hardened, so that removal is extremely difficult. It will be easier.

Further, the abrasive has an average particle size of 1
If alumina, silicon carbide boron carbide, chromium oxide, iron oxide, artificial diamond or silica fine particles of 0 μm or less are added, a very small amount of the substrate surface is removed without impairing the gloss of the substrate surface during application, it is convenient because the direct least-halo silyl-cleaning surface can react with an organic chemical adsorbent molecules with one.

Next, according to the production method of the present invention, after preparing a non-aqueous viscous liquid or solid medium in advance,
Inorganic silyl compounds containing multiple chloro groups (inorganic chloro
A silyl compound) , and dehydration by dehydrohalogenation (for example, dehydrochlorination reaction) with water contained in the non-aqueous viscous liquid or solid medium to generate a siloxane compound. Thereafter, by mixing a chemisorbed compound having at least one chlorosilyl group, the chemisorbed compound can be maintained in an active state. In addition, as an inorganic silyl compound containing a plurality of chloro groups,
SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or SiC
l ₃ O (SiCl ₂ O) _n SiCl ₃ (n is 0 or an integer)
It is convenient to use Also contains multiple chloro groups
The amount of the inorganic silyl compound to be added may be appropriately added in an amount necessary for removing water contained in a non-aqueous viscous liquid or a solid medium.

The non-aqueous viscous liquid or solid medium usually contains some water. When mixing the organic chemical adsorbing compound having at least one direct halo silyl group viscous liquid or solid medium therefor nonaqueous, thus deactivated reacts with the said water. Therefore, after preparing a non-aqueous viscous liquid or solid medium in advance and mixing a tertiary amine or amide containing no active hydrogen,
A siloxane compound is formed by mixing a substance containing a plurality of chlorosilyl groups and dehydrochlorinating with water or a thiol-based or amino-based impurity contained in the non-aqueous viscous liquid or solid medium. That is, the water reacts to form siloxane and hydrochloric acid and is dehydrated. Further, thiol-based or amino-based impurities react with SiCl groups to form Si-
An S or Si-N bond is generated to be fixed as a siloxane compound . Here, tertiary amine containing no active hydrogen or active
If an amide containing no hydrogen is added and mixed,
Hydrochloric acid is neutralized to chloride and stabilized
included. If no amine or amide is added,
In this case, it becomes a gas and is removed. Note that the generated poly
Siloxane and other siloxane compounds have few halosilyl groups.
Stable for at least one organic adsorption compound
No need to remove. Rather, polysiloxane compounds are glossy
It is more convenient to keep it as it has an effect. Further
Having at least one chlorosilyl group thereafter
When mixed with a sorbent compound, water, thiol or amino impurities contained in a non-aqueous viscous liquid or solid medium are removed by a dehydrochlorination reaction with substances already containing multiple chlorosilyl groups. because there, has the effect of organic chemical adsorbing compound having at least one halo silyl group can be produced include a surface treatment agent in an active state.

The method of using the surface treating agent of the present invention is as follows.
The base material containing a hydrophilic group on the surface, and applying at least halo shea <br/> surface treating agent containing a viscous liquid or solid medium of the organic chemical adsorption compound and a non-aqueous system having one Lil group,
Then reacting the molecule with one at least halo silyl group with the substrate surface at room temperature. At this time, the molecular dehydrochlorination reaction in the that contains active hydrogen on the substrate surface Kurorushiriru group and an active hydrogen with one at least halo silyl group occurs is fixed covalently to the substrate surface via the Si atom You. Thereafter, the unreacted surface treatment agent is wiped off or washed off with a detergent and water. At this time, the organic chemical adsorbing molecules having one at least halo silyl group reacts with moisture in the air, the viscous liquid or solid medium of non-aqueous systems, dehydrochlorination reaction between the active hydrogen and halo silyl group of the substrate surface Has the function of protecting the reaction at the interface between the surface treatment agent and the substrate, that is, at the surface of the substrate, from moisture in the air that hinders the reaction.

[0020] Thus, this process, ultra-thin organic molecules having one at least halo <br/> silyl group is covalently immobilized to the substrate surface via the Si atom can form on the substrate surface. As described above, there is significant that you put the surface treatment agent and the organic chemical adsorbing compound having at least one halo silyl group in the active state.

[0021] In this case, at least the halo silyl group in the organic molecules having one made to contain a fluorocarbon group, it is advantageous because it forms a fluorocarbon polymer film a strong water and oil repellency to the substrate surface. At least halo silyl group as the organic molecules having _{one, CF 3 - (CF 2)} n -
(R) _m -SiX _p Cl _3-p (n is 0 or an integer, R is an alkyl group, vinyl group, ethynyl group, aryl group, a substituent containing a silicon or oxygen atom, m is 0 or 1, X
Is preferably a substituent of H, an alkyl group, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group, and p is preferably 0, 1 or 2).

The substrate may be a metal, ceramics, glass, plastic, if the surface contains active hydrogen.
Applicable to paper, fiber, leather, etc. In the case of a plastic or a fiber having no active hydrogen on the surface, the surface may be preliminarily treated with an oxygen-containing plasma or corona atmosphere to make the surface hydrophilic.

[0023]

EXAMPLES The surface treatment composition of the present invention contains at least
Produced by hydrolysis of organic chlorosilyl compounds
A sun compound and at least one halosilyl group
Mechanically adsorbed compounds and non-aqueous viscous liquids or solids
And a medium as a main component. Or at least, inorganic
Siloxane formed by hydrolysis of lorosilyl compound
Organic compound having at least one halosilyl group with a compound
Non-aqueous viscous liquid or solid medium
To a tertiary amine containing no active hydrogen.
Or amide chlorides containing no active hydrogen
You.

In the above, as the organic molecule having at least one halosilyl group, for example, the following hydrocarbon molecules can be used. CH ₃ (CH ₂ ) _{r
SiX p Cl 3-p, CH} 3 (CH 2) s O (CH 2) t SiX
_{p Cl 3-p, CH 3} (CH 2) u Si (CH 3) 2 (CH 2) v
_{SiX p Cl 3-p, CF} 3 COO (CH 2) w SiX p Cl
_{3-p, Cl 3-p} SiX p (R) m (CF 2) n (R) m SiX
_p Cl3 _-p (where r is preferably 1 to 25, s
Is 0 to 12, t is 1 to 20, u is 0 to 12, v is 1 to 2.
0 and w represent 1 to 25. ) CF ₃ (CF ₂ ) _n (R) _m S
iX _p Cl _3-p (where n is 0 or an integer, R is an alkyl group, vinyl group, ethynyl group, aryl group, a substituent containing a silicon or oxygen atom, m is 0 or 1, X is H, The substituent of the alkyl group, the alkoxyl group, the fluorinated alkyl group or the fluorinated alkoxy group, and p represents 0, 1 or 2.) In addition to the above compounds, the following compounds can also be used. CH ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃ ,
CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl
₃ , CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiC
l ₃ , CH ₃ COO (CH ₂ ) ₁₅ SiCl ₃ , CF ₃ (C
F ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , Cl ₃ Si (CH ₂ )
₂ (CF ₂ ) ₆ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ )
₅ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ C ₆ H ₄ SiC
l _{3 The} tertiary amine containing no active hydrogen includes triethylamine, trimethylamine, pyridine, N-methylpyrrole, N, N-dimethylaniline, triazine, dimethylbutylamine, dipyridine, indole, N, N
N-methylpyrrolidinone and the like can be used as the amide containing no active hydrogen. The addition amount of the tertiary amine or amide in the present invention, at least a plurality black rosiglitazone hydrochloride amount organic molecules are generated by decomposition of all with one substance and halo silyl groups containing Lil groups and equimolar or more preferably . That is, when the chemical adsorption molecules contains one halo silyl group, may be equimolar to chemisorption molecules are contained. Also if the chemical adsorption molecules contains two halo silyl group,
It may be twice the mole of the chemisorbed molecules contained. Furthermore, if the chemical adsorption molecules contains three halo silyl group, it is sufficient 3-fold molar chemisorption molecules are contained. Of course, there is no problem even if it is excessively added.

The preferred content of the chemically adsorbed molecules in the surface treating agent of the present invention is 1 to 30% by weight. Also,
Any non-aqueous solvent can be used as the viscous liquid or solid medium, but petroleum solvents, silicone,
Paraffin wax can be used at a low cost. 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 viscous liquid or solid medium in the present invention is 5
0 to 90 wt%.

If the viscosity is 1000 cps or more after the adjustment, the flow of the processing liquid during coating is small and the handling is convenient, but it is difficult to use the coating liquid if it is too hard. Furthermore, if a mixture of a viscous liquid or a solid medium having a boiling point of 100 ° C. or higher and a boiling point of room temperature to 100 ° C. or lower is used, the low-boiling components evaporate quickly after application and the coating film is hardened. Becomes extremely easy.

Furthermore, when alumina, silicon carbide boron carbide, chromium oxide, iron oxide, artificial diamond or silica fine particles of about several microns are added as an abrasive, an extremely small amount of the base material surface is cut off at the time of application, and a clean surface is obtained. it is convenient because it reacting an organic molecule having one direct least-halo silyl groups as. The preferred content of the abrasive in the present invention is 1 to 10 wt%.

On the other hand, as a production method , SiCl ₄ , SiHCl ₃ , Si
H ₂ Cl ₂ and SiCl ₃ O (SiCl ₂ O) _n SiCl ₃
(N is 0 or an integer)
Chlorosilyl compound is added and included in the mixture
Reacting with existing water to form a siloxane compound
And organic chemisorption having at least one halosilyl group
Mix the compounds. Further, in the above manufacturing method,
Chlorosilyl compound is added and included in the mixture
Reacting with existing water to form a siloxane compound
Before or after the tertiary amine containing no active hydrogen or
A step of adding and mixing an amide containing no active hydrogen.

Here, as the inorganic silyl compound containing a plurality of halogen groups, SiCl ₄ , SiHCl ₃ , S
iH ₂ Cl ₂ , SiCl ₃ O (SiCl ₂ O) _n SiCl ₃ (n
Is preferably at least one compound selected from 0 or an integer.

The method of use is such that the surface of the substrate having active hydrogen is thoroughly washed and dried, and then the surface composition is applied.
Then, at room temperature, active hydrogen such as a hydroxyl group (−
Organic chemisorption with at least one OH) and halosilyl group
Compounds, for example, having at least one chlorosilyl group
With organic molecules ( organic chemisorbed molecules). A dehydrochlorination reaction occurs between the active hydrogen on the surface of the substrate and the chlorsilyl group, and the chemisorbed molecules are fixed to the surface of the substrate via covalent bonds via Si atoms. Thereafter, the unreacted surface treatment agent is wiped off or washed off with a detergent and water. At this time, at least the chemisorbed molecules also react with the moisture in the air, but the non-aqueous viscous liquid or solid medium is formed from the moisture in the air that prevents the dehydrochlorination reaction between the active hydrogen and the chlorosilyl group on the substrate surface. It has the function of protecting the interface between the surface treatment agent and the substrate, that is, the reaction at the surface of the substrate so as not to be hindered.

Therefore, by this treatment, the chemisorbed molecule becomes S
It is covalently immobilized on the surface of the base material via the i-atoms to form a chemisorption film. This chemisorption film is an ultrathin film having a thickness of Angstrom or nanometer order.

The substrate which can be used in the present invention includes a substrate having a hydroxyl group (-OH) on its surface, for example, a metal such as Al, Cu or stainless steel, glass, ceramics, paper, fiber, leather or other hydrophilic substrate. No. If the surface of the material does not have a hydroxyl group, such as plastic, the surface may be previously treated in a plasma atmosphere containing oxygen.
The treatment may be performed with W for 20 minutes or corona treatment to make the surface hydrophilic, that is, hydroxyl groups may be introduced on the surface. However, in the case of a polyamide resin or a polyurethane resin, an imino group (> NH) is present on the surface, and hydrogen of the imino group (> NH) and chlorosilyl group (—SiCl) of the chemical adsorbent are dehydrochlorinated. Reacts with the silicon-nitrogen bond (-
Since SiN <) is formed, no special surface treatment is required. Furthermore, by this, a fluorocarbon polymer film is formed with good adhesion and thinness on the base material, so that electric appliances such as hot plates and rice cookers, automobiles, industrial equipment, glass, mirrors, spectacle lenses, interior goods, apparel, etc. An object of the present invention is to improve the performance of a substrate that requires heat resistance, weather resistance, and abrasion resistance coating of a product or the like.

The present invention can be widely applied to the following uses. (A) Examples of base material: The base material can be applied to materials composed of metal, ceramics or 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, miller blades , Lawn mower blade, punch, press cutter, stapler blade, can opener blade, or surgical knife. (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, teacup, cup, bottle, coffee kettle, pot, mortar, cup, etc.), vase (water 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, bangles, brooches, tie pins, earrings, necklaces, precious metal decoration products, 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 for refrigerators , 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) Methacryl 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, mechanical pencils, pencil cases, binders, desks, chairs, bookshelves, racks, telephone stands, rulers, 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.
The outer wall materials include wood (including processed wood), mortar, concrete, ceramic sizing, metal sizing, bricks, stones, 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 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 equipment: musical instruments such as percussion instruments, string instruments, keyboard instruments, woodwind instruments, brass instruments, and acoustic instruments such as microphones and speakers. Specifically, percussion instruments such as drums, cymbals, violins, cellos, guitars, kotos, pianos, flutes, clarinets, shakuhachi, horns, instruments such as stringed 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 power transmission or spark plugs, etc., which have a high water-repellent, oil-repellent and anti-fouling effect and have a high withstand voltage.

The embodiments will be described below in order with reference to FIG. 1 which is a schematic diagram. In the following examples,% means% by weight unless otherwise specified. Example 1 (1) Preparation of surface treatment agent n-octane (bp. 143 ° C.) as a petroleum solvent: 30 g silicone oil as silicone (Shin-Etsu Chemical KF-96, 1000 cps): 20 g paraffin as paraffin wax (Kanto) Chemical product, mp 84-86 ° C.): 20 g Alpha alumina (average diameter 1 μm) as an abrasive: 5 g SiCl ₃ OSiCl ₃ as an inorganic silyl compound substance containing a plurality of chloro groups: 4 g was put in an Erlenmeyer flask and mixed. When the mixture was stirred while being heated to ℃, hydrochloric acid gas was generated to obtain a suspension. Thereafter Further, as the organic molecules having one at least halo silyl group, heptadecafluorodecyltrichlorosilane: CF
_{3 (CF 2) 7 - (} CH 2) a ₂ -SiCl ₃ were mixed and put into 6g Erlenmeyer flask, and cooled to room temperature, became solid soft wax. (2) Coating treatment The wax thus obtained was treated as a surface treatment agent as follows to evaluate the water / oil repellency and durability.

As a surface treatment substrate, a window glass 1 of an automobile
Was used (FIG. 1). The surface of the glass 1 contains a large amount of OH groups 2 containing active hydrogen. Therefore, the surface treatment agent adjusted as described above is applied using a sponge so as to be rubbed on the glass surface. After that, when left for 20 to 30 minutes, n-decane evaporated, and a white coating film 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 in FIG.
As shown in (2), heptadecafluorodecyltrichlorosilane 3 and OH group 2 on the substrate surface meet. At this time, sharing the substrate surface with active hydrogen of the O H groups and Kurorushiriru group of the heptadecafluorodecyltrichlorosilane is dehydrochlorination reaction is heptadecafluorodecyltrichlorosilane molecules to the substrate surface via the SiO bond Fixed with a bond.
After that, when the excess surface treatment agent is wiped off with a rag, a large number of heptadecafluorodecyltrichlorosilane molecules as shown in FIG. (Thickness of several tens of angstroms) 4 could be formed on the substrate surface.

At this time, the heptadecafluorodecyltrichlorosilane molecule also reacts with moisture in the air, but silicon oil or paraffin, which is a non-aqueous viscous liquid or solid medium, reacts with active hydrogen on the surface of the base material and halo. There was a function of preventing moisture in the air that hinders the dehydrochlorination reaction with the silyl group from entering the interface between the surface treating agent and the substrate, ie, the surface of the substrate.

Further, this film did not peel off even when the go-th test was performed. The water release angle was also 116 degrees. Even when rubbed with tempura oil, it could be easily removed by wiping with tissue paper.

Example 2 The same evaluation as in Example 1 was carried out by preparing the following surface treating agents. n-octane (bp. 126 ° C.) 20 g n-decane (bp. 143 ° C.) 30 g silicone oil (Shin-Etsu Chemical KF-96, 1000 cps) 20 g paraffin (Kanto Chemical mp. 54-56 ° C.) 20 g alpha alumina (1 micron) ) 5g SiCl ₃ OSiCl ₂ OSiCl ₃ to 4g n-methyl pyrrolidinone 3g mixed placed in an Erlenmeyer flask, then further heptadecafluorodecyltrichlorosilane CF ₃ (CF _{2) 7} - a (CH _{2) 2} -SiCl ₃ 7g Mixing and cooling to room temperature resulted in a solid soft wax. With this surface treatment agent, almost no hydrochloric acid was generated at the time of coating, and the same results as in Example 1 were obtained except that a white coating film was formed when the coating was left for 10 to 15 minutes after coating. Table 1 shows the results. Example 3 The heptadecafluorodecyltrichlorosilane of Example 2 was replaced with tridecafluorooctyltrichlorosilyl CF
An experiment was conducted in the same manner as in Example 2 except that ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ —SiCl ₃ was used. Table 1 shows the results.

Example 4 An experiment was conducted in the same manner as in Example 2 except that the glass of Example 2 was used as a mirror. Table 1 shows the results.

Example 5 The glass of Example 2 was used as a painted automobile door.
An experiment was performed in the same manner as in Example 2. Table 1 shows the results.

Example 6 An experiment was conducted in the same manner as in Example 2 except that the glass of Example 2 was used as a bonnet. Table 1 shows the results.

Example 7 The alpha alumina of Example 2 was replaced with silica (average particle diameter 1
μm), and an experiment was conducted in the same manner as in Example 2. Table 1 shows the results.

Example 8 An experiment was conducted in the same manner as in Example 1 except that the amount of n-decane in Example 1 was changed to 40 g. The obtained processing solution is approximately 3000
It became a viscous liquid wax of ０００4000 cps. Table 1 shows the processing results.

Comparative Example 1 The same experiment as in Example 1 was performed except that SiCl ₃ OSiCl ₃ of Example 1 was not added. Table 1 shows the processing results.

Comparative Example 2 The same experiment as in Example 2 was performed except that SiCl ₃ OSiCl ₂ OSiCl ₃ of Example 2 was not used. Table 1 shows the processing results
Shown in

[0046]

[Table 1]

As is clear from Table 1, in the case where the surface was treated with the surface treating agent of this embodiment, the surface retains water / oil repellency or hydrophilicity even after the surface is repeatedly rubbed and washed with a cloth containing water. Was. On the other hand, in Comparative Examples 1 and 2, water repellency and oil repellency were slightly poor even though the same amount of a molecule having one chlorosilyl group was added.

As described above, the method of this embodiment is as follows.
Since the polymer film is fixedly formed using active hydrogen on the surface of the base material, a protective film can be efficiently formed on plastics, ceramics, glass, and other various materials.

A non-aqueous viscous liquid or solid medium is prepared in advance, mixed with a tertiary amine or amide containing no active hydrogen, and then mixed with a silyl compound containing a plurality of chloro groups. Dehydrochlorination with water, thiol-based or amino-based impurities contained in viscous liquid or solid-state medium to form polysiloxane compound, and stabilizes water, thiol-based or amino-based impurities as siloxane and chloride And then add
Without being deactivated organic chemical adsorbing compound having at least one halo silyl group, there is an effect capable of producing active surface treatment agent.

[0050] Furthermore, when using a compound containing a fluorocarbon group and a halo silyl groups as film-forming material, Al, C
Even with a metal substrate such as u or stainless steel, a highly water- and oil-repellent film with excellent water and oil repellency, antifouling property, durability, etc. It can be formed thin.

The method for producing a chemisorption film according to the present invention is applicable to an ultra-thin heat-resistant, weather-resistant, and wear-resistant coating of electronic products, particularly electric appliances such as hot plates and rice cookers, automobiles, industrial equipment, mirrors and spectacle lenses. There is also an effect that can be applied to necessary equipment.

[0052]

As described above, according to the surface composition (surface treatment agent) of the present invention, a siloxane compound, an organic chemisorption compound having at least one halosilyl group,
By containing a non-aqueous viscous liquid or solid medium, it is a so-called wax type surface treatment agent, which not only has excellent luster and water repellency, but also has a protective film chemically bonded to the substrate surface. It is possible to form a protective film having high durability and robustness and further having oil repellency. Further, for example, if a treatment similar to the treatment method of car wax is performed using the surface treatment agent, a chemically adsorbed compound is fixed by a covalent bond to an arbitrary base material surface, so that extremely thin water / oil repellency and durability are obtained. An excellent protective film can be formed very easily. Further, the coating operation is easy and does not require extensive reaction equipment.

Next, according to the production method of the present invention, after preparing a non-aqueous viscous liquid or solid medium in advance,
Inorganic silyl compounds containing multiple chloro groups (inorganic chloro
A silyl compound) , and dehydration by dehydrohalogenation (for example, dehydrochlorination reaction) with water contained in the non-aqueous viscous liquid or solid medium to generate a siloxane compound. then, when mixing the organic chemical adsorbing compound having at least one halo silyl group can hold the chemisorption compound in the active state.

[Brief description of the drawings]

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

FIG. 2 is a schematic cross-sectional view when a substrate of Example 1 is coated with a surface treatment agent.

FIG. 3 is a schematic cross-sectional view when the surface treatment agent is chemically adsorbed on the base material of Example 1.

[Explanation of symbols]

 Reference Signs List 1 base material 2 OH group 3 interface between coating film and base material 4 fluorocarbon polymer film

Claims (8)

(57) [Claims] 1. The method according to claim 1, wherein the first and _second SiCl ₄ , SiHCl ₃ , and SiH ₂ Cl _{2 are provided.}
And SiCl ₃ O (SiCl ₂ O) _n SiCl ₃ (n is 0
Or an integer), at least one inorganic chlorosilyl compound selected from the group consisting of Si (OH)
_{4, SiH (OH) 3,} SiH 2 (OH) 2 and Si (O
H) ₃ O [Si (OH) ₂ O] _n Si (OH) ₃ (n is 0 or
Or an integer) , a surface treatment composition comprising at least one inorganic siloxane compound, an organic chemisorption compound having at least one halosilyl group, and a non-aqueous viscous liquid or solid medium. 2. An organic chemisorption compound having at least one halosilyl group is A-SiX _p Y _3-p (where A is an alkyl group, a vinyl group, an ethynyl group, an aryl group, a substituent containing a silicon or oxygen atom) X is a substituent of H, an alkyl group, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group, and Y is at least one group selected from Cl, Br, F, and I. The surface treatment composition according to claim 1, wherein a halogen group and p is 0, 1 or 2). 3. The surface treatment composition according to claim 1, wherein the viscosity of the non-aqueous viscous liquid or solid medium is 1000 cps or more. 4. A viscous liquid or solid medium having a boiling point of 1
The surface treatment composition according to claim 1, which is a mixture of one having a temperature of 00C or higher and one having a boiling point of 25C to 100C. 5. The surface treatment composition according to claim 1, wherein the composition contains inorganic particles having an average particle diameter of 10 μm or less. 6. A any surface treatment composition according to claim 1-5, further amides containing no tertiary amine or an active hydrogen containing no active hydrogen, characterized in that it contains as chlorides surface Treatment composition. 7. A non-aqueous viscous liquid or solid medium,
SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ and SiCl ₃
O (SiCl ₂ O) _{n At} least one inorganic chlorosilyl compound selected from SiCl ₃ (n is 0 or an integer) is added and reacted with water contained in the mixture to form Si
(OH) ₄ , SiH (OH) ₃ , SiH ₂ (OH) ₂ and S
i (OH) ₃ O [Si (OH) ₂ O] _n Si (OH) ₃ (n
Wherein the surface treatment composition comprises a step of producing at least one inorganic siloxane compound selected from the group consisting of 0 or an integer) and a step of mixing an organic chemisorption compound having at least one halosilyl group. Manufacturing method. 8. A tertiary amine containing no active hydrogen or an amide containing no active hydrogen, before or after the step of adding an inorganic chlorosilyl compound and reacting with water contained in the mixture to form a siloxane compound. The method for producing a surface treatment composition according to claim 7, comprising a step of adding and mixing.