JP2732777B2 - Manufacturing method of chemisorption membrane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a chemical adsorption film on a substrate surface. For more information,
A method for forming a chemisorbed monomolecular film or a chemisorbed polymer film by a coating method, and a method for forming another chemisorbed monolayer through a siloxane-based chemisorbed monomolecular film or a siloxane-based chemisorbed polymer film by a coating method. The present invention relates to a method for producing a chemically adsorbed film characterized by accumulating a molecular film or a polymer film.

[0002]

2. Description of the Related Art In general, it is well known that a monomolecular film can be formed in a liquid phase by using a chemisorption method. That is, a method has been known in which a substrate is immersed in a chemical adsorption solution dissolved in a non-aqueous organic solvent and allowed to react for a certain period of time (e.g., EPC Publication No. 0476543A2). The principle of manufacturing a chemically adsorbed monolayer in such a solution is to form a monolayer by using a dehydrochlorination reaction between a hydroxyl group on the substrate surface and a chlorosilyl group of a chlorosilane-based chemical adsorbent. .

[0003]

However, the conventional liquid-phase chemisorption method is carried out by an immersion method, and the reaction is carried out in a liquid tank obtained by diluting an adsorption reagent with a solvent. In this case, there is a problem that a large tank and a large amount of a chemical solution are required.

The present invention provides a method for manufacturing a chemically adsorbed film which can efficiently form an adsorbed film in a short time with a small amount of a chemical solution, without being limited to the shape of a substrate, in order to solve the problems of the prior art. The purpose is to do.

[0005]

In order to achieve the above object, a method for producing a chemically adsorbed film according to the present invention is characterized in that a chlorsilyl group is provided on at least one end of a molecule on the surface of a substrate containing an active hydrogen group on the surface. and straight-chain hydrocarbon group, a fluorocarbon group, and linear chlorosilane Keika Science adsorbent comprising at least one group selected from a siloxane based on the coating solution as one component, a relative humidity of 35% or lower humidity In an atmosphere, and applied in the form of a spray , after a condensation reaction between the active hydrogen groups on the surface of the substrate and the chlorsilyl group of the chemical adsorbent , the remaining chlorsilyl group is reacted with moisture to form the substrate. It is characterized by forming a chemisorption film covalently bonded to the surface.

In the above structure, after the condensation reaction, the solution containing the unreacted chlorosilane-based adsorbent remaining on the substrate is washed and removed using a non-aqueous organic solvent, and then the remaining chlorosilyl group is removed. Preferably, it is reacted with moisture and then dried to form a monomolecular chemically adsorbed film covalently bonded to the substrate surface.

In the above structure, after a silyl group is subjected to a condensation reaction, the coating solution is evaporated, then reacted with moisture, and then dried to form a polymer-type chemically adsorbed film covalently bonded to the substrate surface. Preferably, it is formed.

In the above structure, a chlorosilane-based chemical adsorbent for an inner layer film containing a plurality of chlorosilyl groups in a molecule is brought into contact with the surface of the base material containing an active hydrogen group on a surface thereof in a dry atmosphere. After a condensation reaction between the active hydrogen group and the chlorosilyl group of the chemical adsorbent to form an inorganic siloxane-based chemical adsorption inner layer film, the molecule has a chlorosilyl group at at least one end, and a linear hydrocarbon group. ,
A coating solution containing, as a component, a chlorosilane-based chemical adsorbent containing at least one group selected from a fluorocarbon group and a linear siloxane group is applied in the form of a spray and shared on the surface of the inorganic siloxane-based chemical adsorption inner layer film. Preferably, a bonded chemisorption film is formed.

In the above structure, the chlorosilane-based chemical adsorbent for the inner layer film is preferably applied in a spray form. Further, in the above configuration, after a condensation reaction between the active hydrogen group on the substrate surface and the chlorosilyl group of the chemical adsorbent, the unreacted chlorosilane-based adsorbent remaining on the substrate using a non-aqueous organic solvent Is preferably washed and removed, and then the remaining chlorsilyl group is reacted with moisture, and then dried to form a monomolecular monolayer chemically adsorbed inner layer.

In the above structure, after a condensation reaction between the active hydrogen groups on the surface of the substrate and the chlorsilyl group of the chemical adsorbent is performed, the coating solution is evaporated, followed by contacting with moisture and then drying. To form a polymer-like chemical adsorption inner layer film.

In the above structure, at least a part of the hydrocarbon chain of the chlorosilane-based chemical adsorbent has --CF ₂
It preferably comprises a compound substituted with a group.
Further, in the above configuration, the chlorosilane-based chemical adsorbent is CF ₃ (CF ₂ ) _n (R) _m SiX _p Cl _3-p (n
Is 0 or an integer, R is an alkyl group, a vinyl group, an ethynyl group, an aryl 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 It is preferred to use 0, 1 or 2) as the substituent of the fluorine-containing alkoxy group.

In the above structure, the chlorosilane-based chemical adsorbent substance for the inner layer film is made of SiCl ₄ , SiHC
l ₃ , SiH ₂ Cl ₂ , and Cl (SiCl ₂ O) _n S
It is preferably at least one compound selected from iCl ₃ (where n is an integer).

[0013] In the above structure, the base material may be a metal,
Ceramics, glass, plastic, polymer, paper,
It is preferred to be selected from fiber and leather. Further, in the above configuration, it is preferable that the surface of the substrate is previously treated with a plasma or a corona atmosphere containing oxygen to give active hydrogen.

In the above structure, it is preferable that the chemical adsorption process is performed in a low humidity atmosphere having a relative humidity of 30% or less. Further, in the above configuration, the solvent of the solution containing the chlorosilane-based adsorbent has a boiling point of 100 ° C or higher and 300 ° C or higher.
It is preferable that the temperature be in the range of not more than ℃ when forming a monomolecular film.

Further, in the above structure, the solvent of the solution containing the chlorosilane-based adsorbent has a boiling point of room temperature (25 ° C.) or higher.
It is preferable that the temperature be in the range of 00 ° C. or less when forming a polymer film.

Further, in the above configuration, it is preferable to spray the coating solution by a spray in order to obtain microdroplets on the order of microns.

[0017]

According to the structure of the present invention described above, a solution containing a chlorosilane-based surfactant is applied to the surface of a substrate to perform chemical adsorption, thereby eliminating the need for an adsorption tank and limiting the shape of the substrate. It is possible to form a chemically adsorbed film on the surface of the base material in a short time without using. In addition, a chlorosilane compound or a solution containing a chlorosilane compound is applied to the surface of the base material in advance to form a siloxane-based monomolecular film or a polysiloxane-based polymer adsorption film, and further, a chlorosilane-based surfactant or a chlorosilane-based surfactant is formed. By applying a solution containing an agent and performing chemisorption, it is possible to form a chemisorption film on the surface of a substrate in a short time with high efficiency without the need for an adsorption tank and without being limited by the shape of the substrate. Becomes possible.

In the method of the present invention, the siloxane-based thin film may be a monomolecular film or a polymer film. However, a monomolecular film is preferable because of excellent transparency because the inner layer film can be formed uniformly and extremely thinly.

In the method of the present invention, a hydrocarbon-based compound such as a hydrocarbon-based compound can be widely used as a chemical adsorption film. In particular, a compound containing fluorine further improves water repellency, oil repellency, and antifouling properties. preferable. The use of a chemical adsorbent containing a straight-chain siloxane group is preferred because water repellency and water dropping property are improved.

In the method of the present invention, the surface of the base material and the siloxane-based thin film are covalently bonded to each other, and the siloxane-based thin film and the chemisorption film on the surface are also covalently bonded. Adhesion with the material surface is greatly improved.

In the structure of the present invention, the base material is selected from metals, ceramics, glass, plastics, polymers, fibers, paper, leather, etc., and is hardly limited.

In the above structure, a hydrocarbon-based compound or the like can be used as the chlorosilane-based adsorbent. However, the chlorosilane-based adsorbent is preferably made of a compound in which at least a part of the hydrocarbon chain is substituted with a --CF ₂ -group. It is preferable to improve properties such as water-based property and antifouling property.

In the above-mentioned production method, the chlorosilane-based adsorbent is CF ₃ (CF ₂ ) _n (R) _m SiX _p C
l _3-p (n is 0 or an integer, R is an alkyl group, vinyl group, ethynyl 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. It is more preferable to use 0 or 1 or 2) as the substituent of the group or the fluorinated alkoxy group.

When a plastic is used as a base material in the above-mentioned production method, a plastic whose surface has been treated in advance with a plasma or a corona atmosphere containing oxygen to make the surface hydrophilic may increase the number of active groups on the surface. It is preferable to chemically adsorb siloxane molecules at high density.

In the above-mentioned structure of the production method, the substance containing a plurality of chlorosilyl groups in the molecule may be SiCl ₄ ,
SiHCl ₃ , SiH ₂ Cl ₂ , or Cl (SiCl
_At least one selected from the group consisting of 2O) _n SiCl ₃ (where n is an integer) is preferable in order to efficiently form a siloxane-based molecular film.

Further, in the configuration of the above manufacturing method,
It is preferable that all the processing steps be performed in a dry atmosphere in order to efficiently form the chemical adsorption film. In the structure of the above-mentioned production method, it is preferable that the solvent of the solution containing the chlorosilane-based adsorbent has a boiling point in the range of 100 to 300 ° C. in order to efficiently form a chemically adsorbed monolayer.

In the structure of the above-mentioned production method, the boiling point of the solvent of the solution containing the chlorosilane-based adsorbent is room temperature (25
C.) or higher and 100 ° C. or lower in order to efficiently form a chemisorbed polymer film.

According to the method of the present invention, the following six kinds of films can be basically formed as an example. (1) Chemisorption monomolecular film (2) Chemisorption polymer film (3) Chemisorption monomolecular film on siloxane-based monolayer inner film (4) Chemisorption monomolecular film on polysiloxane-based inner film (5) ) Chemisorbed polymer film on siloxane-based monomolecular inner film (6) Chemisorbed polymer film on polysiloxane-based monomolecular inner film Also, without being limited by the shape and size of the base material,
The chemisorption monomolecular film can be efficiently and rationally manufactured, and the chemisorption monomolecular film is formed by chemical bonding on the surface of the base material. There is no hole (pinhole free), and it is possible to provide a monomolecular film-like chemically adsorbed monomolecular accumulation film excellent in heat resistance, durability and the like.

According to the method of the present invention, a polymer thin film is formed by chemical bonding on the surface of the substrate without the need for an adsorption tank and without being limited by the shape and size of the substrate. Therefore, it is possible to provide a chemically adsorbed film having no pinholes (pinhole free) and excellent in heat resistance, durability and the like.

Further, according to the method of forming a chemically adsorbed film on the inner layer film of the present invention, no adsorption tank is required and the shape and size of the substrate are not limited, and A siloxane-based molecular film (inner layer film) or a siloxane-based polymer film is formed on the surface in a state chemically bonded to the substrate surface, and a chemically adsorbed monomolecular film (surface layer film) or polymer film is formed on the surface. Since it is formed in a chemically bonded state, it is possible to provide a thin film which is extremely thin and uniform in thickness as a whole, has no pinholes, and is excellent in heat resistance, durability and the like. That is, at this time,-
The SiOH bond is bonded to the substrate via a siloxane bond (covalent bond). Further, when the silane-based adsorbent containing a chlorosilane group is adsorbed and accumulated on the monomolecular film having the SiOH bond in the form of a monomolecular film or a polymer, the monomolecular film has a large number of -SiOH bonds formed on the surface of the base material in the previous step. -OH groups of a polysiloxane monomolecular film or a polymer film;
A dehydrochlorination reaction occurs with the chlorosilyl group of the silane-based adsorbent, and the monomolecular film or the polymer film is chemically bonded to the base material through a -SiO bond. Therefore, there is an effect that a monomolecular film having extremely excellent adhesion can be formed.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a substrate which can be used in the present invention, 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 Is mentioned. 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. It reacts to form a siloxane bond (-SiO-), so that no special surface treatment is required.

On the other hand, an inner layer film usable in the present invention is formed.
As a substance containing a chlorosilyl group, for example, SiCl
_Four, SiHCl_Three, SiH_TwoCl_Two, Or Cl (Si
Cl _TwoO)_nSiCl_Three(Where n is an integer) and the like.
You.

In particular, it is preferable to use SiCl ₄ , since the molecules are small and the activity for hydroxyl groups is large, and the effect of uniformly hydrophilizing the substrate surface is large. The gas for the dry atmosphere used when spray-coating a solution containing a substance containing a chlorosilyl group is dry air (35% relative humidity).
%), And a non-hydrous gas such as nitrogen gas.

The concentration of the chlorosilyl group-containing substance depends on the type of the chlorosilyl group-containing substance or the solvent to be used, but is about 0.01% to 100% by weight (preferably about 0.1% to 50% by weight). Can be used. When the solution is applied to the substrate surface in a dry atmosphere and allowed to stand for about 30 minutes, a dehydrochlorination reaction occurs on the surface because there is some hydrophilic OH group on the substrate surface, and a substance containing a chlorosilyl group is produced. Adsorbed and fixed. Therefore, after washing well with a non-aqueous solvent and further reacting with water, an excess substance containing a chlorosilyl group is removed to form a siloxane monomolecular film (inner layer film). Note that, at this time, the step of washing with a non-aqueous solvent after the substance containing the chlorosilyl group is adsorbed and fixed, and evaporating the solution containing the substance containing the chlorosilyl group,
A polysiloxane film is formed. In this case, the lower the boiling point of the solvent of the solution containing the substance containing the chlorosilyl group, the lower the boiling point.
0 ° C. or higher is preferred.

Next, a surface layer film forming step is performed. Many hydroxyl groups (-OH) are formed on the surface of the inner layer film. (If the surface of the substrate is extremely hydrophilic at this time, Since the film forming step is not always necessary, the surface layer can be directly laminated on the surface of the base material.) Therefore, a hydrocarbon-based adsorbent or fluorocarbon-based adsorbent having a chlorosilyl group in its hydroxyl group can be reacted.

Accordingly, a chemical adsorption compound having a chlorosilyl group (for example, a hydrocarbon adsorbent, a fluorocarbon adsorbent, or an adsorbent containing a linear siloxane bond).
Is applied (the concentration of the chemically adsorbed compound varies depending on the type of the compound having a chlorosilyl group or the solvent, but is preferably about 0.1 to 10% by weight) for 30 minutes. When the substrate is left to stand for a long time, since a large number of hydrophilic OH groups are present on the surface of the base material, a dehydrochlorination reaction occurs on the surface, and the hydrocarbon-based adsorbent or fluorocarbon-based adsorbent having a chlorosilyl group is adsorbed and fixed. Next, after washing well with a non-aqueous solvent, when further reacting with water, a solution containing an excess hydrocarbon-based adsorbent having a chlorosilyl group or a fluorocarbon-based adsorbent is removed to form a monomolecular film (outer layer film). You. In this case, the higher the boiling point of the solvent of the solution containing the substance containing the chlorosilyl group, the slower the evaporation and the longer the adsorption time, which is convenient.
The range of 00-300 degreeC is good. The step of washing with a non-aqueous solvent after the adsorption of the hydrocarbon-based adsorbent having a chlorosilyl group or the fluorocarbon-based adsorbent is omitted, and when the applied solution is evaporated, the hydrocarbon-based adsorbent having a chlorosilyl group or the fluorocarbon-based adsorbent has a A polymer film of the adsorbent is formed. This reaction also proceeds by the dehydrochlorination reaction as described above. In this case, the lower the boiling point of the solvent of the solution containing the substance containing the chlorosilyl group, the lower the boiling point.
The following is good.

As the adsorbent for forming the surface layer film, for example, a compound containing a fluorocarbon group and a chlorosilane group can be mentioned. As a specific material, CF ₃ (CF ₂ )
_{n (R) m -SiX p Cl} 3-p ( wherein n is 0 or an integer, substituents preferably containing 1 to 22 integer, R represents an alkyl group, a phenyl group, a vinyl group, an ethynyl group, 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, and p is 0, 1 or 2). The use of the compound containing fluorine and a chlorosilyl group is preferable because water repellency, oil repellency, antifouling property, lubricity and the like are imparted.

As other chemical adsorbents for forming the surface layer film, for example, the following hydrocarbon-based chemical adsorbents or siloxane-based chemical adsorbents can be used. CH ₃ (CH
_{2) r SiX p Cl 3-} p, 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 S
_{iX p Cl 3-p CH 3} {Si (CH 3) 2 O} r SiX p Cl 3-p Cl {Si (CH 3) 2 O} r SiX p Cl 3-p ( where, r and the preferred range 1 to 25, s is 0 to 1
2, t represents 1 to 20, u represents 0 to 12, v represents 1 to 20, and w represents 1 to 25. In addition to the above adsorbents, the following specific adsorbents are mentioned.
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 SiCl
_{3, CH 3 COO (CH 2} ) 15 SiCl 3 CF 3 (CF 2) 7 (CH 2) 2 SiCl 3 CF 3 (CF 2) 5 (CH 2) 2 SiCl 3 CF 3 (CF 2) 7 C 6 H ₆ SiCl ₃ CH ₃ ｛Si (CH ₃ ) ₂ O｝ ₃ -SiCl ₃ Cl ｛Si (CH ₃ ) ₂ O｝ ₃ -Si (CH ₃ ) ₂ Cl In the present invention, when the substrate is a metal substrate, alkyl is used. Thiols may be used. Examples of alkylthiols include CH
₃ (CH ₂ ) _n SH, F (CF ₂ ) _n (CH ₂ ) _m S
H, CF ₃ (CF ₂ ) _m (CH ₂ ) _n SH (m, n = 1)
To an integer of 18).

In the method for producing a chemisorption film of the present invention,
Fine droplets of a non-aqueous solution containing a chlorosilane compound (or thiol compound) are formed using a sprayer. When a chlorosilane-based surfactant is used, the non-aqueous organic solvent used in the method for producing a chemically adsorbed film of the present invention is preferably a solvent having no active hydrogen. For example, hexadecane, isooctane, toluene, xylene, cyclohexane, tetralin, petroleum ether, chloroform, carbon tetrachloride, perfluorocarbon, perfluoroalkyl tertiary amine, perfluoroalkyl cyclic ether and the like can be mentioned as examples. When an alkyl thiol is used, an alcohol-based solvent such as ethanol can be used in addition to a non-aqueous solvent. When selecting the adsorption solvent, it is necessary to select a solvent that does not dissolve the substrate.

Fibers and polymers having no active hydrogen (hydroxyl group, amino group, carboxyl group, etc.) on the surface need to oxidize the surface before adsorption to form active groups before adsorption.
As the method, for example, oxygen plasma treatment, UV /
Examples of the method include ozone treatment, corona treatment, and a method of immersing in a mixed solution of concentrated sulfuric acid and potassium dichromate (chromium mixed acid solution treatment).

In the case of forming a chemisorption film of a thiol compound on a metal, an adsorption film can be formed at a high density by removing the oxide by electrolysis or acid / alkali solution treatment on the metal surface. 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, milling Machine blades, lawn mower blades, punches, push cutters, stapler blades, can opener blades, scalpels, etc. (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, 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 , 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, artworks, 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.

Examples and schematic diagrams of FIGS. 1 to 11 are shown below.
The description will be made in order with reference to FIG. In the following examples,
Unless otherwise stated,% means% by weight. Example 1 An aluminum substrate 1 was used as a substrate (FIG. 1). On the surface of this aluminum substrate 1, a small amount of hydrophilic -OH
Since the groups are exposed, SiCl ₄ (tetrachlorosilane) is first selected as an adsorbent for forming the inner layer film, and 85% of hexadecane containing 5% of this tetrachlorosilane, 10% of chloroform (others such as xylene and tetralin instead of hexadecane) Any solution may be used as long as it is a non-aqueous solvent having a boiling point of about 100 ° C. or higher.) A solution is prepared and sprayed on the surface of the aluminum substrate 1 in a room purged with dry nitrogen, and then left for about 30 minutes. As described above, a dehydrochlorination reaction occurs on the surface, and the molecule is fixed to the substrate surface via a -SiO- bond as shown in the following formulas (Chemical Formula 1) and / or (Chemical Formula 2). At this time, since hexadecane has a boiling point of 287 ° C., it hardly evaporates.

[0043]

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[0044]

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Thereafter, the substrate is washed with a non-aqueous solvent such as chloroform or the like, and further washed with water to remove SiCl ₄ molecules that have not reacted with the base material, and the adsorbed reagent reacts with water. As shown in FIG. 3, a siloxane monomolecular film 4 containing many silanol groups on the substrate surface was obtained (FIG. 3). This is shown in the following formulas (Formula 3) and / or (Formula 4).

[0046]

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[0047]

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Since the siloxane monomolecular film 4 or polysiloxane film formed at this time is completely bonded to the base material through a chemical bond of —SiO—, it does not peel off.

The obtained monomolecular film 4 or polysiloxane film has a large number of SiOH bonds on its surface.
Approximately three times the number of the original hydroxyl groups is generated. Furthermore, at this time, cyclohexane (bp. 80 ° C.) was used as a solvent for the solution containing tetrachlorosilane (others such as normal hexane and Fluorinert (3M)).
Any non-aqueous solvent having a boiling point of about 100 ° C. or less and dissolving tetrachlorosilane may be used. If the step of washing with a non-aqueous solvent after application was omitted and the film was naturally evaporated, a polysiloxane film 4 ′ containing many silanol groups could be formed (FIG. 4).

Then, a surface layer film is further formed in a dry nitrogen atmosphere. For example, CF ₃ (CF ₂ ) ₇ (C) containing a fluorocarbon group and a chlorosilane group as a chemical adsorbent
After spray-coating a solution of 85% of hexadecane containing 5% of H ₂ ) ₂ SiCl _{3 and} 10% of chloroform, the mixture is allowed to stand for about 30 minutes, and then washed with a non-aqueous solvent to obtain CF ₃ (CF ₂₎ which has not reacted with the base material. ) ₇ (CH ₂ ) ₂ SiCl
_Three molecules are removed. When the reagent was further taken out into the air, the adsorbed reagent reacted with the moisture in the air to form a siloxane monomolecular film or a polysiloxane film as shown in FIG. The reaction formula of this chemisorbed molecule is shown in the following formula (Formula 5).

[0051]

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FIG. 5 shows the bonding state of the molecules generated on the surface of the siloxane monomolecular film 4. As shown in FIG. 5, the monomolecular film 5 containing fluorine was formed in a state of being chemically bonded (covalently bonded) to the inner siloxane monomolecular film 4.

At this time, CF ₃ (CF ₂ ) ₇ (CH
₂ ) Cyclohexane (bp. 80 ° C.) is used as a solvent for the solution containing ₂ SiCl ₃ (others such as normal hexane and Fluorinert (3M)) have a boiling point of 100 ° C.
Any non-aqueous solvent capable of dissolving tetrachlorosilane at a level lower than that may be used. If the step of washing with a non-aqueous solvent after application is omitted and the film is naturally evaporated, the fluorocarbon-based polymer film 5 'is coated with the siloxane monomolecular film 4 (FIG. 6) or the polysiloxane film 4' (FIG. 7) on the surface. Could be formed.

The monomolecular film did not peel off even when the cross test was performed. Furthermore, in the above embodiment, CF ₃ was used as a fluorocarbon-based adsorbent for forming a surface layer film.
Although (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ was used, if a vinyl group or an ethynyl group is added to or incorporated in an alkyl chain portion, crosslinking can be performed by electron beam irradiation of about 5 megarads after formation of a monomolecular film. Therefore, it is possible to further improve the hardness of the thin film.

Further, the present invention is not limited to the fluorine-containing adsorbent, and is useful, for example, for an ultra-thin hydrocarbon-based film having mechanical strength. When a material containing a large amount of OH groups such as glass is used as the base material, the step of forming a siloxane monomolecular film or a polysiloxane film is omitted, and a fluorocarbon monomolecular film or a fluorocarbon polymer film is directly formed. It may be formed on the surface of the substrate.

Example 2 As shown in FIG. 8, a rearview mirror 11 having an acrylic resin as a transparent portion was used. Since the surface of the acrylic resin is water-repellent, the surface of the
The substrate was treated with 0 W for 2 minutes to make it hydrophilic. Since this surface is hydrophilic but has a small proportion of hydroxyl groups (FIG. 8), octachlorosiloxane (formula (Formula 6) below) was further used as an adsorbent for forming an inner layer film as a substance containing chlorosilyl groups.

[0057]

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A solution is prepared by dissolving the adsorbent for forming the inner layer film shown in Chemical formula 6 in xylene, a non-aqueous solvent, and spray-coated in a dry air (relative humidity 35% or less) using a spray. When left for about 20 minutes, a certain amount of hydrophilic OH groups 12 are present on the surface of the rearview mirror 11, so that a dehydrochlorination reaction occurs on the surface. Further, when the solution remaining on the surface is washed and removed with Freon 113, FIG. As shown, a chlorosilane monomolecular film was formed. Here, if the adsorbent shown in Chemical Formula 6 is used as a substance containing a chlorosilyl group, a dehydrochlorination reaction occurs on the surface of the rearview mirror 11 even if only a small amount of hydrophilic OH group is present on the surface of the rearview mirror 11. As shown in the following formulas (Chem. 7) and / or (Chem. 8), molecules are fixed to the surface via -SiO- bonds (FIG. 9).

[0059]

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[0060]

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Thereafter, a non-aqueous solution (for example, Freon 11)
After washing in 3) and further washing with water, a siloxane monomolecular film 14 of the following (Chem. 9) and / or (Chem. 10) was obtained on the surface of the rear-view mirror 11 as shown in FIG.

[0062]

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[0063]

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In this case, when the step of washing with a Freon solvent was omitted and xylene was completely evaporated, a polysiloxane film could be formed. The siloxane monomolecular film 14 or polysiloxane film formed at this time is completely bonded to the surface of the rear-view mirror 11 through a covalent bond of —SiO—, and thus does not peel off at all. Moreover, the obtained siloxane monomolecular film 14 has many -SiOH bonds on the surface. About 7 times the number of the original hydroxyl groups is generated.

Next, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ S
A xylene solution in which iCl ₃ is dissolved at a concentration of about 2%
In a dry air atmosphere (relative humidity 35% or less), the surface of the rear-view mirror 11 on which the siloxane monomolecular film 14 or the polysiloxane film is formed is spray-coated with a spray, and
When left for about a minute, the siloxane monomolecular film 14 and the polysiloxane film have the above-mentioned bond (Chemical Formula 5) formed on the surface thereof.
Chemical adsorption monomolecular film 15 containing fluorine as shown in FIG.
Was formed in a thickness of about 1.5 nm over the entire mirror surface in a state of being chemically bonded to the lower siloxane monomolecular film 14.

At this time, the step of washing with a non-aqueous solvent was omitted, and the xylene was evaporated by leaving the coating film for about 1 hour, whereby a fluorocarbon polymer film could be formed. The monomolecular film and the polymer film did not peel at all even when a peeling test was performed. In addition, actual use was attempted using the rearview mirror of this example, but water droplets attached due to the water repellency of fluorine on the surface had a diameter of about 2 mm. Also, hair was applied to the rearview mirror surface by mistake, assuming that the hair was touched by mistake.However, the oil was repelled by the oil repellency of the monomolecular film chemically adsorbed on the surface, and there was almost no fogging. Was.

Example 3 The acrylic resin of Example 2 was changed to a polycarbonate resin, and heptadecafluorodecyltrichlorosilane was replaced with tridecafluorooctyltrichlorosilane CF ₃ (C
F _{2) 5} (CH ₂₎ in place of ₂ SiCl _3, was tested in the same manner as in Example 2. Example 4 The same experiment as in Example 1 was performed, except that the acrylic resin of Example 2 was changed to a polypropylene resin, and heptadecafluorooctyltrichlorosilane was changed to perfluorododecyltrichlorosilane.

Example 5 The same experiment as in Example 1 was conducted, except that the acrylic resin of Example 2 was changed to ABS resin. Example 6 The same experiment as in Example 1 was performed, except that the acrylic resin of Example 2 was changed to an epoxy resin.

Example 7 The acrylic resin of Example 2 was changed to a polyurethane resin.
The same experiment as in Example 1 was performed.

Example 8 An experiment was conducted in the same manner as in Example 1 except that the acrylic resin of Example 2 was changed to a butadiene-styrene rubber resin.

Example 9 An experiment was conducted in the same manner as in Example 1 except that the acryl resin in Example 2 was changed to butyl rubber resin.

Example 10 The acrylic resin of Example 2 was changed to a nitrile rubber resin.
An experiment was performed in the same manner as in Example 1.

Example 11 The heptadecafluorodecyltrichlorosilane of Example 2 was changed to 18-nonadecenyltrichlorosilane, and after forming a chemisorbed monomolecular film, 300 keV, 0.1 .ANG.
An electron beam of 02 Mrad / s was irradiated for 1 minute.

Example 12 An experiment was conducted in the same manner as in Example 2 except that octachlorosiloxane in Example 2 was changed to tetrachlorosilane.

Comparative Example 1 A silane coupling agent (heptadecafluorodecyltrimethoxysilane) was added to the surface of a polycarbonate resin.
After spin coating with a wt% methanol solution,
For 1 hour.

Comparative Example 2 A chemically adsorbed monomolecular film of heptadecafluorodecyltrichlorosilane was formed without oxidizing the acrylic resin of Example 2.

Comparative Example 3 A suspension of polytetrafluoroethylene was spray-coated on the surface of the acrylic resin of Example 2, and dried by heating at 60 ° C. for 1 hour.

The contact angles of the samples of Examples 1 to 13 and Comparative Examples 1 and 2 with respect to ultrapure water and oil (salad oil of Nisshin Co., Ltd.) were examined. The contact angle was measured immediately after forming the chemisorption film or the coating film and after rubbing the surface 10,000 times with a cloth wetted with water. Table 1 shows the results.

[0079]

[Table 1]

As is clear from Table 1, the substrate of this example retained water / oil repellency or hydrophilicity even after the surface was repeatedly rubbed and washed with a water-containing cloth. In No. 1, the water / oil repellency was lost. Further, in the sample of Comparative Example 2 in which the surface of the substrate was not subjected to the oxidation treatment, a chemical adsorption film having a siloxane bond could not be formed.

The anti-fouling property of the present invention in which the surface of which the chemisorbed monomolecular film containing an alkyl fluoride group was formed was excellent. After the friction test, the sample of Example 1 was immersed in salad oil,
When wiped off with tissue paper, the oil was wiped off cleanly, but in the sample of Comparative Example 1, an oil film was still sticky on the surface even after wiping with tissue paper several times.

The present invention can also be used as an optical material. The transmittance of the polycarbonate resin of Example 3 to visible light was 92%, which was the same as before forming the chemisorbed monomolecular film, but the transmittance of the sample coated with polytetrafluoroethylene of Comparative Example 3 was 50%. % Or less and the transparency was poor like ground glass.

Example 14 A substance containing a plurality of chlorosilyl groups, for example, SiCl ₄ , SiHCl ₃ , S
iH ₂ Cl ₂ , Cl (SiCl ₂ O) _n SiCl ₃ (n
Is an integer), but if SiCl ₄ is used, the molecules are small and the activity to hydroxyl group is large, so that the effect of uniformly hydrophilizing the scissor surface is great. Spraying the cyclohexane solution of (2) with a spool, leaving it for about 30 minutes, and taking it out to the air, the surface of the scissors has some OH groups that are hydrophilic. And a polysiloxane-based film containing a silanol bond was formed. Since the film formed at this time is completely bonded to the scissors via the chemical bond of -SiO-, the film does not peel off unless there is a decomposition reaction or the like. Further, the obtained polysiloxane film has many SiOH bonds on the surface. About 10 times the number of initial hydroxyl groups is produced.

Next, a chemical adsorbent (for example, a fluorocarbon group)
And chlorosilyl groups) and non-aqueous solvents
Adsorption liquid, for example, CF_Three(CF_Two)₇(CH_Two)_TwoSi
Cl _Three80% n- dissolved at a concentration of about 10%
Hexadecane, 12% carbon tetrachloride, 8% chloroform dissolved
A solution is prepared, and this solution is applied by spraying with a spray.
Let stand for about an hour and then
Wash and remove reactants and then react with water or air
When exposed to the air to react with moisture in the air,
CF on the surface of the polysiloxane film_Three(CF_Two)₇(CH
_Two)_TwoSi (O-)_ThreeIs formed and contains fluorine
Monomolecular film chemically bonded to underlying polysiloxane film
Approximately 20 angstroms (2.0 nm) over the entire surface with scissors
It was able to form with the film thickness of. In addition, the cumulative film performs a goth test.
There was no peeling even when it was performed.

Example 15 In the case of aluminum yakan which is hydrophilic but has a small proportion of hydroxyl groups, SiCl ₄ was selected as a substance containing a plurality of chlorosilyl groups, and was dissolved at 1% in a xylene solvent as a non-aqueous solvent. This solution is spray-applied with a spray 2
Upon standing about 10 minutes, since the aluminum kettle surface is present hydrophilic OH groups are more or less, surface dehydrochlorination reaction occurs Si (Cl) ₃ O- or -OSi (Cl) ₂ O- molecules as Are fixed to the surface via -SiO- bonds.

Thereafter, by washing with a non-aqueous solvent, for example, chloroform, and further washing with water, SiCl ₄ molecules that have not reacted with the aluminum yakan are removed, and Si (OH) ₃ O— or —OSi A siloxane monomolecular film such as (OH) ₂ O— was obtained.

Since the monomolecular film formed at this time is completely bonded to the aluminum can surface through a chemical bond of —SiO—, it does not peel off. Moreover, the obtained monomolecular film has many SiOH bonds on the surface. About three times the number of the original hydroxyl groups are generated.

Then, a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group, for example, CF
_{Using 3} (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , a chloroform solution dissolved at a concentration of about 1% was prepared, spray-coated on an aluminum kettle, left at room temperature for about 1 hour, and further mixed with water. When reacted or exposed to air to react with moisture in the air, CF ₃ (C
A bond of F ₂ ) ₇ (CH ₂ ) ₂ Si (O—) ₃ is generated, and the fluorocarbon-based polymer film containing fluorine is chemically bonded to the underlying siloxane monomolecular film, and is formed over the entire surface of the aluminum kettle. 20 angstroms (2.0n
m). This polymer film did not peel even when a peel test was performed.

Example 16 An iron hot plate having a hydrophilic property but containing a small number of hydroxyl groups was selected, and a solution containing 15% SiCl ₄ dissolved in a chloroform solvent as a substance containing a plurality of chlorosilyl groups was applied by spraying. After standing for about a minute, the chloroform evaporates, and since some hydrophilic OH groups are present on the surface of the iron hot plate, a dehydrochlorination reaction occurs on the surface to form -SiO- groups. After washing with water, -SiCl not reacting with the hot plate surface
And SiCl ₄ molecules also reacted to form a polysiloxane film on the hot plate surface.

Since the polysiloxane film formed at this time is completely bonded to the hot plate surface through a chemical bond of —SiO—, it does not peel off. Further, the obtained polysiloxane film has many SiOH bonds on the surface.

Then, further, a fluorocarbon group and a chlorosilane
Non-aqueous solution mixed with a substance containing a lan group, for example, CF
_Three(CF_Two)₇(CH_Two)_TwoSiCl_ThreeDissolved 5%
Dry Fluorinert FX3252 (3M) solution
A poly with many SiOH bonds on the surface in a dry atmosphere
Spray on hot plate with siloxane film
Spray coating and let it react with water after leaving it for about 1 hour,
When exposed to the air and reacted with moisture in the air,
CF_Three(CF_Two)₇(CH_Two)_TwoSi (O-) _ThreeJoin
Fluorocarbon polymer containing fluorine
With the film chemically bonded to the underlying polysiloxane film,
About 200-300 angstrom over the entire surface of the plate
It could be formed with a film thickness of ROHM (20 to 30 nm). In addition,
This polymer film can be peeled off even if a peeling test is performed.
Did not.

Example 17 A hydrophilic porcelain bowl was selected, and a fluorocarbon group and a cup were prepared.
Non-aqueous solvent mixed with a substance containing lorosilane group, such as
If CF_Three(CF_Two)_Five(CH_Two)_TwoSiCl _ThreeFor
Prepare a tetralin solution dissolved at a concentration of about 5%
And leave this solution for about 1 hour after spray application
And then wash unreacted materials with a non-aqueous solution such as chloroform.
・ Remove and react with water or expose to air
When reacted with moisture in the air, CF_Three(CF_Two)
_Five(CH_Two)_TwoSi (O-)_ThreeIs generated and the flow
The carbonaceous monomolecular film is directly over the entire surface of the bowl.
Can be formed with a thickness of 15 angstrom (1.5 nm)
Was. Note that this monomolecular film is extremely transparent and
Did not peel off.

Example 18 A hydrophilic porcelain dish was selected, and a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group, for example, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ was used. Prepare a chloroform solution dissolved at a concentration of about 5%, spray-coat this solution and let it stand for about 1 hour to evaporate all the chloroform and further react with water or expose it to air to remove air. When it reacts with the moisture inside, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (O
-) Bonds of ₃ were formed, and a fluorocarbon-based polymer film could be formed directly on the entire surface with a thickness of about 100 angstroms (10 nm). This polymer film was also transparent and did not peel off even when a peeling test was performed.

As described above, according to the embodiment of the present invention, a fluorocarbon-based monomolecular film or a polymer film is thinly formed on a substrate with good adhesion and without pinholes, so that electric appliances such as hot plates and rice cookers can be used. It can improve the performance of base materials that require heat-resistant, weather-resistant, and wear-resistant coatings on automobiles, industrial equipment, mirrors, spectacle lenses, interior goods, apparel goods, and the like.

In addition, any of Examples 1 to 18 of the present invention can efficiently produce a chemically adsorbed monomolecular film or a polymer film. Example 19 In a nitrogen atmosphere, a glass plate (soda glass: 1 m × 2 m
(× 0.5 cm) Using a sprayer, fine droplets of a 1% by volume of cyclohexane solution of heptadecafluorodecyltrichlorosilane were sprayed onto the surface and applied, and then left for 1 hour. Then it was washed with ethanol.

In this embodiment, as shown in FIG. 12, fine droplets 24 of a non-aqueous solution 23 containing a chlorosilane compound are sprayed onto a substrate 21 having an active hydrogen group on its surface by a sprayer 22 to apply the substrate. A chemical adsorption film is formed on 21. FIG. 13 is an enlarged view showing a state in which a chemical adsorption film 33 is formed on a substrate 31 via a siloxane bond 32 to a molecular level. When a thiol-based chemical adsorbent is used instead of the chlorosilane-based chemical adsorbent,
As shown in FIG. 14, a chemical adsorption film 43 is formed on the substrate 41 via the -S- bond 42.

Example 20 A similar experiment was performed with the glass plate of Example 19 changed to an aluminum plate. Example 21 The glass plate of Example 19 was placed on a copper plate, and 1 vol% of heptadecafluorodecyltrichlorosilane in a cyclohexane solution was applied in an amount of 1 v.
A similar experiment was performed, except that the ol% heptadecafluorodecylthiol solution in ethanol was used.

Example 22 The same experiment as in Example 19 was carried out except that the glass plate was changed to an alumite plate. Example 23 A similar experiment was performed by replacing the glass plate of Example 19 with a ceramic coffee dish.

Example 24 A similar experiment was conducted by changing the glass plate of Example 19 to a nylon fiber fabric. Example 25 A similar experiment was performed by changing the glass plate of Example 19 to a polypropylene injection molded plate.

Example 26 A similar experiment was conducted, except that the glass plate of Example 19 was replaced with a hinoki plate. Example 27 A similar experiment was performed with the glass plate of Example 19 changed to plain paper.

Comparative Example 4 The glass plate of Example 19 was cut into a size of 5 cm × 5 cm × 0.5 cm, immersed in a 1% by volume heptadecafluorodecyltrichlorosilane solution in cyclohexane for 18 hours under a nitrogen atmosphere, and washed with cyclohexane. Subsequently, the substrate was washed with pure water.

Comparative Example 5 The copper plate (5 cm × 5 cm) of Example 22 was immersed in a 1 vol% heptadecafluorodecylthiol ethanol solution for 18 hours, and washed with ethanol.

Each of the samples of Examples 19 to 27 was 5 cm × 5 cm
And the contact angle with water was measured with an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., CA-Z type) together with the sample of the comparative example. Table 2 shows the results.

[0104]

[Table 2]

As is evident from Table 2, the contact angle with water of the chemically adsorbed film obtained in this example was the same as that of the chemically adsorbed film obtained in the comparative example (immersion method).

[0106]

As described above, the method according to the present invention comprises:
Efficient chemical adsorption to plastics, ceramics, glass, and other materials, regardless of the shape of the substrate, because the adsorbent is applied to the substrate surface in a dry atmosphere to form a monomolecular film or polymer film A film can be formed.

Further, a siloxane-based monomolecular film or a polysiloxane film is formed, and further, a chemisorption monomolecular film or a polymer film is formed via the siloxane-based monomolecular film or the polysiloxane film. A chemically adsorbed monomolecular film or polymer film can be formed efficiently and with good adhesion on metals, plastics, ceramics, glass, and other various materials having few active hydrogen groups such as a hydroxyl group, an amino group, and an imino group.

When a compound containing a fluorocarbon group and a chlorosilyl group is used as an adsorption reagent, Al, Cu
Or, even on metal substrates such as stainless steel, water and oil repellency,
With a fluorocarbon-based monomolecular film with excellent antifouling properties and durability, chemically bonded to the substrate, there is no pinhole at high density,
It can be formed very thin with a uniform thickness. Therefore, a high-performance fluorocarbon-based ultrathin film having extremely high durability can be provided.

Therefore, the method for producing a chemisorption film of the present invention
There is also an effect that it can be applied to electronic products, particularly electrical appliances such as hot plates and rice cookers, automobiles, industrial equipment, mirrors, spectacle lenses, and other equipment requiring heat resistance, weather resistance, and wear resistance.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view illustrating a process of a method for accumulating an organic monomolecular film according to a first embodiment of the present invention, in which a substrate surface is enlarged to a molecular level.

FIG. 2 is a schematic cross-sectional view showing a step of a method of accumulating an organic monomolecular film according to a first embodiment of the present invention, in which a stage of forming a chlorosilane monomolecular film on a substrate surface is enlarged to a molecular level. is there.

FIG. 3 shows the steps of a method for accumulating an organic monomolecular film according to a first embodiment of the present invention, in which an intermediate stage of forming a siloxane-based monomolecular film-like inner layer film on the surface of a substrate is reduced to a molecular level. FIG. 3 is an enlarged schematic sectional view.

FIG. 4 shows the steps of the method for accumulating an organic monomolecular film according to the first embodiment of the present invention, in which an intermediate stage in which a polysiloxane film containing many silanol groups (inner layer film) is formed on the surface of a substrate. It is the schematic cross section expanded to the molecular level.

FIG. 5 is a schematic cross-sectional view showing a step of a method of accumulating an organic monomolecular film according to a first embodiment of the present invention, in which a fluorine-based chemisorption film is formed on an inner layer film.

FIG. 6 is a schematic cross-sectional view showing a step of a method of accumulating an organic monomolecular film according to the first embodiment of the present invention, in which a fluorine-based chemisorption film is formed on an inner layer film.

FIG. 7 shows a process of a method for accumulating an organic monomolecular film according to the first embodiment of the present invention, in which a step of accumulating a surface layer of a fluorocarbon monolayer on an inner layer on the surface of a substrate is shown. It is the schematic cross section expanded to the molecular level.

FIG. 8 is a schematic cross-sectional view showing a step of a method of accumulating an organic monomolecular film according to a second embodiment of the present invention, in which a substrate surface is enlarged to a molecular level.

FIG. 9 is a schematic cross-sectional view showing a step of a method of accumulating an organic monomolecular film according to a second embodiment of the present invention, in which a stage of forming a chlorosilane monomolecular film on a substrate surface is enlarged to a molecular level. is there.

FIG. 10 shows steps of an organic monomolecular film accumulating method according to a second embodiment of the present invention, in which an intermediate step of forming a siloxane-based monomolecular film-like inner layer film on the surface of a base material is reduced to a molecular level. FIG. 3 is an enlarged schematic sectional view.

FIG. 11 shows a process of a method for accumulating an organic monomolecular film according to a second embodiment of the present invention, in which a step of accumulating a surface layer of a fluorocarbon monolayer on an inner layer on the surface of a substrate is shown. It is the schematic cross section expanded to the molecular level.

FIG. 12 is a sectional view of a spray atomizer used in Embodiment 19 of the present invention.

FIG. 13 is a cross-sectional view of a chemical adsorption film (using a chlorosilane compound) formed in Example 19 of the present invention, which is enlarged to a molecular level.

FIG. 14 is a cross-sectional view of a chemically adsorbed film (using a thiol compound) formed in Example 19 of the present invention, which is enlarged to a molecular level.

[Explanation of symbols]

 1,11,21,31,41 Base material 2,12 OH group 3,13 Chlorosilane monomolecular film 4,14 Siloxane monomolecular film 5,15 Fluorine-containing monomolecular film 22 Nebulizer 23 Non-aqueous solution containing chlorosilane compound 24 microdroplet 32 siloxane bond 33 monomolecular chemisorption film 42 -S-bond 43 monomolecular chemisorption film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C03C 17/28 C03C 17/28 A 17/30 17/30 A // C08J 5/18 C08J 5 / 18 (72) Inventor Shigeo Ikuta 1006 Kazuma Kadoma, Kadoma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (56) References JP-A-63-137750 (JP, A) JP-A-3-289148 (JP, A) JP-A-4-255345 (JP, A) JP-A-4-255344 (JP, A) JP-A-4-256710 (JP, A) JP-A-4-258278 (JP, A) JP-A-4-214880 (JP, A) JP-A-4-330925 (JP, A) JP-A-5-138020 (JP, A) JP-A-4-239635 (JP, A)

Claims (16)

(57) [Claims] Claims: 1. A surface of a substrate containing an active hydrogen group on the surface,
At least one end Kurorushiriru group of the molecule, and the coating solution to the linear hydrocarbon group, a chlorosilane Keika Science sorbent one component comprising at least one group selected from fluorocarbon groups, and linear siloxane groups Is applied in a low-humidity atmosphere having a relative humidity of 35% or less and in the form of a spray to cause a condensation reaction between active hydrogen groups on the surface of the base material and chlorsilyl groups of the chemical adsorbent.
A method for producing a chemisorption film, comprising reacting a lyl group with water to form a chemisorption film covalently bonded to the substrate surface. 2. After the condensation reaction, the solution containing the unreacted chlorosilane-based adsorbent remaining on the substrate is washed and removed using a non-aqueous organic solvent, and then the remaining chlorsilyl group is reacted with moisture. The method for producing a chemisorption film according to claim 1, wherein the method is followed by drying to form a monomolecular film-like chemisorption film covalently bonded to the substrate surface. 3. A condensation reaction of the silyl group, followed by evaporating the coating solution, then reacting with water, and then drying to form a polymer-type chemically adsorbed film covalently bonded to the substrate surface. 2. The method for producing a chemisorption film according to item 1. 4. A chlorosilane-based chemical adsorbent for an inner layer film containing a plurality of chlorosilyl groups in a molecule is brought into contact with a surface of a substrate containing an active hydrogen group on a surface thereof in a dry atmosphere to form an active hydrogen group on the surface of the substrate. And a chlorosilyl group of the chemical adsorbent, thereby forming an inorganic siloxane-based chemical adsorption inner layer film, and then performing the step of claim 1 to form a chemical bond covalently bonded to the surface of the inorganic siloxane-based chemical adsorption inner layer film. The method for producing a chemical adsorption film according to claim 1, wherein the adsorption film is formed. 5. The method for producing a chemical adsorption film according to claim 4, wherein the chlorosilane-based chemical adsorbent for the inner layer film is applied in a spray form. 6. A condensation reaction between an active hydrogen group on the surface of a substrate and a chlorosilyl group of a chemical adsorbent, followed by removing unreacted chlorosilane-based adsorbent remaining on the substrate using a non-aqueous organic solvent. The method for producing a chemisorption film according to claim 4, wherein the solution containing the solution is washed and removed, the remaining chlorsilyl group is reacted with moisture, and then dried to form a monomolecular film-like chemisorption inner layer film. 7. A condensation reaction between an active hydrogen group on the surface of a base material and a chlorsilyl group of a chemical adsorbent, followed by evaporating the coating solution, then reacting with water, and then drying to form a polymer-like chemical. The method for producing a chemically adsorbed film according to claim 4, wherein the adsorbed inner layer film is formed. 8. The method for producing a chemically adsorbed film according to claim 1, wherein at least a part of the hydrocarbon chain of the chlorosilane-based chemical adsorbent comprises a compound substituted with a —CF ₂ — group. . 9. The chlorosilane-based chemical adsorbent is CF.
₃ (CF ₂ ) _n (R) _m SiX _p Cl _3-p (n is 0 or an integer, R is an alkyl group, a vinyl group, an ethynyl group, an aryl 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 fluorinated alkyl group or a fluorinated alkoxy group,
8. The method according to claim 1, wherein p is 0, 1 or 2). 10. The chlorosilane-based chemical adsorbent material for the inner layer film is SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , and Cl (SiCl ₂ O) _n SiCl ₃ (where n is an integer)
The compound is at least one compound selected from the group consisting of:
7. The method for producing a chemically adsorbed film according to any one of 7. 11. The method according to claim 1, wherein the base material is selected from metals, ceramics, glass, plastics, polymers, paper, fibers, and leather. 12. The method for producing a chemically adsorbed film according to claim 11, wherein the substrate has been previously treated with an oxygen-containing plasma or corona atmosphere to give active hydrogen. 13. The method for producing a chemical adsorption film according to claim 1, wherein the chemical adsorption treatment step is performed in a low humidity atmosphere having a relative humidity of 30% or less. 14. The method according to claim 2, wherein the solvent of the solution containing the chlorosilane-based adsorbent has a boiling point in the range of 100 ° C. or more and 300 ° C. or less. 15. The method for producing a chemisorption film according to claim 3, wherein the solvent of the solution containing the chlorosilane-based adsorbent has a boiling point of room temperature or higher and 100 ° C. or lower. 16. The method for producing a chemically adsorbed film according to claim 1, wherein the coating solution is sprayed.