JPH07166122A - Base material and article having stainproofing properties - Google Patents

Abstract

PURPOSE:To provide a base material coated with a composition composed essentially of plural specified compounds, excellent in stainproofing properties, abrasion resistance, chemical resistance, weather resistance, etc., respectively semipermanently durable and useful for a transport apparatus, etc. CONSTITUTION:This base material has a coating film formed from a composition composed essentially of (A) an isocyanatosilane compound and (B) a compound having a tetrafluoroethylene polymer unit on the surface. In addition, the component (A) is represented by formula I or II [R<1> to R<7> are each H or a 1 to 30C organic group; (a), (b), (c) and (d) are each 0, 1 or 2 and satisfy 0<=a+b<=2 and 0<=c+d<=2; Y is a divalent organic group; (e), (f) and (g) are each 0 to 3 and satisfy 1<=e+f+g<=3] and the component (B) is a spherical particle composed of a compound having the structural unit of (CF2CF2)h(h is >=5) and 1000 to 100000 molecular weight, especially preferably polytetrafluoroethylene and having <=10mum average particle diameter.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to antifouling substrates and articles. More specifically, there is little dirt attached, and even if it is attached, it has a surface that makes it easy to remove dirt,
Further, the present invention relates to a base material and an article that can be applied in a wide range of fields because the effect lasts for a long time.

[0002]

2. Description of the Related Art Various base materials and various base materials having a surface treatment layer have been used in various fields, but the adverse effect of stains on their surfaces has been a problem.

For example, an outer layer member such as an outer plate, a window glass, a mirror, a display device surface material, an inner layer member such as an instrument panel surface material in a transportation device such as an electric train, an automobile, a ship, an aircraft, etc. It is preferred that the surface is always clean.
Raindrops, dust, dirt, etc. may adhere to these surfaces,
When dirt condenses under the influence of humidity and temperature in the atmosphere, its appearance is impaired. If the surface is in direct contact with or in contact with the human eye, it causes discomfort and hygiene problems.
Furthermore, the original function of the article for transportation equipment is significantly deteriorated.

In particular, when the article for transportation equipment is an article (for example, a window glass, a mirror, etc.) which is required to be transparent and transparent, the impairing of the transparency and the transparent characteristic is the original purpose of the article. It may lead to serious accidents, leading to things that cannot be achieved.

Means for removing dirt (eg, wiping, wiper removal) can sometimes cause microscopic scratches on the surface. In addition, foreign particles contained in dirt or the like may make such scratches more remarkable.
Fine irregularities on the surface caused by the dirt itself or damage caused by removal of the dirt reduce the original function of the article, and
The intense light scattering causes inconvenience in securing a field of view and may cause a serious accident.

[0006] In addition, dirt has a detrimental effect on the surface of articles for transportation equipment and promotes damage, contamination, coloring, corrosion, etc., and electrical characteristics, mechanical characteristics, optical characteristics, etc. of articles for transportation equipment. May induce changes in. The adverse effect of this type of dirt is not limited to articles for transportation equipment, but is a problem in various fields such as articles for construction / construction equipment and articles for electric / electronic devices.

In order to solve such a problem, it is necessary to provide the surface of the substrate with a property of preventing the attachment of dirt or a property of easily removing the adhered dirt (hereinafter, simply referred to as antifouling property). , Is strongly demanded.

Conventionally, in order to impart antifouling property to the surface of a substrate, a surface treatment agent has been proposed which directly coats a silicone oil consisting of a silicone wax or an organopolysiloxane, a surfactant, or a fluorine resin. There is.

However, many conventional surface treatment agents require pretreatment, and there is a problem that coating unevenness is likely to occur during coating. Further, since the adhesion of the treating agent itself to the substrate is low, the stainproof property cannot be maintained for a long period of time, but the application range is limited.

Furthermore, not only the articles manufactured in the future,
When it is desired to impart antifouling properties to an already used article, it is necessary to directly treat each part at room temperature. For example, when considering a treatment for imparting antifouling properties to an automobile windshield that is already on the market, it is difficult to replace the windshield of each automobile for economic reasons. Moreover, it is practically impossible to bake the entire automobile after coating. From this point of view, there has been a problem that none of the surface treatment agents proposed hitherto is satisfactory.

[0011]

The present invention has been made in order to solve the above-mentioned problems, and has excellent antifouling properties, performances such as abrasion resistance, chemical resistance and weather resistance. It is also an object of the present invention to provide a base material and an article which are excellent in that performance and whose performance lasts semipermanently.

[0012]

The inventor of the present invention is excellent in that it can be applied to various kinds of base materials in the process of researching and investigating a treating agent capable of solving the drawbacks of the conventional techniques. We have found a treatment agent that exhibits antifouling properties. Moreover, it was confirmed that various base materials treated with the treatment agent are extremely suitable as base materials having antifouling properties, particularly for transportation equipment, construction, or construction equipment.

That is, the present invention provides a substrate having on its surface a coating formed from a composition containing an isocyanate silane compound and a compound containing polymerized units of tetrafluoroethylene as essential components.

The isocyanate silane compound in the present invention means a compound having a structure in which at least one isocyanate group is directly bonded to a silicon atom. The isocyanate compound may have at least one organic group, or may be a compound having no organic group such as tetraisocyanatesilane.

The isocyanate silane compound in the present invention is preferably an organoisocyanate silane compound having at least one organic group directly bonded to a silicon atom (the silicon atom and the organic group are bonded by a carbon-silicon bond). Further, as described below, the antifouling performance can be further improved by selecting the organic group of the organoisocyanate compound.

In the present invention, the isocyanate silane compound is considered to be chemically and physically bound to the substrate. Moreover, since the isocyanate group of the isocyanate silane compound is reactive, it is considered that the isocyanate group is bonded to the surface of the substrate mainly by a chemical reaction. That is, it is considered that the isocyanate group is changed in the bonded state.
For example, when the substrate is glass, it is considered that the isocyanate group reacts with the silanol group on the glass surface and is bonded.

At least a part of performances such as antifouling property, abrasion resistance, chemical resistance and weather resistance imparted to a substrate having a coating formed from the composition of the present invention depends on the reactivity of the isocyanate group. It is believed that the other part is due to the silicon atom directly bonded to the isocyanate group.

The isocyanate silane compound of the present invention is
From the viewpoint of bondability to the base material, a structure in which the number of isocyanate groups bonded to one silicon atom is 2 or more is desirable.

Preferred examples of the isocyanate silane compound of the present invention include compounds represented by the following formula (A) or formula (B). In addition, below, the compound represented by Formula (A) is described as a compound (A), and the compound represented by Formula (B) is described as a compound (B).

[0020]

[Chemical 3]

[0021]

[Chemical 4]

However, in the formula (A), R ¹ , R ² ,
R ³ and R ⁴ each represent a hydrogen atom or an organic group having 1 to 30 carbon atoms. a and b are respectively
An integer that is 0, 1, or 2 and satisfies 0 ≦ a + b ≦ 2 is shown. c and d are 0, 1, or 2, respectively, and represent integers satisfying 0 ≦ c + d ≦ 2. Y represents a divalent organic group.

In formula (B), R ⁵ , R ⁶ , and R
⁷ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
e, f, and g are 0, 1, 2, or 3 respectively.
And an integer satisfying 1 ≦ e + f + g ≦ 3.

The compound (A) represents a compound having two silicon atoms bonded with an isocyanate group, and the compound (B)
Represents a compound having one silicon atom bonded to an isocyanate group. In the compound (A) and the compound (B), the number of isocyanate groups bonded to a silicon atom is preferably 2 or more per silicon atom. This is because it is considered that the bond to the surface of the base material becomes stronger as the number of isocyanate groups increases.

It is desirable that R ^{1 to} R ⁷ represent an organic group having 1 to 30 carbon atoms. In particular, R ^{1 to} R ^{7 present}
It is preferred that all of the above represent organic groups.

When R ^{1 to} R ⁷ represent an organic group, a hydrocarbon group such as an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, a halogenated hydrocarbon group such as a chloroalkyl group or a polyfluoroalkyl group, a hydroxyl group , Amino groups, mercapto groups, carboxy groups, hydrocarbon groups having other functional groups or halogenated hydrocarbon groups, ester bonds in the carbon chain, ether bonds, thioether bonds, imino bonds, amide bonds, urethane bonds, other It is preferably a hydrocarbon group having a bond or a halogenated hydrocarbon group. In particular, an organic group having a hydrocarbon group and a polyfluoroalkyl moiety is preferable.

Examples of the preferred compound (A) and compound (B) include organoisocyanate silane compounds having two or more fluorine atoms.

That is, in the compound (A), Y is 2
It is preferable that the above divalent organic group having a fluorine atom be shown, or at least one of R ^{1 to} R ⁴ present be a monovalent organic group having two or more fluorine atoms. Of course, both Y and at least one of R ^{1 to} R ⁴ may represent an organic group having two or more fluorine atoms.

In the compound (B), R ^{5 to} R ⁷ are
It is preferable that each represents a hydrocarbon group or an organic group having a polyfluoroalkyl moiety, and further, R ^{5 to} R
^It is preferable that at least one of ⁷ represents an organic group having a polyfluoroalkyl moiety, and it is particularly preferable that all of R ^{5 to} R ⁷ represent an organic group having a polyfluoroalkyl moiety.

In each of the compound (A) and the compound (B), the organic group having no fluorine atom is preferably the above hydrocarbon group. In the case of an organic group having two or more fluorine atoms, it is preferable that the silicon atom is bonded to a carbon atom having no fluorine atom (for example, a methylene group).

In the present invention, the isocyanate silane compound is particularly preferably the compound (B) because it has the advantage that it can be cured at room temperature.

In the compound (B), when any one of R ^{5 to} R ⁷ represents an organic group having a fluoroalkyl moiety, a polyfluoroalkyl group, a polyfluorooxaalkyl group, a polyfluorothioalkyl group, or these It is preferable that any group and a hydrocarbon group such as an alkylene group be bonded to a silicon atom at the other end of the hydrocarbon group via an organic group bonded by an ester bond or the above-mentioned linking bond. Furthermore, the polyfluoroalkyl group, polyfluorooxaalkyl group, and polyfluorothioalkyl group have an alkylene group, preferably a dimethylene group, at or near the end bonded to the silicon atom, and the other part is a perfluoro group. Those groups are preferable. The perfluoro moiety is a perfluoroalkyl group having 3 or more carbon atoms,
A perfluorooxaalkyl group or a perfluorothioxaalkyl group is preferable, and particularly, a carbon number of 3 to 16
The perfluoroalkyl group of is preferable.

Compound (A) and compound (B) of the present invention
Specific examples of the above are shown below, but the present invention is not limited to these examples. In the chemical formulas below, n and m are integers of 1 or more, R is an alkyl group, Z is an isocyanate group, R _f is a polyfluoroalkyl group, and R is an R group.
_F represents a perfluoroalkyl group. Further, it is preferable that R represents a lower alkyl group and R _f represents a perfluoroalkyl group having a dimethylene group. In particular, R _f
As C _s F _{2s + 1} C _k H _2k − (where s is 3 to 1)
The integer of 6 and k show the integer of 2-4. ) Perfluoroalkyl group having dimethylene group represented by is, as the _{R F, C t F 2t +} 1 - ( however, t is preferably a perfluoroalkyl group represented by an integer) of 3 to 16.

Examples of compound (A).

[0035]

[Chemical 5]

[0036]

[Chemical 6]

[0037]

[Chemical 7]

[0038]

[Chemical 8]

[0039]

[Chemical 9]

[0040]

[Chemical 10]

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

[0044]

[Chemical 14]

Examples of compound (B).

[0046]

[Chemical 15]

[0047]

[Chemical 16]

[0048]

[Chemical 17]

The composition of the present invention contains, as an essential component, the above-mentioned isocyanate silane compound and a compound containing a polymerized unit of tetrafluoroethylene. By including the compound in the composition, the antifouling effect in the case of forming a coating film can be dramatically improved (hereinafter, a compound containing a polymer unit of tetrafluoroethylene is referred to as a compound (C). ).

The compound (C) is not particularly limited,
Examples thereof include linear and branched compounds containing a polymerized unit of tetrafluoroethylene, and linear compounds are preferable. The proportion of polymerized units of tetrafluoroethylene in the compound is 20% by weight or more, preferably 40% by weight in the compound.
The above is preferable.

The compound (C) is-(CF ₂ CF ₂ ) _n- (however,
n represents an integer of 5 or more. Compounds having) as a structural unit are preferred.

Examples of the compound (C) include a polymer of tetrafluoroethylene, a copolymer of tetrafluoroethylene and another polymerizable monomer, and the like. Examples of the other polymerizable monomer include a known or known polymerizable monomer having a polymerization site capable of being polymerized with tetrafluoroethylene, but from the viewpoint of film-forming property when forming a film, Ethylene, propylene, acrylate, methacrylate and the like are preferable. Even when the compound (C) is a copolymer, the proportion of tetrafluoroethylene in the copolymer is preferably 20% by weight or more, and more preferably 40% by weight or more.

The preferred compound (C) is polytetrafluoroethylene, which is a homopolymer of tetrafluoroethylene.

The molecular weight of the compound (C) is 1000 to 10
A range of about 0000 is preferable. If the molecular weight is too small, the antifouling performance may decrease, and if the molecular weight is too large, the durability performance may decrease. Further, since the transparency tends to decrease as the molecular weight increases, it is necessary to select the molecular weight according to the substrate to be applied.

The form of the compound (C) is not particularly limited, but spherical fine particles are preferable. The average particle diameter of the spherical fine particles is preferably 10 μm or less. If the particle size becomes too large, the mechanical abrasion property will decrease, which is not preferred in the present invention.

In the present invention, a film is formed from the composition containing the above-mentioned isocyanate silane compound and the above-mentioned compound (C) as essential components. The coating is an excellent coating having a much lower energy surface as compared with the coating formed from each of the above-mentioned isocyanate silane compound or compound (C) alone. Therefore, it exhibits antifouling properties, chemical resistance, abrasion resistance, and other properties that cannot be achieved by a coating film obtained from a single component.

Although the mechanism for expressing such performance is not always clear, the coating film of the present invention is
Due to the combined effect of two compounds having different three-dimensional structures, the denseness of the film is increased, and the fluorine concentration in the film is increased,
As a result, micro voids and polar parts are reduced. The reduction of micro voids leads to the reduction of physical dirt adsorption,
It is believed that the reduction of polar moieties leads to a reduction in the adsorption of chemical stains.

Further, both the isocyanate silane compound and the compound (C) of the present invention are substances having a small surface free energy, and since the density of fluorine concentration is increased on the surface, the effective antifouling property is exhibited. It is a thing.

Further, since there is a difference in surface free energy between the isocyanate silane compound and the compound (C), specifically, the isocyanate silane compound has a smaller surface free energy than the compound (C). There will be a high fluorine concentration region to the inside,
It is considered that this is one of the reasons for the excellent durability performance.

The mixing ratio of the isocyanate silane compound and the compound (C) is not particularly limited and may be appropriately changed depending on the purpose. Usually, 5 to 20 parts of the compound (C) is added to 100 parts by weight of the isocyanate silane compound.
About 0 parts by weight is preferable. When the amount of the compound (C) is small, the antifouling property decreases, and when it is too large, the abrasion resistance decreases, which is not preferable.

In the present invention, excellent antifouling performance can be imparted to the surface of the base material by treating the surface of the base material with the composition containing the above-mentioned isocyanate silane compound and compound (C). Further, the composition is a compound other than the above-mentioned isocyanate silane compound and compound (C),
It may contain additives and the like.

The method of treating the surface of the substrate is not particularly limited. Usually, by coating the surface of the substrate with the above composition and binding the isocyanate silane compound to the surface of the substrate. At this time, it is desirable that the composition is a solution containing an organic solvent from the viewpoint of ease of application.

The total amount of the isocyanate silane compound and the compound (C) contained in the solution is determined in consideration of the film forming property (workability), stability, coating thickness, and economic efficiency, but it is usually In the case of, it is preferably 0.1 to 30% by weight.

As the organic solvent, a fluorine-containing organic solvent is preferable from the viewpoint of solubility of the compound (C), and various solvents such as acetic acid esters, aromatic hydrocarbons, ketones and ethers are added. You may. However, those having a reactive hydrogen atom react with the isocyanate group of the isocyanate silane compound, which is not desirable.

Other compounds, additives and the like are added to the composition of the present invention depending on the purpose. The type and amount of the additive can be appropriately changed in consideration of the reactivity and compatibility with the isocyanate silane compound and the compound (C). Examples of the additive include ultrafine particles of various metal oxides, various resins, and the like. If coloring is required, dyes, pigments, etc. may be added. The amount of these additives is preferably about 0.1 to 20 parts by weight based on 100 parts by weight of the total of the isocyanate silane compound and the compound (C). Excessive addition is not desirable because it lowers the antifouling property and abrasion resistance of the present invention.

As a method for forming a film from the composition of the present invention, in general, a liquid material containing the prepared composition and an organic solvent is applied to the surface of a substrate, and the composition is exposed to air or nitrogen air at room temperature. The method of drying with. As a coating method, various methods such as brush coating, flow coating, spin coating, dip coating and spray coating can be exemplified. In addition, heating may be performed for the purpose of increasing the drying rate. When heating, the temperature, time, etc. may be set in consideration of the heat resistance of the substrate. Further, the thickness of the coating film formed can be appropriately controlled depending on the concentration of the liquid containing the composition, coating conditions, heating conditions, and the like.

No special pretreatment is required on the surface of the base material, but it may be carried out according to the purpose without any particular problem. For example, acid treatment with diluted hydrofluoric acid, hydrochloric acid or the like, sodium hydroxide or potassium hydroxide aqueous solution may be used. Examples of the treatment include alkali treatment with the like, discharge treatment with plasma irradiation, and the like.

Since the coating film of the present invention has a low refractive index, it can impart not only antifouling property but also low reflectivity to the substrate. When such an effect is expected, the film thickness of the film may be controlled to a film thickness that causes optical interference. The film thickness of the coating is theoretically required to be a monolayer or more in order to exhibit the antifouling property. Therefore, in order to achieve both the antifouling property and the low reflection property, if the economic effect is taken into consideration, the film thickness is 2 μm or less. It is desirable to have.

The base material of the present invention is not particularly limited. Examples thereof include metals, plastics, ceramics, glass, other inorganic materials and organic materials, or composite materials which are combinations thereof, laminated materials, and the like. Further, the surface of the base material is not limited to the one made of the material of the base material itself, but a surface of a material different from the base material itself such as a coating film surface of a coating metal or a surface-treated layer surface of a surface-treated glass or the like. May be As the surface of the surface treatment layer, for example,
The surface provided with a sol-gel film, a sputtered film, a CVD film, a vapor deposition film and the like can be exemplified.

The shape of the base material is not limited to a flat surface,
It may have any shape depending on the intended use of the substrate, such as one having a curvature on the entire surface or a part thereof.

The base material of the present invention is preferably a base material made of a transparent material such as glass or plastic capable of utilizing the transparency of the coating film, and particularly preferably glass. When glass is used as the substrate, the isocyanate silane compound of the present invention reacts with the silanol groups of the glass,
Since it is firmly bonded to the glass surface, a coating having excellent durability can be obtained.

The article having the base material of the present invention as a constituent element is not particularly limited, but when the base material is a transparent material, an article that can make full use of the transparency is preferable. Examples of the article include articles for transportation equipment and articles for construction and construction. This is because in these articles, the visibility is likely to be deteriorated due to the attachment of raindrops, dust, dirt, and the like, and serious problems may occur due to the occurrence of problems due to the deterioration.

As the articles for transportation equipment, outer plates, window glasses, mirrors, exterior materials such as surface materials for display devices, interior materials such as instrument panel surface materials in transportation equipment such as trains, buses, trucks, automobiles, ships and aircrafts. Examples include members, parts and components used or used for other transportation equipment. The article may consist only of the substrate having the coating of the present invention, or may have the substrate having the coating of the present invention incorporated therein. An example of the former is a window glass for an automobile, and an example of the latter is a rearview mirror member for an automobile in which a glass mirror is incorporated.

Further, as the articles for transportation equipment, train bodies, window glasses, pantographs, automobiles, buses,
Examples thereof include bodies such as trucks, windshields, side glasses, rear glasses, mirrors, bumpers, bodies of ships and the like, window glasses and the like, bodies of aircraft and the like, window glasses and the like.

The coating film of the present invention is also excellent in water repellency. Therefore, in such an article, the water repellency of the coating film of the present invention can repel water droplets adhering to the surface. In particular, when the article is for transportation equipment, the wind pressure and water repellency received by the movement of the transportation equipment can cause water droplets to move extremely quickly from the surface of the article, and The adverse effects of staying in place can be eliminated. In particular, in a transparent field portion such as various window glasses, movement or scattering of water droplets makes it very easy to secure the field of view, and the safety of the vehicle can be improved. Also, in an environment where water droplets freeze, it is possible to prevent freezing.
Even when frozen, the effect of remarkably quick thawing is recognized.
Furthermore, since it reduces the adhesion of dirt due to the adhesion of water droplets, it is very advantageous from the viewpoint of aesthetic protection,
The number of regular cleaning operations can be reduced, and cleaning is extremely easy.

The building and building articles comprising the base material of the present invention as a component are used as an article to be attached to a building, an article already attached to a building, or a building without being attached to a building. Building articles such as furniture, furniture, furniture, and the like.

Specific examples of construction and building articles include window glass sheets, window glass, various roofs including glass sheets for roofs and glass roofs, glass sheets for doors, doors in which they are fitted, and partitions. Consists of glass plate, greenhouse glass plate or greenhouse, transparent plastic plate used in place of glass and the building articles (window materials, roofing materials, etc.) having the same as above, ceramics, cement, metal and other materials Examples include wall materials, mirrors, furniture having the same, glass for display shelves and showcases, and the like. These articles may consist only of the base material having the coating of the present invention, or may have the base material incorporated therein. For example, the former is a glass plate for windows and the latter is a furniture in which a glass mirror is incorporated.

In such a surface-treated base material, stains coming into contact with the surface are less likely to adhere due to the antifouling property, and even if adhered, the amount thereof is small, and the adhered stains can be easily removed. Further, since it has not only antifouling performance but also water repellency, it does not freeze even in an environment where water drops freeze, and even if it freezes, thawing is extremely fast. Furthermore, since there is almost no dirt attached, the number of regular cleaning operations can be reduced, and cleaning is extremely easy, which is very advantageous from the viewpoint of aesthetic protection.

[0079]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.

Various evaluation methods in the examples are as follows.

[Evaluation Method of Amount of Adhered Dirt] A sample was left at an angle of 30 degrees along a road with a lot of traffic. The sample was taken out after 2 months of standing, the weight of the sample was measured with a balance, and the sample was wiped with Kimwipe L-100 until the appearance was clean. The weight of the sample was measured again with the balance, and the difference in weight before and after the wiping was taken as the amount of dirt attached.

[Evaluation Method of Degree of Contamination] A sample was left at a 30 ° inclination along a road with a large amount of traffic. Samples were taken out after 6 months and 1 year, and the state of the stain was visually observed. Table 1 shows the judgment criteria with the naked eye.

[0083]

[Table 1]

[Evaluation method of easiness of wiping off oil-based ink]
Oil-based magic ink (No.500) on the sample surface
After marking for 1 minute and leaving it for 1 minute, it was wiped off with Kimwipe L-100, and the remaining amount of the magic ink was visually judged. Table 2 shows the criteria for easiness of wiping off the oil-based ink.

[Evaluation method of easiness of wiping off stains] The sample was left standing at an angle of 30 degrees along a road having a high traffic volume. After leaving for 6 months, the sample was taken out and wiped dry 5 times with Kimwipe L-100, and the degree of remaining stain was visually observed to judge the ease of wiping. Table 2 shows the criteria for easiness of wiping off dirt.

[0086]

[Table 2]

[Abrasion Resistance Evaluation Method] The flannel cloth was reciprocally moved under a load of 1 kg, the contact angle of water after 10,000 reciprocations was measured, and the values before and after the test were compared.

[Evaluation method of weather resistance] After irradiation with ultraviolet rays for 8 hours (temperature: 70 ° C.), wet exposure for 4 hours (temperature: 50 ° C.)
The weather resistance test was carried out for 300 cycles, with the step of (° C.) as one cycle. The contact angle of water after the test was measured, and the values of the contact angle of water before and after the test were compared.

[Evaluation Method of Haze] The sample was left at an angle of 30 degrees along a road having a high traffic volume and left. After leaving for 6 months, the sample was taken out, wiped 5 times with Kimwipe L-100, and then measured by HGM-2BP direct reading haze computer manufactured by Suga Test Instruments. The value before standing and the value after dry wiping were measured, and the value after (dry wiping-value before standing) / (value before standing) was taken as the rate of change in haze. The larger the value, the greater the degree of fogging.

The abbreviations of the compounds used in the following examples and comparative examples have the following meanings.

(A) C ₉ F ₁₉ C ₂ H ₄ (NCO) ₃ (b) Molecular weight 3000
Polytetrafluoroethylene dispersion solution (dispersion medium: 1,1,2-trichloro-1,2,2-trifluoroethane) (c) Polytetrafluoroethylene fine particles (d) 1,1 having a particle diameter of 0.15 μm , 2-trichloro-
1,2,2-Trifluoroethane [Example 1] 10.0 g of (b) and 30.0 g of (d) were added to a flask equipped with a stir bar and a thermometer, and the mixture was kept at 25 ° C for 30 minutes. It was stirred. Furthermore, 5 of (d)
After adding 8.2 g and 1.8 g of (a), stirring was continued for one day while maintaining the liquid temperature of this solution at 25 ° C. to obtain a treating agent 1.

Next, pre-cleaned 10 cm × 10 cm
10 cc of the treating agent 1 was dropped on a (thickness 3 mm) glass plate and spread with a cloth in the same manner as waxing to prepare a sample. The results of evaluating this test piece are shown in Tables 3 and 4.

Example 2 In a flask equipped with a stir bar and a thermometer, 3.0 g of (a) and 97.
0 g was added, the solution was maintained at 25 ° C. and stirred overnight. Furthermore, after adding 0.5 g of (c) to this solution, stirring was continued for one day while maintaining the solution liquid temperature at 25 ° C. to obtain a treating agent 2.

Next, pre-cleaned 10 cm × 10 cm
10 cc of the treating agent 2 was dropped on a (thickness 3 mm) glass plate, and spread with a cloth in the same manner as waxing to prepare a sample. The results of evaluation of this test piece by the above method are shown in Table 3.
And shown in Table 4.

Comparative Example 1 A test piece was prepared in the same manner as in Example 1, except that silicone oil was used as a treating agent.
The results of evaluating this test piece are shown in Tables 3 and 4.

Comparative Example 2 A test piece was prepared in the same manner as in Example 1, except that only (b) was used as the treating agent. The results of evaluating this test piece are shown in Tables 3 and 4.

Comparative Example 3 3.0 g of (a) and 97. of (b) were placed in a flask equipped with a stir bar and a thermometer.
0 g was added, the solution was maintained at 25 ° C. and stirred overnight. Using this solution as the treating agent 3, a test piece was prepared in the same manner as in Example 1. The results of evaluating this test piece are shown in Tables 3 and 4.

Comparative Example 4 Tables 3 and 4 show the results of evaluation of untreated float glass.

[0099]

[Table 3]

[0100]

[Table 4]

Example 3 The test piece obtained in Example 1 was immersed in the chemicals shown in Table 2 for 24 hours, taken out and immediately washed, and then the appearance change of this test piece and the ease of wiping off the oil-based ink were evaluated. evaluated. The results are shown in Table 5.

[0102]

[Table 5]

Example 4 The same treatment agent as in Example 1 was applied to the surface of an automobile front laminated glass in the same manner as in Example 1 to form a film. The obtained front laminated glass was attached to the front of an automobile. We conducted a running test of running this car for 3 months for 4 hours during the day, and every day, we checked the front surface for dirt and dust,
Furthermore, the state of attachment of water droplets in the rain was visually observed.

As a result, the generation of water stains due to dirt, dust adhesion, and water droplet adhesion was not observed at all, and even if these occurrences were rarely observed, they were easily removed by gently wiping with a tissue paper. Also, in rainy weather, water drops on the surface were repelled, and when traveling, it quickly moved due to wind pressure, so there was no need to use a wiper, and the field of view could be secured.

[Embodiment 5] An automobile equipped with the same windshield as in Embodiment 4 was subjected to a running test in an environment of 0 ° C to -5 ° C, and no icing was observed on the windshield. When a running test was conducted in a more severe low temperature environment (-10 ° C to -15 ° C), the ice on the windshield was quickly thawed.

[Comparative Example 5] Untreated front laminated glass was mounted on an automobile in the same manner as in Example 4, and the temperature was 0 ° C to -5 ° C.
When a running test was carried out in the environment, the water drops adhering to the windshield or the water in the air was condensed and frozen on the windshield. In a more severe low temperature environment (-10 ° C to -15 ° C), almost no frost was thawed.

[Embodiment 6] The same effects as in Embodiments 4 and 5 were confirmed as a result of carrying out a running test by changing the front laminated glass of Embodiment 4 to a side glass and a side mirror.

[Embodiment 7] The surface of a front laminated glass for an automobile, which has been used for 1 year, is polished with cerium oxide, rinsed with a sufficient amount of water, water is removed with a dryer, and water accumulated on the surface is removed. Reds, dirt, dust, etc. were removed. When this surface was treated in the same manner as in Example 1 and the same running test as in Examples 4 and 5 was carried out, the same effect as in Examples 4 and 5 was confirmed.

[Embodiment 8] The surface of a painted body of an automobile, which has been used for 1 year, is polished with cerium oxide, rinsed with a sufficient amount of water, and dried with a dryer to remove water stains, dirt and dust. Removed. This surface was treated in the same manner as in Example 1. When the same running test as in Examples 4 and 5 was carried out, the same effect as in Examples 4 and 5 was confirmed.

Example 9 The treatment agent of Example 1 was applied to the surface of architectural glass in the same manner to form a film.
The obtained building glass was attached to a building. This window glass was left standing for 3 months, and the state of dirt and dust adhering to the surface of the window glass, and the adhering state of water drops in rainy weather was observed daily with the naked eye. As a result, generation of water stains due to dirt, dust adhesion, and water drop adhesion was not observed at all, and even if these occurrences were rarely observed, they were easily removed by gently wiping with tissue paper.

In rainy weather, water drops on the surface are repelled,
There was no spreading of water and the field of view was secured. On a rainy day with strong wind, it was easier to secure the field of view because the water droplets quickly moved due to wind pressure.

[Example 10] The same building glass as in Example 9 was attached to a building and left for 3 months in an environment of 0 ° C to -5 ° C, but no freezing was observed on the window glass. It was In a more severe low temperature environment (-10 ° C to -15 ° C), frost on the window glass was quickly thawed.

Comparative Example 6 Untreated architectural glass was attached to a building and left in the same environment as in Example 10. 0 ° C
At -5 ° C, water droplets adhering to the window glass or condensed water in the air was frozen in the window glass. -10 ℃ ~
At −15 ° C., freezing was significantly slower than in Example 10.

[Embodiment 11] The building window glass of Embodiment 9 is used as a building heat ray reflection glass (Asahi Glass Co., Ltd./Sunlux S).
As a result of changing to S8) and leaving it in the same environment as in Examples 9 and 10, the same effect as in Examples 9 and 10 could be confirmed.

[Example 12] The surface of a building window glass that has been installed for 1 year has been polished with cerium oxide, rinsed with sufficient water, and dried with a dryer to remove water stains, dirt and dust on the surface. Etc. were removed. The surface of the washed window glass was treated in the same manner as in Example 1. Further, as a result of being left in the same environment as in Examples 9 and 10, the same effect as in Examples 9 and 10 was confirmed.

[0116]

EFFECTS OF THE INVENTION The base material of the present invention and the article equipped with the base material are: It has excellent antifouling properties, does not have dust, dirt, water droplets attached, or water stains due to it, and even if there are rare cases, it can be easily removed and the adverse effect of dirt can be blocked, Cleaning can be simplified. Also,
Even when removing dirt, scratches are less likely to occur. 2. It has excellent stain resistance and can maintain its state semipermanently.
3. Due to its excellent chemical resistance, it can be applied along the coastline or in areas where seawater is in direct contact, and can be applied to a wide range of fields. 4. When the composition of the present invention is treated, no special pretreatment is required, so that it is economically effective. In addition, since it can be treated at room temperature, it can be used for repairing already-made articles. 5. Since it also has excellent water repellency, it can prevent the formation of water stains and stains caused by water. In a low temperature environment,
It also has the property of quickly thawing water droplets. 6. When applied to articles in the fields of transportation equipment, construction and construction,
It is possible to simplify cleaning, maintain aesthetics, and ensure safety.

The above-mentioned effects cannot be expected with conventional materials, and it can be expected that the range of application thereof will be expanded to fields where it was impossible to use until now.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C09K 3/00 F 112 E 3/18 104 (72) Inventor Go Morimoto Hazawa, Kanagawa-ku, Yokohama, Kanagawa Prefecture 1150, Machi Asahi Glass Co., Ltd. Central Research Laboratory

Claims (13)

[Claims] 1. A substrate having on its surface a coating formed from a composition containing an isocyanate silane compound and a compound containing polymerized units of tetrafluoroethylene as essential components. 2. An isocyanate silane compound represented by the following formula (A):
The base material according to claim 1, which is a compound represented by (B). Embedded image (A) (NCO) _3-ab (R ¹ ) _a (R ² ) _b Si-Y-Si (R ³ ) _c (R ⁴ ) _d (NCO)
_{3-cd embedded image} (B) (R ⁵ ) _e (R ⁶ ) _f (R ⁷ ) _g Si (NCO) _4-efg However, in the formula (A), R ¹ , R ² , R ³ , and R ⁴ each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Each of a and b is 0, 1, or 2, and represents an integer satisfying 0 ≦ a + b ≦ 2.
c and d are 0, 1, or 2, respectively, and represent integers satisfying 0 ≦ c + d ≦ 2. Y represents a divalent organic group. In formula (B), R ⁵ , R ⁶ , and R
⁷ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
e, f, and g are 0, 1, 2, or 3 respectively.
And an integer satisfying 1 ≦ e + f + g ≦ 3. 3. The base material according to claim 1, wherein the isocyanate silane compound is a compound represented by the formula (B). 4. A compound represented by the formula (B), wherein R is
The base material according to claim 2 or 3, wherein ⁵ , R ⁶ and R ⁷ represent an organic group having 1 to 30 carbon atoms. 5. In the compound represented by formula (B), R
^{5. The} substrate according to claim 2, wherein at least one of ⁵ , R ⁶ and R ⁷ represents an organic group having a polyfluoroalkyl moiety. 6. A compound containing a polymerized unit of tetrafluoroethylene is a compound having — (CF ₂ CF ₂ ) _h — (wherein h is an integer of 5 or more) as a structural unit.
A substrate according to any one of 5 to 5. 7. The base material according to claim 1, wherein the compound containing a polymerized unit of tetrafluoroethylene has a molecular weight of 1,000 to 100,000. 8. A compound containing polymerized units of tetrafluoroethylene is spherical particles and has an average particle diameter of 10 μm.
The base material according to any one of claims 1 to 7, which is m or less. 9. A compound containing a polymerized unit of tetrafluoroethylene is polytetrafluoroethylene.
The base material of any one of 8. 10. The base material is made of a transparent material.
Any of the base materials. 11. The substrate according to claim 10, wherein the substrate is glass. 12. An article comprising the base material according to claim 1 as a constituent element. 13. The article according to claim 12, which is an article for transportation equipment, construction, or construction.