JP2003064348A - Antifouling surface treating agent and composition for antifouling surface treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling surface treating agent capable of imparting stain resistance, abrasion resistance, slipperiness and the like to the surface of glass and the like. SOLUTION: This antifouling surface treating agent comprises an alkoxysilane compound represented by the formula (1) and having a high molecular weight perfluoropolyether group having >=2,000 average molecular weight. And, using the agent, a treating film 2 excellent in water and oil repellency, stain resistance, abrasion resistance, slipperiness and the like is formed on the surface of a silicon oxide-containing substrate 1 such as glass. (R is perfluoropolyether group; R<1> is O, NH or S; R<2> is an alkylene chain; and R<3> is an alkyl chain).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antifouling surface treatment agent and a composition for antifouling surface treatment, which gives a cured film excellent in water repellency, oil repellency and abrasion resistance.

[0002]

2. Description of the Related Art In the case of window glass, automobile glass, or an optical component in which a silicon oxide layer is formed on a plastic substrate to have antireflection property, if rainwater or contaminants adhere to these components It takes time and effort to wipe and clean a kimono, especially oil stains, and it is difficult to always keep it clean.

As described above, substrates such as glass whose surface is mainly formed of silicon dioxide have a high surface hardness, but on the other hand, dirt due to hand dust, fingerprints, sweat, hair liquid, hair spray, etc. is easily noticeable. Also, it has the drawback that it is difficult to remove. Further, there is a problem that the scratches at the time of damage tend to become thick due to poor surface slippage. Further, since it has high wettability with water, when raindrops or water droplets adhere, it spreads greatly, and for example, in an eyeglass lens or the like, an object appears distorted over a large area.

In recent years, CRT, LCD, PDP (P
lasma Display Panel), EL (E
Although displays such as retro luminescence have been developed and used in various fields, an antireflection film for making images easier to see is increasingly provided on the display surface.
This antireflection film is generally formed by providing a material having a lower refractive index than the lower layer on the outermost surface by an optical film thickness of ¼ of the wavelength of the target light. As a method of forming this outermost surface layer, a method of providing a material such as magnesium fluoride or silica by vacuum deposition or a sputtering method, a method of solution-coating a hydrolyzate of alkoxysilane, or a fluorine-based polymer film is used. Although a method of forming by vapor deposition or coating is used, there is a problem that fingerprint stains are particularly noticeable due to the low refractive index of these layers.

In order to solve these problems, it has been attempted to prevent the contamination by applying water repellent treatment to the glass surface. For example, JP-A-1-126244 discloses a method of immersing an inorganic glass in a solution composed of polydimethylsiloxane and a liquid hydrocarbon at room temperature, applying the inorganic glass by a dipping method, and then baking at 250 to 350 ° C. ing. Further, JP-A-5-24885, JP-A-6-16455, and JP-A-8-2677.
Japanese Patent No. 4 discloses a silane compound containing a polyfluoroalkyl group. Japanese Unexamined Patent Publication (Kokai) No. 5-170486 discloses a method of applying a mixture obtained by adding an alkoxysilane to a fluoroalkyl group-containing silane compound.

[0006]

However, the treated film with the conventional silicone-based coating agent or fluorine-based coating agent is easily dissolved in water or various solvents, and if it is simply coated, its effect is obtained by the solvent treatment. It was deteriorated and had low chemical stability. In addition, any of the treated films temporarily imparts a function, its effect is deteriorated by a mechanical action of a wiper or the like, and it is not durable and poor in durability. In particular, the conventional fluorine-based coatings have a drawback that the water repellency increases, but the coating thickness increases and coating unevenness is likely to occur, and satisfactory results cannot be obtained with respect to friction or abrasion.

Therefore, in the treated film of water repellent glass,
In order to have sufficient chemical stability and abrasion resistance and to have durability, it is required to increase the film strength of the treated film and to increase the bonding force between the glass substrate surface and the treated film. . In particular, these are important when it is desired to reduce the thickness of the treated film.

The present inventors previously developed a method for forming a coating film of an alkoxysilane compound having a perfluoropolyether group on a glass or plastic substrate made of silicon dioxide (Japanese Patent Laid-Open No. 11-92177). Gazette). That is, in order to have a strong interaction with SiO ₂ on the surface of the base material, an alkoxysilano group is incorporated into the molecular structure to improve solvent resistance. Although the abrasion resistance and the solvent resistance were significantly improved by the formation of this film, there were cases where the sliding property was not always sufficient.

The present invention has been made in order to solve the above-mentioned problems of the prior art, and it is possible to obtain a coating film having improved water repellency and slipperiness, and excellent stain resistance and abrasion resistance. It is an object of the present invention to provide an antifouling surface treating agent and an antifouling surface treating composition that can be used.

[0010]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above-mentioned problems, and as a result, have reached the invention described below. That is, according to the invention of claim 1, in the antifouling surface treating agent containing the alkoxysilane compound represented by the following general formula (1), the average molecular weight of the perfluoropolyether group of the alkoxysilane compound is in the range of 2000 to 10,000. It is characterized by being in.

[0011]

[Chemical 4]

The invention of claim 4 is an antifouling surface treatment composition comprising an alkoxysilane compound represented by the above general formula (1) and a fluorinated hydrocarbon solvent, the alkoxysilane compound The average molecular weight of the perfluoropolyether group of is in the range of 2000 to 10,000.

In the alkoxysilane compound of the antifouling surface treating agent and the antifouling surface treating composition of the present invention, the perfluoropolyether group in the molecule has a ratio Mw of the weight average molecular weight Mw to the number average molecular weight Mn. It is preferable to have a molecular weight distribution in which / Mn is 1.2 or less. When the average molecular weight of the perfluoropolyether group is smaller than 2000 and Mw / Mn is larger than 1.2, the low molecular weight perfluoropolyene having a higher surface energy than the alkoxysilane compound having the high molecular weight perfluoropolyether group. The increase in the ratio of the alkoxysilane compound having an ether group reduces the surface slipperiness of the obtained treated film, and if it exceeds 10,000, it is not preferable in terms of stability and handling. Examples of the perfluoropolyether group contained in the molecule of such an alkoxysilane compound include those having a molecular structure represented by the following formula (2).

[0014]

[Chemical 5]

Such an alkoxysilane compound having a perfluoropolyether group can be synthesized from a perfluoropolyether compound having an ester group at both ends. The synthesized alkoxysilane compound is
When used as an antifouling surface treatment agent, a volatile solvent,
It is preferably 0.01 when diluted with a fluorinated hydrocarbon solvent.
After preparing a treatment film composition having a concentration of from 10% by weight, it is applied onto a substrate to be surface treated, preferably a substrate having a surface layer containing silicon oxide. Incidentally, the antifouling surface treatment composition comprising an alkoxysilane compound and a fluorinated hydrocarbon solvent, if necessary, an acid, a base, a phosphate ester,
And one or more kinds of catalysts selected from β-diketones. As a result, good surface characteristics can be obtained even in a film forming process at a low temperature.

The coated alkoxysilane compound undergoes a so-called sol-gel reaction, which is a so-called sol-gel reaction, caused by dealcoholization with, for example, silicon dioxide on the surface of the substrate to form a strong bond. In addition, a water-repellent effect is exhibited by containing a fluorine compound in the molecule, and a lubricating effect is exhibited by containing a perfluoropolyether group. Furthermore, since the alkoxysilane compound having a high molecular weight perfluoropolyether group has a lower surface energy than that of an alkoxysilane compound having a low molecular weight perfluoropolyether group, the slipperiness of the surface is improved and the wear resistance is improved. Also exhibits excellent durability.

Therefore, the antifouling surface treating agent and the antifouling surface treating composition containing the alkoxysilane compound of the present invention can easily control the film thickness, have excellent solvent resistance, and are less likely to be contaminated. Can be easily removed even when adhered to, and it has excellent water repellency, and since the surface is slippery, it is possible to form a coating having advantages such as scratch resistance.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows an embodiment treated with an antifouling surface treatment agent of the present invention, in which a treatment film 2 made of an antifouling surface treatment agent is provided on a substrate 1 containing silicon oxide such as glass. Is deposited.

The antifouling surface treating agent of the present invention contains the alkoxysilane compound represented by the above general formula (1). The alkoxysilane compound used in the present invention basically has a perfluoropolyether group and an alkoxysilano group, and there is essentially no limitation on the molecular structure other than the perfluoropolyether group. But,
Actually, there is a range from the viewpoint of easiness of synthesis to some extent, that is, feasibility. Hereinafter, each structural part will be described from that point of view.

In the general formula (1), the molecular structure of the perfluoropolyether group Rf is not particularly limited, and includes perfluoropolyether groups having various chain lengths. Those having a molecular structure shown in () are preferable. In this molecular structure, p and q are preferably in the range of 1 to 50, and the perfluoropolyether group Rf in the compound has an average molecular weight of 2000.
It is preferable to have a molecular weight distribution such that the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn is 1.2 or less and is 10,000 to 10,000, preferably 2000 to 4000. If the average molecular weight is less than 2000, Mw /
When Mn is larger than 1.2, the ratio of the alkoxysilane compound having a low molecular weight perfluoropolyether group having a higher surface energy than that of the alkoxysilane compound having a high molecular weight perfluoropolyether group is increased. The surface slipperiness of the treated film is reduced,
When it is larger than 00, it is not preferable in terms of stability and handling.

Further, in the general formula (1), R ¹ represents a divalent atom or group, which is a bonding group of R ² and Rf (perfluoropolyether group), and is not particularly limited, but in terms of synthesis. , And atoms or atomic groups such as O, NH, and S other than carbon are preferable. R ² is a hydrocarbon group and has 2 to 10 carbon atoms.
Is preferred. Examples of R ² include an alkylene group such as a methylene group, an ethylene group, and a propylene group, a phenylene group, and the like. R ³ is an alkyl group constituting an alkoxy group, and usually has a carbon number of 3 or less, that is, an isopropyl group, a propyl group, an ethyl group, and a methyl group, but the carbon number may be more.

Since the alkoxysilane compound having a perfluoropolyether group represented by the formula (1) is a curable substance, the antifouling surface treatment agent of the present invention is applied by diluting it with a volatile solvent. That is, the solvent of the coating composition forming the antifouling surface treatment agent is not particularly limited, but in use, stability of the composition, a group containing a silicon oxide such as glass or an antireflection film which is the surface to be coated is used. Material 1
It should be determined in consideration of the wettability and volatility of the surface of, and it is preferable to use a fluorohydrocarbon solvent here. For example, perfluoroheptane, perfluorooctane, trade name Vertrel manufactured by Mitsui DuPont
-XF hydrofluoropolycarbons, trade names H-GALDEN-ZV75 and ZV8 manufactured by Autogemont
5, hydrofluoropolyethers such as ZV100, C and D, perfluoropolyethers such as SV110 and SV135, and perfluoroalkanes such as FC series manufactured by Sumitomo 3M can be exemplified. Among these fluorohydrocarbon-based solvents, those having a boiling point in the range of 40 to 240 ° C. can be selected, and one of these can be used alone or two or more can be mixed and used. The boiling point of the other solvent added is not particularly limited.

In the present embodiment, the alkoxysilane compound is preferably diluted with the fluorohydrocarbon solvent to a concentration of 0.01 to 10% by weight from the viewpoint of coating properties. If the concentration is too low, the desired effect cannot be obtained because the film thickness of the organic layer is too thin, and if the concentration is too high, the film thickness of the organic layer is too thick, resulting in uneven coating. You can't get the effect.

When preparing the above coating composition of the alkoxysilane compound, it is preferable to add an acid or a base as a reaction catalyst, if necessary. As the acid catalyst, for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acid clay, boric acid, trifluoroacetic acid or the like can be used, and as the base catalyst, an alkali metal such as sodium hydroxide, potassium hydroxide or lithium hydroxide can be used. A hydroxide or the like can be used. The addition amount of these catalysts is preferably about 0.001 to 1 mmol / L. In addition to these acids and bases, phosphoric acid ester-based catalysts such as phosphoric acid dilauryl ester and phosphoric acid perfluoropolyether ester, or β such as acetylacetone.
It is possible to add diketones to enhance their catalytic effect. By adding the catalyst in this way, the interaction involving the binding reaction between the silano group of the compound represented by the general formula (1) and SiO ₂ on the surface of the base material can be performed at a low temperature or without heating. Good progress. For this reason, it is possible to react the formed surface-treated film without adversely affecting it such as deformation, and in the case of a thin film material on SiO ₂ , there is a severe demand from the film thickness to durability. Therefore, good durability can be expected. The amount of such phosphoric acid ester or carbonyl compound added is
It can be about 0.1 to 100 mmol / L.
The drying temperature after applying the coating composition containing such a catalyst is preferably about 20 to 170 ° C.

As the method for applying the coating composition on the surface of the substrate 1, various methods used in ordinary coating operations can be applied, but uniformity,
Further, from the viewpoint of controlling the reflection interference color, spin coating, dipping coating, curtain flow coating and the like are preferably used. Further, from the viewpoint of workability, a method of impregnating a material such as paper or cloth with a liquid and applying and casting it is also preferably used.

From the viewpoint of the balance between water repellency, stain resistance, coatability, and surface hardness, the treated film 2 has a film thickness of 0.5.
˜100 nm, more preferably 0.5 to 50 nm. When the film thickness becomes too thick, the surface may be wiped with a solvent to remove the excess organic layer, and the film may be adjusted to an appropriate thickness.

Of course, when the antifouling surface treatment agent of the present invention is applied, it is preferable that the surface of the substrate 1 to be applied is cleaned. For cleaning, stain removal with a surfactant, degreasing with an organic solvent, steam cleaning with Freon, etc. are applied. further,
Various pretreatments are also effective means for improving adhesion and durability, and particularly preferably used methods include activation gas treatment, chemical treatment with acid, alkali and the like.

Thus, the alkoxysilane compound having a perfluoropolyether group is diluted with a fluorohydrocarbon solvent to prepare a coating composition having a concentration of 0.01 to 10% by weight. By coating and drying the coating composition on the substrate 1 at least the surface of which contains silicon oxide, the treated film 2 made of the above alkoxysilane compound is formed on the surface of the substrate.

Here, antireflection performance can be obtained by using a material having a low refractive index as the alkoxysilane compound for forming the treated film 2. For example, in spectacle lenses and the like, it is called ghost or flare. It is possible to prevent a reflected image from being generated and causing discomfort to the eyes.

Since the treated film 2 formed of the alkoxysilane compound having the perfluoropolyether group contains an alkoxysilano group in its molecular structure, it undergoes a so-called sol-gel reaction with the silicon oxide present on the surface of the base material and becomes strong. Different bonds can be formed. As a result, for example, problems such as wiping with an organic solvent and characteristic deterioration due to cleaning are overcome, chemical stability, which has hitherto been insufficient, is improved, and the above-described effects are permanently retained.

The alkoxysilane compound according to the present embodiment has flexibility and abrasion resistance and abrasion resistance because the molecule has a perfluoropolyether group having excellent flexibility and lubricity. An excellent processed film 2 can be formed.

Although the lubricating property can be obtained only with the perfluoropolyether compound, in this case, as described above, the bond with the base material is weak and the chemical stability is poor.
On the other hand, by using an alkoxysilane compound having a perfluoropolyether group, both chemical stability and abrasion resistance can be achieved.

As described above, since the substrate 1 treated with the antifouling surface treatment agent of the present invention contains an alkoxysilane compound having a perfluoropolyether group as a main component, it is not subjected to usual surface treatment. It has the advantages that it is less likely to be soiled than the base material, is more easily removed when soiled, has excellent water repellency, and is less likely to be scratched due to good surface slippage. Furthermore, it has excellent durability against wear,
It also has excellent chemical stability against solvents. Also, these effects are lasting permanently.

[0034]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. In the examples, “part” means part by weight.

(Experimental Example 1) <Synthesis of alkoxysilane compound> As a raw material, a perfluoropolyether compound having an ester group at both ends represented by the following formula (3) (average molecular weight 4000, weight average molecular weight Mw and number average molecular weight) The ratio Mw / Mn of Mn is 1.2 or less) is used.

[0036]

[Chemical 6]

This perfluoropolyether compound 10
1.8 g of γ-aminopropyltriethoxysilane was added dropwise to g, and the mixture was stirred at room temperature for 2 hours, and then FT-IR shown in FIG.
And the absorption band of the carbonyl group of the ester is 1799 cm ^-1
From 1212c derived from the carbonyl group of a primary amide
changes to m ^-1 and two N-H stretching absorption band (3378cm ^-
1 , 3,301 cm ^-1 ; disappearance of primary amide) and one N-
After confirming the completion of the reaction from the formation of the H stretching absorption band (3317 cm ⁻¹ ; primary amide), a colorless transparent liquid 11.6
g (yield: 95% or more) was obtained. When the obtained compound is referred to as compound 1, ¹ H-NMR data of this compound 1 are shown below.

¹ H-NMR (TMS standard, ppm) --CH ₂ CH ₂ Si ... 0.54-0.58 --CH ₂ CH ₂ CH ₂ --1.60-1.66 --CONHCH ₂ CH ₂ --3. _{26-3.30 -CONHCH 2 CH 2 - 7.05 -Si} (OCH 2 CH 3) 3 3.71-3.76 -Si (OCH 2 CH 3) 3 1.10-1.15

From the above results, the compound 1 is represented by the following formula (4)
It was found to be an alkoxysilane compound represented by

[0040]

[Chemical 7]

<Substrate> A slide glass plate having a thickness of 2 mm was used as a substrate, and the slide glass plate was previously placed in piranha water (mixed solution of concentrated sulfuric acid and hydrogen peroxide solution) at 80 ° C. for 20 minutes.
After heating for a minute, it was washed with distilled water and ethanol in this order and dried.

<Preparation of coating composition and surface treatment> 2 parts of the alkoxysilane compound synthesized from the compound 1 was added to a fluorofluorocarbon having a boiling point of 55 ° C. (Mitsui DuPont Co., Ltd., trade name Vertrel-XF) fluorine system. After dissolving in 200 parts of a solvent and further adding 0.08 part of phosphoric acid perfluoropolyether ester to form a uniform solution, the solution was filtered with a membrane filter to obtain a coating composition. The coating composition was dip-coated on the surface of the slide glass plate at a pulling rate of 5 cm / min, and dried at room temperature for 24 hours to form a treated film having a film thickness of about 2 nm.

<Performance Evaluation> The performance of the surface of the sample surface-treated as described above was evaluated by conducting a test according to the following method. (A) Contamination resistance 5 ml of tap water was dropped on the surface of the sample, and the sample was allowed to stand for 48 hours in a room temperature atmosphere. After that, the remaining state of scale was observed when it was wiped with a cloth. When the scale could be removed, it was marked with ◯, and when it could not be removed, it was marked with x. (B) Surface slipperiness When a sample surface was scratched with a pencil, the degree of catching was evaluated. The judgment method was ◯ when it was not scratched at all, Δ when it was strong, and X when it was weak. (C) Water and oil repellency It was evaluated by the contact angle of water and methylene iodide (CH ₂ I ₂ ). The contact angle is measured by CA-XE manufactured by Kyowa Interface Science Co., Ltd.
It was done using a mold. (D) Abrasion resistance sample surface eraser (Jet Eraser Re
files 813R (75100): Eberhar
After being rubbed 100 times with a load of 200 g under a load of d Faber), the contact angle was measured, and it was visually inspected whether scratches were formed. When there was no scratch, it was marked with O, when it was attached but could be easily removed, it was marked with Δ, and when it was noticeable after it was marked, it was marked with X. (E) Solvent resistance After the surface of the sample was washed with ethanol, the above performance test was conducted again to evaluate the solvent resistance.

(Experimental Example 2) As a perfluoropolyether compound in which both ends of the raw material were esterified with alcohol, those having an average molecular weight of 2000 and Mw / Mn of 1.2 or less were used. The surface treatment was performed in the same manner as in Experimental Example 1 except that the alkoxysilane compound described above was synthesized, and the performance of the obtained sample surface was evaluated. The alkoxysilane compound synthesized in Experimental Example 2 is referred to as Compound 2.

(Comparative Example 1) A surface treatment was conducted in the same manner as in Experimental Example 1 except that a coating composition was prepared by using Compound 3 represented by the following formula (5) in place of Compound 1. The performance of the sample surface was evaluated.

[0046]

[Chemical 8]

Tables 1 and 2 show the structures of the antifouling surface treating agents of Experimental Examples 1 and 2 and Comparative Example 1, respectively, and the results of performance evaluation of the sample surface. In Table 1, the average molecular weight of the perfluoropolyether group is shown for Compounds 1 and 2 and the molecular weight of the compound is shown for Compound 3. Further, in Table 2, the items “before” and “after” show the test results before and after the sample surface was washed with ethanol, respectively.

[0048]

[Table 1]

[0049]

[Table 2]

As is clear from Tables 1 and 2, the average molecular weight 2
000 or more, weight average molecular weight Mw and number average molecular weight Mn
Experimental Examples 1 and 2 in which the surface treatment of the glass plate was performed using an alkoxysilane compound having a perfluoropolyether group having a ratio Mw / Mn of 1.2 or less, were excellent in stain resistance, water and oil repellency, It shows that it has good surface slipperiness, and has excellent durability against abrasion and the like and chemical stability against solvents and the like. On the other hand, Comparative Example 1 is inferior in abrasion resistance, water / oil repellency and solvent resistance.

(Experimental example 3) <Substrate> As a transparent substrate made of plastic, the thickness is 100 μm.
m transparent polyethylene terephthalate (PET) film was used. One side of this PET film has been previously subjected to a hard coat treatment to secure the surface hardness, and ITO is pre-deposited to a thickness of 120 nm as an antireflection film by a vacuum vapor deposition method on the PET film. S
It was formed by evaporating iO ₂ to a thickness of 70 nm. Incidentally, the hard coat treatment here is generally applied acrylic cross-linkable resin raw material, cross-linked and cured by ultraviolet rays or electron beams, silicon-based, melamine-based, epoxy-based resin raw material is applied, It is performed by heat curing.

<Preparation of coating composition and surface treatment> 2 parts of the alkoxysilane compound synthesized from the compound 1 was mixed with hydrofluoropolyether having a boiling point of 130 ° C. (manufactured by Ausimont Co., trade name H-GALDEN) fluorinated solvent 200. Part, and 0.08 part of phosphoric acid perfluoropolyether ester was further added to form a uniform solution, which was then filtered with a membrane filter to obtain a coating composition. The coating composition was dip-coated on the surface of the PET film at a pulling rate of 7 cm / min, and then dried at 70 ° C. for 1 hour to form a treated film.

<Performance Evaluation> The performance of the surface of the sample surface-treated as described above was evaluated by conducting a test according to the following method. (A) Contamination resistance 5 ml of tap water was dropped on the surface of the sample, and the sample was allowed to stand for 48 hours in a room temperature atmosphere. After that, the remaining state of scale was observed when it was wiped with a cloth. When the scale could be removed, it was marked with ◯, when some scale remained, it was marked with Δ, and when it could not be removed, it was marked with x. (B) Surface slipperiness When a sample surface was scratched with a pencil, the degree of catching was evaluated. The judgment method was ◯ when it was not scratched at all, Δ when it was strong, and X when it was weak. (C) Abrasion resistance After the surface of the sample was rubbed 30 times under the load of 200 g of steel wool # 0000, it was evaluated whether or not it was scratched. The evaluation method was ◯ when no scratches were made, Δ when fine scratches were made, and X when significantly scratched. (D) Adhesion resistance to hand stains The surface of the sample was visually evaluated for how difficult it is to get hand stains on it. The judgment method was ◯ when it was not noticeable even when it was attached, Δ when it was attached but could be easily removed, and X when it was noticeable. (E) Water and oil repellency It was evaluated by the contact angle of water and methylene iodide (CH ₂ I ₂ ). The contact angle is measured by CA-XE manufactured by Kyowa Interface Science Co., Ltd.
It was done using a mold. (F) Solvent resistance After cleaning the surface of the sample with ethanol, the above performance test was performed again to evaluate the solvent resistance.

(Experimental Example 4) Compound 2 synthesized in Experimental Example 2
A coating composition was prepared and the PET film was surface-treated in the same manner as in Experimental Example 3 except that (an average molecular weight of 2000 and Mw / Mn of 1.2 or less) was used.
The performance of the surface of the obtained sample was evaluated.

(Experimental Examples 5 and 6) Experimental Examples 5 and 6 were carried out in the same manner as in Experimental Examples 3 and 4 except that the phosphoric acid perfluoropolyether ester catalyst was removed in the preparation of the coating compositions of Experimental Examples 3 and 4. , 6 coating compositions were prepared and the surface treatment of each PET film was performed, and the performance of the sample surface obtained was evaluated.

(Comparative Example 2) A sample in which the surface of the PET film was not surface-treated with the coating composition was prepared and the surface performance was evaluated as Comparative Example 2.

Table 3 shows the performance evaluation results of the sample surfaces of Experimental Examples 3 to 6 and Comparative Example 2. In Table 3, the items “before” and “after” show the test results before and after the sample surface was washed with ethanol, respectively.

[0058]

[Table 3]

As is clear from Table 3, the average molecular weight is 20
Alkoxysilane compounds having a perfluoropolyether group having a ratio Mw / Mn of weight average molecular weight Mw to number average molecular weight Mn of 1.2 or less of 00, a fluorinated hydrocarbon solvent and a perfluoropolyether ester phosphate catalyst Experimental Examples 3 and 4 in which the surface treatment of the PET film was performed using the coating composition consisting of, were excellent in stain resistance, anti-stick property, water and oil repellency, and had good surface slipperiness.
Furthermore, it is shown that it has excellent durability against abrasion and the like and chemical stability against solvents and the like. On the other hand, in Experimental Examples 5 and 6 in which no catalyst was used, general deterioration of properties such as surface slipperiness, abrasion resistance, water / oil repellency and solvent resistance was observed, and in particular, anti-sticking property was It turns out to be inferior. On the other hand, Comparative Example 2 in which the surface treatment of the PET film is not performed does not meet all the requirements.

(Experimental Examples 7 to 10) In Experimental Example 3, in the surface treatment of Experimental Example 3, except that the drying temperature condition of the treated film was changed from 70 ° C. to 30 ° C., 50 ° C., 100 ° C. and 150 ° C., respectively. Similarly, each sample obtained by subjecting the PET film to the surface treatment was prepared, and the surface performance was evaluated.

(Experimental Examples 11 to 14) In Experimental Example 5, in the surface treatment of Experimental Example 5, the drying temperature condition of the treated film was changed from 70 ° C. to 30 ° C., 50 ° C., 100 ° C. and 150 ° C., respectively. Similarly, each sample obtained by subjecting the PET film to the surface treatment was prepared, and the surface performance was evaluated.

Experimental Examples 7 to 10 and Experimental Examples 11 to 14
Table 4 and Table 5 show the performance evaluation results of the sample surface of
Shown in. For reference, the evaluation results of Experimental Example 3 are shown in Table 4.
Table 5 also shows the evaluation results of Experimental Example 5.

[0063]

[Table 4]

[0064]

[Table 5]

As is clear from Table 4, the sample formed with the coating composition containing the catalyst had good surface properties (anti-stick property, abrasion resistance, water repellency) even when treated at a temperature near room temperature. It is recognized that oil repellency) can be obtained. The stain resistance and surface slipperiness were also good results. Good results can be obtained even if the heat treatment temperature is 70 ° C or higher, but 100
When the temperature is higher than 0 ° C, heat stress is applied to the treated film, which causes film deformation and film cracking, which is not preferable. Further, when the heat capacity of the substrate is large, it is not preferable from the viewpoints that it takes time under high temperature heating conditions and that the heat source is selected.

On the other hand, as shown in Table 5, in the case of the sample formed with the coating composition without a catalyst, in the temperature treatment range from near room temperature to 100 ° C., anti-sticking property, abrasion resistance and water repellency were obtained. The oil repellency was not sufficiently obtained, and the surface characteristics were cleared by the 150 ° C. treatment. However, since the treatment temperature is high, deformation due to heat stress is observed on the surface film, and the appearance is not sufficient.

[0067]

As described above, according to the inventions of claims 1 to 7, an alkoxysilane compound having a high molecular weight perfluoropolyether group is used as an antifouling surface treatment agent and an antifouling surface treatment composition. By containing,
It is possible to form a treated film having excellent water repellency, good surface slipperiness, durability against abrasion, etc., and excellent chemical stability against solvents etc. on a substrate.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an embodiment treated with an antifouling surface treatment agent of the present invention.

FIG. 2 is an infrared absorption spectrum of the alkoxysilane compound synthesized in Experimental Example 1.

[Explanation of symbols]

1 ... Substrate, 2 ... Treatment film

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 183/12 C09D 183/12 (72) Inventor Hirofumi Kondo 6-735 Kitashinagawa, Shinagawa-ku, Tokyo F term in Sony Corporation (reference) 4G059 AA01 AC22 FA05 FA22 FA27 FB05 4J005 BD05 BD06 BD08 4J038 DF021 GA15 HA096 HA176 HA336 HA376 HA416 HA476 JA11 JA34 JA37 JC24 KA06 KA14 MA07 MA09 MA14 NA05 NA07 NA11

Claims (7)

[Claims] 1. In an antifouling surface treatment agent containing an alkoxysilane compound represented by the following general formula (1), the average molecular weight of the perfluoropolyether group of the alkoxysilane compound is in the range of 2,000 to 10,000. A characteristic antifouling surface treatment agent. [Chemical 1] 2. The antifouling surface treating agent according to claim 1, wherein the perfluoropolyether group has a molecular weight distribution such that the ratio of weight average molecular weight / number average molecular weight is 1.2 or less. 3. The antifouling surface treating agent according to claim 1, wherein the perfluoropolyether group is represented by the following general formula (2). [Chemical 2] 4. The antifouling surface treating agent according to claim 1, wherein the alkoxysilane compound is dissolved in a fluorinated hydrocarbon solvent. 5. The concentration of the alkoxysilane compound is 0.01 to 10% by weight.
The antifouling surface treatment agent described. 6. An antifouling surface treatment composition comprising an alkoxysilane compound represented by the following general formula (1) and a fluorinated hydrocarbon solvent, which comprises a perfluoropolyether group of the alkoxysilane compound. Average molecular weight is 200
A composition for antifouling surface treatment, which is in the range of 0 to 10,000. [Chemical 3] 7. The antifouling surface treatment composition is selected from the group consisting of acids, bases, phosphates, and β-diketones.
The antifouling surface-treating composition according to claim 6, which contains one kind or two or more kinds of catalysts.