JP2800786B2 - Composition exhibiting water repellency and antifouling property at ordinary temperature, water repellent and antifouling substrate, and treatment method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to compositions that provide excellent coating water repellency, antifouling, glass, about the possible applied at the beginning various substrates and plastics technology. Application and development of a wide range of I Ri each base stocks to the invention becomes possible.

[0002]

BACKGROUND OF THE INVENTION various substrates, especially transparent substrate is used state is not a multi-surface that is in direct contact with the human eye. The transparency of the material is often lost due to the adsorption of dust and oil stains on the surface , or the bad influence of water on the surface . Therefore , there are many demands for improving the water repellency or antifouling property of the transparent substrate.

[0003] product life, such as plastic or glass, appearance, often place water itself, or, Ri by the action of foreign particles that are involved in water, deterioration in response to the evil influence. Such adverse effects include damage to appearance, dirt, color, corrosion, changes in electrical properties, loss of gloss, and the like. Some of the proposals in order to solve these problems have been made.

[0004] However, it is dissatisfaction in a variety of reasons in the currently available material. That is, it has drawbacks such as lack of durability of the effect and resistance to solvents and cleaning agents. Further, scratch resistance was low, disadvantage that the surface when treated like glass thus rather easy scratched Kuna' also had (such as JP 50-15473).

[0005] In addition, in the case after the coating cloth firing require more,
In some cases, the process is difficult, and the cost is disadvantageous.

Furthermore , above all, the water repellency and antifouling properties obtained from these materials were unsatisfactory, and their usable fields were limited.

[0007]

The object of the present invention is to solve the above are working to solve the drawbacks of conventional materials are perforated, grantable composition excellent water repellency and antifouling property against a wide variety of substrates To provide things.

[0008]

That SUMMARY OF THE INVENTION The present invention is a compound represented by the following formula (A), and a set <br/> Narubutsu you contains a solvent, wherein for the composition the total amount (A) Represented by
Characterized in that the compound amount is 0.1 to 30% by weight.
A water stain resistant composition, and treating and drying the composition on a substrate surface.
Water-repellent and stain-proof substrate obtained by drying, and treatment of the composition
That provides a physical way.

[0009]

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Rf ¹ : carbon optionally containing an etheric oxygen atom
An organic group containing a perfluoroalkyl group, having 8 to 16. R ^{1 represents a} hydrogen atom or an organic group having 1 to 16 carbon atoms . a : 1 or 2. b : 0 or 1 . However, 1 ≦ a + b ≦ 2 .

Hereinafter, the components will be described in detail.

The composition of the present invention is represented by the formula (A)
The compound is an essential component for exhibiting antifouling property and water repellency. A compound represented by the following formula (A) is combined with the component (A)
Say. The same applies to other compounds.

The component (A) includes, for example, the following compounds. However , RF 'is a perfluorocarbon having 8 to 16 carbon atoms.
An alkyl group, R is a substituted or unsubstituted monovalent hydrocarbon group , and m is an integer of 1 or more .

[0014]

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In the composition of the present invention, the component (A) is essential.
However, even if the component (B) is contained together with the component (A)
No problem.

[0016]

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Rf ² and Rf ^{3 each} independently represent an organic group containing a perfluoroalkyl group which may contain an etheric oxygen atom. R ² and R ³ independently represent a hydrogen atom or an organic group having 1 to 16 carbon atoms. c, d: independently , 0 , 1 or 2 and 0 ≦ c + d ≦
2. e, g: independently 0 , 1 or 2 and 0 ≦ e + g ≦
2. Y: a divalent organic group (however, in the case of c + e = 0, a divalent organic group containing a perfluoroalkylene group which may contain an etheric oxygen atom).

As the component (B), for example, the following compounds
There is. Wherein n is an integer of 1 to 16, R is substituted or
Unsubstituted monovalent hydrocarbon group, RF is C ₂ H ₄ CF ₃ , C ₂ H ₄ (CF ₂ ) _n
CF ₃ , C ₂ H ₄ OCOCF _{3 and} other perfluoroalkyl group-containing
Organic group.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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The addition amount of the component ( B) can be arbitrarily selected according to the purpose.

Addition of other components and additives to the components (A) and (B) according to the purpose can be used without any problem. By adding other components and additives, the application range of the composition is greatly widened. There Ru. The following can be considered as other components and additives.

There is a compound represented by the following formula (C) for increasing the durability and durability of the treatment effect. Where R ³ ,
R ⁴ is <br/> independently a hydrogen atom or number 1-16 organic group carbon. h and i are each independently 0, 1, or 2;
≤h + i≤3.

[0030]

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Examples of the component (C) include the following compounds.

[0032]

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[0033]

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In addition, it is also possible to add ultrafine particles of various metal oxides and various resins. In addition, processing (workability)
It is also possible to use surfactants to increase the viscosity.

The above components are used after being diluted with a solvent.
You. Considering the economic efficiency and the stability of the composition , the formula (A)
The compound weights expressed are relative to the total weight of the composition . 1 to
30% by weight . Various solvents can be used as diluents
That although those having a reactive -OH group (A), (B)
Since it reacts with the isocyanate group of the component, it is not desirable because of the stability of the liquid.

In the processing, no special pre-processing is required, but it can be performed according to the purpose. Hydrofluoric acid,
It is possible to perform an acid treatment with hydrochloric acid or the like, an alkali treatment with sodium hydroxide, potassium hydroxide or the like, or a discharge treatment such as a plasma treatment.

There is no particular limitation on the processing method.
What is necessary is just to select according to the objective.

Dip coating, spin coating, spray coating, flow coating, roller coating and the like can be applied. Further, the composition of the present invention is applied to various substrates, but exhibits excellent water repellency and soil resistance when dried at room temperature, may be fired in order to more firmly adhere to the substrate . In the case of baking, at a temperature of 50 to 500 ° C. for 5 minutes to 120 in consideration of the heat resistance of the base material.
An excellent treatment effect can be expected if baking is performed separately.

The thickness of the treated layer can be controlled by the composition, the solvent, the weight ratio of the composition to the total weight, the coating conditions, the firing conditions, and the like, and may be controlled according to the purpose. For example, the composition of the present invention has a low refractive index because it is a fluorine- containing component. Therefore, low reflectivity can be exhibited, and if this effect is expected, the thickness of the treatment layer may be controlled to a thickness at which optical interference occurs. Further, antifouling properties, the thickness of the treated layer in theory to water repellency is sufficient if more monomolecular layers, which in taking into account the economic effects, the thickness of the treated layer 2μ or less Is desirable. Furthermore, it can be expected that the friction on the surface is reduced by the fluorine component contained in the composition of the present invention, and the scratch resistance on the surface of the substrate is significantly improved.

[0040]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In the following, Examples 1 to 7 and Examples 9 to 21
Is an example of the present invention, and Example 8 is a reference example. Also,
There next <br/> Families Ride the evaluation method of the molded body used in Example.

(1) Confirmation of Antifouling Effect (1-1) The contact angle of hexadecane was measured. (1-2) After the fingerprint of the hand was adhered to the treated surface, it was wiped with a cotton cloth for 20 reciprocations and the appearance was inspected and evaluated according to the following criteria. A. Oil dirt can be completely wiped off, B. C. A little oil stain remains. Significant oil stains remain.

[0042] (2) The contact angle was measured for confirmation (2-1) Water of the effect of water repellency. (2-2) The test was performed by spraying tap water from a nozzle held at a distance of 20 cm from the sample. Appropriate time to stop the spray after applying a spray of water to the process the entire surface of the test sample, inspect the water droplets remaining in the sample with the naked eye was determined by the following evaluation criteria. A. No water droplets remain on the sample surface, B. B. Some water droplets remain on the sample surface. D. A considerable amount of water remains on the sample surface. Water spreads on the sample surface.

(3) Evaluation of Durability A sample was placed in an accelerated testing machine at a humidity of 90% and a temperature of 50 ° C.
After standing for a month, the effect of antifouling property and water repellency was confirmed.

[0044] Further, the components used in the following Examples the following compounds.

[0045]

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( Example 1, Comparative Example 1) 10.0 g of the component (A-1) and 10.0 g of the component (B-1) were mixed in a three-necked flask equipped with a stirrer. Further, 1980 g of toluene was added. A glass plate ( 10 cm × 10 cm, thickness 5 mm) washed in advance was immersed in the composition obtained as described above, and then pulled up at a speed of 6 cm / min to obtain a transparent molded body. Table 1 shows the results of evaluating the transparent molded body obtained as described above. As a comparative example, an untreated glass was evaluated.

[0047] (Example 2) In Example 1 (B-1) in place of Ingredient 10 .0g (B-
2) The same procedure was performed except that 10.0 g of the component was used. Table 1 shows the results
It was shown to.

[0048] (Example 3) In Example 1 (A-1) in place of Ingredient 10 .0g (A-
2) The same procedure was performed except that 10.0 g of the component was used. Table 1 shows the results
It was shown to.

[0049]

[Table 1]

( Examples 4 to 10 and Comparative Examples 2 to 3) Compositions were prepared using only the compounds of the types shown in Table 2 and the amounts thereof, and transparent moldings were obtained in the same manner as in Example 1 except for the above. Table 3 shows the evaluation results.

[0051]

[Table 2]

[0052]

[Table 3]

[0053] (e.g. 10) Toru Meisei form obtained in Example 1 was immersed for 24 hours in chemicals shown in Table 4. After immersion, washing was performed to confirm the effects of water repellency and oil repellency. The results are shown in Table 4.

[0054]

[Table 4]

( Example 11) The transparent molded article obtained in Example 1 was subjected to a Taber abrasion tester, and the change in haze value after rotation speed wear and the effects of stain resistance and water repellency shown in Table 5 were confirmed.

[0056]

[Table 5]

[0057] (Examples 12 to 14) Acrylic plate rather than a glass substrate in Example 1, a polycarbonate plate, except for using CR 39 plates was performed in the same manner to obtain shown to result in Table 6.

[0058] (Comparative Example 4-6) acrylic plate untreated as a comparative example in Example 12, a polycarbonate plate, the same also evaluated CR39 plate, shown in Table 6.

[0059]

[Table 6]

( Example 15) The same procedures as in Example 1 were carried out except that the glass substrate pretreated with a 2% aqueous HF solution for 1 min was used, and the results shown in Table 7 were obtained.

[0061]

[Table 7]

( Example 16, Comparative Example 7) The surface friction coefficient of the glass plate obtained in the same manner as in Example 1 was measured. In addition, the scratch resistance of the surface was evaluated and compared with an untreated glass plate. The evaluation of scratch resistance was performed as follows.

The surface was rubbed with SW (# 0000 manufactured by Bonstar), and the degree of scratching was visually observed. The observation criteria with the naked eye are as follows. A. No scratches are seen. B. Some scratches are observed. C. Scratches quite severely. Table 8 shows the evaluation results.

[0064]

[Table 8]

( Examples 17 to 20) After applying the coating liquid in Example 1, 50, 100, 200, 400
The procedure was performed in the same manner as in Example 1 except that the sintering was carried out at ℃. Table 9 shows the evaluation results. Example 17: 50 ° C, Example 18: 100 ° C, Example 19: 200 ° C, Example 20: 400 ° C.

[0066]

[Table 9]

[0067] (Example 21) Another is performed in the same manner using an aluminum plate instead of the glass substrate in Example 1, was obtained shown to result in Table 10.

[0068] The same also evaluated untreated aluminum plate as a comparative example in (Comparative Example 8) Example 21, shown in Table 10.

[0069]

[Table 10]

(Comparative Example 9) In Example 1, the component (B-1) was replaced with (CH ₃ O) ₃ SiC ₂ H ₄ C ₈ F ₁₆ C ₂
H ₄ Si (OCH ₃ ) ₃ , wherein the component (A-1) is C ₉ F ₁₉ C ₂ H ₄ Si (OCH ₃ ) ₃
Addition to the was Tsu line as well. The results are shown in Table 11.

[0071]

[Table 11]

[0072]

As described in the examples, when the composition obtained by the present invention is applied to a substrate, it has the following characteristics. 1) Excellent water repellency and antifouling properties when applied at room temperature. 2) has excellent chemical resistance, further has sustained water repellency, antifouling effect, the semi-permanent that state be maintained. 3) No special pretreatment is required for a wide range of substrates,
Since the treatment can be performed continuously, the economic effect is high. 4) The friction on the substrate surface is reduced, and it has excellent scratch resistance that has never been seen before.

Since the composition of the present invention is applied to various base materials because of the above-mentioned characteristics, it can be applied to a region where the composition cannot be used conventionally.

Claims (5)

(57) [Claims] 1. A compound represented by the following formula (A), and soluble
Agent is a composition you containing the formula for the total amount of the composition
The amount of the compound represented by (A) is 0.1 to 30% by weight.
A water-repellent and antifouling composition comprising: Embedded image Rf ¹ represents an organic group containing a perfluoroalkyl group having 8 to 16 carbon atoms which may contain an etheric oxygen atom. R ^{1 represents a} hydrogen atom or an organic group having 1 to 16 carbon atoms. a: 1 or 2. b: 0 or 1. However, 1 ≦ a + b ≦ 2. 2. Rf ¹ in the formula (A) is C ₈ F ₁₇ C ₂
H ₄ - a is claim 1 repellant flood antifouling composition according. (3)Claims comprising a compound represented by the following formula (C):
3. The water-repellent and antifouling composition according to 1 or 2. (C) (R ^Three ) _h (R ^Four ) _i Si (NCO) _4-hi R ^Three , R ^Four : Independently a hydrogen atom or a group having 1 to 16 carbon atoms
Organic groups. h, i: 0, 1, or 2 independently. Where 0 ≦ h +
i ≦ 3. 4. The water-repellent and antifouling property according to claim 1, 2 or 3.
Water repellent and stain resistant obtained by treating and drying the composition on the substrate surface
Base material. 5. The water-repellent and antifouling property according to claim 1, 2 or 3.
Processing the composition on the substrate surface, characterized in Rukoto dried
Surface treatment method.