SLIDING AGENT AND ARTICLE COATED WITH COATING FILM FORMED THEREFROM

Abstract

A sliding agent includes: a graft polymer obtained by copolymerizing an organic solvent-soluble fluoropolymer having radical polymerizability, a one-terminal radical-polymerizable polysiloxane, and a non-reactive radical-polymerizable methacrylate-based monomer; a one-terminal reactive silicone oil; a hardener; and an organic solvent, and the sliding agent can improve transparency of coating film formed from the sliding agent and durability that can withstand a long-term use, while excellent sliding property of the coating film is maintained.

Claims

1. A sliding agent comprising: a graft polymer obtained by copolymerizing an organic solvent-soluble fluoropolymer having radical polymerizability, a one-terminal radical-polymerizable polysiloxane, and a non-reactive radical-polymerizable methacrylate-based monomer; a one-terminal reactive silicone oil; a hardener; and an organic solvent.

2. The sliding agent according to claim 1, wherein the one-terminal reactive silicone oil is 1 to 10 parts by mass relative to 100 parts by mass of the graft polymer.

3. The sliding agent according to claim 1, wherein, among all organic solvents comprised in the sliding agent, the proportion of a non-polar solvent having a relative permittivity of 3 or less is 10% by volume or greater.

4. An article having a coating film formed by the sliding agent according to claim 1 on its surface.

5. The article according to claim 4, wherein the thickness of the coating film is 3 to 20 μm.

6. The article according to claim 4, wherein the difference between a haze value of a substrate alone before application of the sliding agent and a haze value of the substrate after application of the sliding agent is 0.1 to 1%.

7. The article according to claim 4, wherein a ultra micro indentation hardness is 0.15 GPa or less when a maximum indentation load on the coating film is 1 mN.

8. The article according to claim 4, wherein, when sliding angles of 10 μL water are measured before and after an abrasion treatment, which is a treatment of reciprocating a non-woven fabric along the surface of the coating film for 1000 times under a condition of a load: 250 g/cm.sup.2, a moving distance: 20 mm, and a moving velocity: 600 mm/min, the difference between the sliding angles before and after the abrasion treatment is 30 degrees or less.

9. The article according to claim 4, wherein the substrate coated with the coating film is a transparent glass.

10. The article according to claim 4, wherein the article coated with the coating film is any one of solar panels, window glasses, traffic mirrors, glasses for agricultural houses, glasses for outdoor signboards and glass bottles.

11. An article having a coating film formed by the sliding agent according to claim 2 on its surface.

12. The article according to claim 11, wherein the thickness of the coating film is 3 to 20 μm.

13. The article according to claim 11, wherein the difference between a haze value of a substrate alone before application of the sliding agent and a haze value of the substrate after application of the sliding agent is 0.1 to 1%.

14. The article according to claim 11, wherein a ultra micro indentation hardness is 0.15 GPa or less when a maximum indentation load on the coating film is 1 mN.

15. The article according to claim 11, wherein, when sliding angles of 10 μL water are measured before and after an abrasion treatment, which is a treatment of reciprocating a non-woven fabric along the surface of the coating film for 1000 times under a condition of a load: 250 g/cm.sup.2, a moving distance: 20 mm, and a moving velocity: 600 mm/min, the difference between the sliding angles before and after the abrasion treatment is 30 degrees or less.

16. The article according to claim 11, wherein the substrate coated with the coating film is a transparent glass.

17. The article according to claim 11, wherein the article coated with the coating film is any one of solar panels, window glasses, traffic mirrors, glasses for agricultural houses, glasses for outdoor signboards and glass bottles.

18. An article having a coating film formed by the sliding agent according to claim 3 on its surface.

19. The article according to claim 18, wherein the thickness of the coating film is 3 to 20 μm.

20. The article according to claim 18, wherein the difference between a haze value of a substrate alone before application of the sliding agent and a haze value of the substrate after application of the sliding agent is 0.1 to 1%.

21. The article according to claim 18, wherein a ultra micro indentation hardness is 0.15 GPa or less when a maximum indentation load on the coating film is 1 mN.

22. The article according to claim 18, wherein, when sliding angles of 10 μL water are measured before and after an abrasion treatment, which is a treatment of reciprocating a non-woven fabric along the surface of the coating film for 1000 times under a condition of a load: 250 g/cm.sup.2, a moving distance: 20 mm, and a moving velocity: 600 mm/min, the difference between the sliding angles before and after the abrasion treatment is 30 degrees or less.

23. The article according to claim 18, wherein the substrate coated with the coating film is a transparent glass.

24. The article according to claim 18, wherein the article coated with the coating film is any one of solar panels, window glasses, traffic mirrors, glasses for agricultural houses, glasses for outdoor signboards and glass bottles.

Description

EXAMPLE 1

[0024] Hereinbelow, the present invention will be described based on examples; however, the present invention is not limited to the contents of these examples.

[0025] Table 1 is a formulation table of the sliding agent used for each specimen.

TABLE-US-00001 TABLE 1 One-terminal Film reactive thickness Base resin silicone oil Hardener Organic solvent (μm) Example 1 100 pts. mass 7 pts. mass Hexamethylene Aromatic 8.7 diisocyanate hydrocarbon solvent 50 pts. mass 38 pts. mass Comparative 100 pts. mass None Hexamethylene Aromatic 8.3 example 1 diisocyanate hydrocarbon solvent 50 pts. mass 38 pts. mass Comparative 100 pts. mass 7 pts. mass Hexamethylene Butyl acetate 10.1 example 2 diisocyanate 100 pts. mass 32 pts. mass Comparative 100 pts. mass 7 pts. mass Hexamethylene Aromatic 2.6 example 3 diisocyanate hydrocarbon solvent 50 pts. mass 38 pts. mass Comparative 100 pts. mass 7 pts. Mass Melamine resin Butyl acetate 8.0 example 4 38 pts. Mass 100 pts. mass

Example 1

[0026] In Example 1, the graft polymer obtained by copolymerizing the organic-solvent soluble fluorocarbon polymer having radical polymerizability, the one-terminal radical-polymerizable polysiloxane, and the non-reactive radical-polymerizable methacrylate-based monomer was used as the base resin, the one-terminal reactive silicone oil was used as the silicone oil, and hexamethylene diisocyanate was used as the hardener.

[0027] Moreover, other than the organic solvents included in the base resin and the hardener, an aromatic hydrocarbon solvent (relative permittivity: 1.8; boiling point: 150° C. or higher) was used as the organic solvent, and the sliding agent comprising 100 parts by mass of the base resin, 7 parts by mass of the silicone oil, 50 parts by mass of the hardener, and 38 parts by mass of the organic solvent was produced.

[0028] This sliding agent was applied to a stainless substrate by a wire bar No. 18 and subjected to a dry heating treatment at 200° C. for one hour to produce the coating film.

[0029] The organic solvents included in the sliding agent of Example 1 are shown in Table 2.

TABLE-US-00002 TABLE 2 Relative Parts Specific Mixed Organic solvent permittivity by mass gravity Volume volume ratio Butyl acetate 5.0 41.3 0.88 46.8 35.8 n-Butanol 17.5 6.2 0.81 7.7 5.9 IPA 19.9 2.8 0.79 3.5 2.7 Methanol 32.7 1.6 0.79 2.0 1.5 Aromatic 1.8 38.0 0.87 43.7 33.4 hydrocarbon Xylene 2.3 23.2 0.86 27.0 20.6

[0030] Accordingly, among all organic solvents included in the sliding agent of Example 1, those that had a relative permittivity of 3 or less were aromatic hydrocarbon and xylene, and the total thereof was 54.0% in the mixed volume ratio.

Comparative Example 1

[0031] As Comparative example 1, sliding agents and coating films were produced similarly to Example 1 except that the silicone oil was not added. The organic solvents included in the sliding agent of Comparative example 1 are shown in Table 3. Since the silicone oil does not contain volatile components, the condition of the organic solvents is the same as in Example 1.

TABLE-US-00003 TABLE 3 Relative Parts Specific Mixed Organic solvent permittivity by mass gravity Volume volume ratio Butyl acetate 5.0 41.3 0.88 46.8 35.8 n-Butanol 17.5 6.2 0.81 7.7 5.9 IPA 19.9 2.8 0.79 3.5 2.7 Methanol 32.7 1.6 0.79 2.0 1.5 Aromatic 1.8 38.0 0.87 43.7 33.4 hydrocarbon Xylene 2.3 23.2 0.86 27.0 20.6

[0032] Accordingly, among all organic solvents included in the sliding agents of Comparative example 1, those that had the relative permittivity of 3 or less were aromatic hydrocarbon and xylene, and the total thereof was 54.0% in the mixed volume ratio.

Comparative Example 2

[0033] As Comparative example 2, sliding agents and coatings film were produced similarly to Example 1 except that 100 parts by mass of butyl acetate was used as the organic solvent. The organic solvents included in the sliding agent of Comparative example 2 are shown in Table 4.

TABLE-US-00004 TABLE 4 Relative Parts Specific Mixed Organic solvent permittivity by mass gravity Volume volume ratio Butyl acetate 5.0 149.3 0.88 169.4 91.2 IPA 19.9 2.8 0.79 3.5 1.9 Xylene 2.3 11.0 0.86 12.8 6.9

[0034] Accordingly, among all organic solvents included in the sliding agents of Comparative example 2, one that had the relative permittivity of 3 or less was xylene, and the value thereof was 6.9% in mixed volume ratio.

Comparative Example 3

[0035] As Comparative example 3, sliding agents and coating films were prepared similarly to Example 1 except that the wire bar No. 4 was used. The organic solvents included in the sliding agents of Comparative example 3 are the same as in Example 1.

Comparative Example 4

[0036] As Comparative example 4, sliding agents and coating films were prepared similarly to Example 1 except that 38 parts by mass of melamine resin was used as the hardener and 100 parts by mass of butyl acetate was used as the organic solvent. The organic solvents included in the sliding agents of Comparative example 4 are shown in Table 5.

TABLE-US-00005 TABLE 5 Relative Parts Specific Mixed Organic solvent permittivity by mass gravity Volume volume ratio Butyl acetate 5.0 141.3 0.88 160.3 82.2 n-Butanol 17.5 10.5 0.81 13.0 6.6 IPA 19.9 2.8 0.79 3.5 1.8 Methanol 32.7 1.5 0.79 1.9 1.0 Xylene 2.3 14.0 0.86 16.3 8.3

[0037] Accordingly, among all organic solvents comprised in the sliding agents of Comparative example 4, one that had the relative permittivity of 3 or less was xylene, and the value thereof was 8.3% in mixed volume ratio.

[0038] <Evaluation Items>

[0039] The coating films were respectively evaluated on the following items.

[0040] Sliding angle of water: 10 μL of pure water was put onto the coating film, and the substrate was tilted to measure the angle when pure water slid. When pure water did not slide at inclination of 90 degrees, it was determined as “x”.

[0041] Sliding angle of oil: 10 μL of an oleic acid was put onto the coating film, and the substrate was tilted to measure the angle when the oleic acid slid. When the oleic acid did not slide at inclination of 90 degrees, it was determined as “x”.

[0042] Transparency of the coating film: The coating film was visually Observed, and it was determined as “transparent” when the substrate could be observed, and “not transparent” when the substrate could not be observed.

[0043] Abrasion test: 1 cm×1 cm of a non-woven fabric was adhered to a planar indenter of a metal plate. Next, the non-woven fabric was superimposed onto the coating film of the specimen, and the surface of the coating film was abrased by the non-woven fabric with a load of 250 g. Specifically, the non-woven fabric of the metal plate was reciprocated along the surface of the coating film for 1000 times under the condition of a moving distance: 20 mm and a moving velocity: 600 mm/min.

[0044] Hardness: A ultra micro indentation hardness test was performed. Specifically, a hardness (in accordance with Z 2255) of when the indenter was indented to the coating film with the following condition was measured.

[0045] Maximum indentation load: 1 mN

[0046] Indenter: Berkovich indenter (diamond, an apex angle of)115°)

[0047] Loading time: 30 seconds

[0048] Retaining time: 10 seconds

[0049] The evaluation results of them are shown in Table 6.

TABLE-US-00006 TABLE 6 Sliding angle of water (degrees) Difference between Sliding Hardness (Gpa) After 1000 initial value and angle After 1000 Transparency times of after 1000 times of oil times of Visual Initial abrasion test of abrasion test Initial Initial abrasion test observation Example 1 29.5 48.8 19.3 13.5 0.113 0.117 Transparent Comparative 28.2 64.8 36.6 — 0.169 0.163 Transparent example 1 Comparative 21.2 55.0 33.8 14.0 0.158 0.158 Not example 2 transparent Comparative 31.3 x — — — — Transparent example 3 Comparative 29.7 — — 12.2 — — Not example 4 transparent

EXAMPLE 2

[0050] In Example 2, it was produced similarly to Example 1 other than a transparent glass was used as the substrate to which the sliding agent was applied.

Comparative Example 5

[0051] In Comparative example 5, the transparent glass substrate alone to which the sliding agent was not applied was used.

[0052] <Evaluation Items>

[0053] Each coating film was evaluated on the sliding angle of water and the sliding angle of oil similarly to Example 1.

[0054] Transparency of the coating film: A turbidity (haze value) of the coating film was measured with a haze meter “NDH 5000” (manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.).

[0055] The evaluation results of them are shown in Table 7.

TABLE-US-00007 TABLE 7 Sliding angle of Sliding angle of Transparency water (degrees) oil (degrees) haze (%) Example 2 30.1 17.5 0.33 Comparative x x 0.29 example 5

[0056] The evaluation results of Table 6 shows that, in Example 1, the coating film was transparent, the sliding angle of water was initially 29.5 degrees, the sliding angle after 1000 times of the abrasion test was 48.8 degrees, the difference between before and after the test was 19.3 degrees, and thus the abrasion property was good.

[0057] Since the silicone oil was not added in Comparative example 1, the sliding angle of water was initially 28.2 degrees and became 64.8 degrees after 1000 times of the abrasion test, the difference before and after the test was 36.6 degrees, and thus the abrasion property was poor.

[0058] Since butyl acetate was used as the organic solvent in Comparative example 2, the mixed volume ratio of the organic solvent having the relative permittivity of 3 or less among all organic solvents comprised in the sliding agent became low, 6.9%, and thus the coating film was not transparent. Hardness was harder than Example 1, the abrasion property was and it was easily worn away.

[0059] Since the film thickness was thin, 2.6 μm, in Comparative example 3, the sliding property of water deteriorated such that water did not fall down even at 90 degrees inclination after 1000 times of the abrasion test.

[0060] Since melamine resin was used as the hardener and butyl acetate was used as the organic solvent in Comparative example 4, the mixed volume ratio of the organic solvent having the relative permittivity of 3 or less among all organic solvents comprised in the sliding agent was low, 8.3%, and thus the coating film was not transparent.

[0061] As stated above, it was found that the coating film of Example 1 is transparent, has a good sliding angle, is soft, and can withstand a long-term use.

[0062] Moreover, the evaluation results of Table 7 shows that Example 2 of which the sliding agent was applied to a glass achieved the sliding angle of water of 30.1 degrees and the sliding angle of oil of 17.5 degrees. In Comparative example 5, which is the substrate alone not applied with the sliding agent, the results of the sliding angles of water and oil were both “x (did not fall down at 90 degrees inclination)”. Therefore, the result of Example 2 may be regarded as a better result. Moreover, the result of measuring transparency with the haze meter was 0.29% in the glass substrate alone, and 0.33% in those that the sliding agent was applied thereto. The difference between the haze value of the glass substrate alone before the sliding agent was applied and the haze value after the sliding agent was applied was 0.04%. From these results, it was found that the transparency almost the same as that of the glass substrate alone could be achieved.

INDUSTRIAL APPLICABILITY

[0063] The sliding agent of the present invention can be applied as materials for providing sliding property to articles in various industrial fields such as solar panels, window glasses, traffic mirrors, glasses for agricultural houses, glasses for outdoor signboards, and glass bottles, and can form a coating film that is transparent and has durability that can he used for a long term, while excellent sliding property is maintained.