SURFACE TREATMENT AGENT

Abstract

A surface-treating agent including (A) a compound represented by the following formula (A1) or formula (A2), and (B) a compound represented by the following formula (B1) or formula (B2), and containing at least one of a compound represented by formula (A2) or a compound represented by formula (B2) as defined herein:

##STR00001##

Claims

1. A surface-treating agent comprising: (A) a compound represented by the following formula (A1): ##STR00017## wherein M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, or Zr, R.sup.1 is each independently a hydrogen atom or a C.sub.1-6 alkyl group, R.sup.4 is each independently a C.sub.1-3 alkyl group or a C.sub.1-3 alkoxy group, m is a valence of M, and n is 0 or more and equal to or less than the valence of M; or a compound represented by the following formula (A2): ##STR00018## wherein R.sup.2a is each independently at each occurrence a hydroxyl group or a hydrolyzable group, R.sup.3a is each independently at each occurrence a hydrogen atom or a monovalent organic group, na is each independently an integer of 1 to 3 for each SiR.sup.2a.sub.naR.sup.3a.sub.3-na unit, and R.sup.9a is each independently a single bond or a divalent group; and (B) a compound represented by the following formula (B1):
M.sup.b (OR.sup.1b).sub.q (R.sup.4b).sub.p-q   (B1) wherein M.sup.b is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, or Zr, R.sup.1b is each independently a hydrogen atom or a C.sub.1-6 alkyl group, R.sup.4b is a C.sub.1-30 alkyl group, a C.sub.1-30 oxyalkyl group, a C.sub.1-30 fluoroalkyl group, or a siloxane group, p is a valence of M.sup.b, and q is 1 or more and equal to or less than (the valence of M.sup.b-1); or a compound represented by the following formula (B2): ##STR00019## wherein R.sup.2b is each independently at each occurrence a hydroxyl group or a hydrolyzable group, R.sup.3b is each independently at each occurrence a hydrogen atom or a monovalent organic group, nb is each independently an integer of 1 to 3 for each SiR.sup.2b.sub.nbR.sup.3b.sub.3-nb unit, R.sup.9b is each independently a single bond or a divalent group, and R.sup.8 is a C.sub.1-30 alkyl group, a C.sub.1-30 oxyalkyl group, a C.sub.1-30 fluoroalkyl group, a siloxane-containing group, or a perfluoropolyether-containing group, the surface-treating agent comprising at least one of the compound represented by the formula (A2) or the compound represented by the formula (B2).

2. The surface-treating agent according to claim 1, wherein the compound represented by the formula (A1) is a metal alkoxide represented by the following formula (A1-1):
M(OR.sup.1).sub.n   (A1-1) wherein M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, or Zr, R.sup.1 is each independently a hydrogen atom or a C.sub.1-6 alkyl group, and n is a valence of M.

3. The surface-treating agent according to claim 1, wherein the compound represented by the formula (A1) is a metal alkoxide represented by the following formula (A1-2):
Si(OR.sup.1).sub.4   (A1-2) wherein R.sup.1 is each independently a hydrogen atom or a C.sub.1-6 alkyl group.

4. The surface-treating agent according to claim 1, comprising the compound represented by the formula (A2).

5. The surface-treating agent according to claim 1, comprising the compound represented by the formula (B2).

6. The surface-treating agent according to claim 1, comprising the compound represented by the formula (A2) and the compound represented by the formula (B2).

7. The surface-treating agent according to claim 1, comprising the compound represented by the formula (A2), the compound represented by the formula (B1), and the compound represented by the formula (B2).

8. The surface-treating agent according to claim 1, wherein na and nb are 3.

9. The surface-treating agent according to claim 1, wherein R.sup.4b is a C.sub.1-30 alkyl group.

10. The surface-treating agent according to claim 1, wherein R.sup.8 is a C.sub.1-30 alkyl group.

11. The surface-treating agent according to claim 1, wherein R.sup.9a is a C.sub.1-6 alkylene group.

12. The surface-treating agent according to claim 1, wherein R.sup.9b is a C.sub.1-6 alkylene group.

13. The surface-treating agent according to claim 1, wherein a molar ratio of the component (A) to the component (B) is 0.01-100:1.

14. The surface-treating agent according to claim 1, further comprising one or more other components selected from an organic solvent, water, and a catalyst.

15. An article comprising a substrate and a layer formed of the surface-treating agent according to claim 1 on the substrate.

Description

EXAMPLES

[0304] Below, the surface-treating agent of the present disclosure will now be described in the Examples, but the present disclosure is not limited to the following Examples.

[0305] The following compounds were prepared as components (A) and (B).

##STR00016##

Surface-Treating Agent Preparation 1

[0306] The compound (A1), the compound (A2), the compound (B1), and the compound (B2) were dissolved in ethanol in predetermined proportions so as to be 20 wt % in total, and 0.01 N hydrochloric acid was added to this solution in a mass ratio of 0.15 to prepare surface-treating agents 1 to 10. The proportions (molar ratios) of each compound is shown in Table 1 below.

TABLE-US-00001 TABLE 1 Molar ratio Compound Compound Compound Compound (A1) (A2) (B1) (B2) Surface-treating 7.5 2.5 1 0 agent 1 Surface-treating 5 5 1 0 agent 2 Surface-treating 2.5 7.5 1 0 agent 3 Surface-treating 0 10 1 0 agent 4 Surface-treating 10 0 0 1 agent 5 Surface-treating 0 10 0.75 0.25 agent 6 Surface-treating 0 10 0.5 0.5 agent 7 Surface-treating 0 10 0.25 0.75 agent 8 Surface-treating 0 10 0 1 agent 9 Surface-treating 10 0 1 0 agent 10

Surface-Treated Sample Preparation 1

[0307] A soda lime glass substrate was spin-coated with the surface-treating agents 1 to 10 prepared above (2000 rpm for 10 seconds) to form surface-treating layers, and thereby surface-treated samples 1 to 10 were obtained. The surface-treated samples 1 to 9 are Examples 1 to 9, and the surface-treated sample 10 is Comparative Example 1. The initial sliding angle and the sliding angle after UV irradiation of the resulting surface-treated samples 1 to 10 were evaluated. The results are shown in Table 2 below.

(Method for Measuring Sliding Angle)

[0308] Water was dripped from a microsyringe onto the surface-treating layer side of a horizontally placed surface-treated sample, and the droplet was observed while tilting the sample at a rate of 2° per second up to 90°. The sliding angle was determined when the droplet traveled 5 mm. The droplet volume was set to be 20 μL, and measurement was made.

Accelerated UV Resistance Test

[0309] The surface-treated samples 1 to 10 were subjected to an accelerated UV resistance test as follows. A UVB-313 lamp (manufactured by Q-Lab, an irradiance of 0.63 W/m.sup.2 at 310 nm) was used, the distance between the lamp and the surface-treating layer of the surface-treated samples was 5 cm, and the temperature of the plate on which the surface-treated samples were placed was 63° C. UVB irradiation was continuously performed, and the surface-treated samples were removed when measuring the sliding angle. Their changes were checked after 480 hours of irradiation.

TABLE-US-00002 TABLE 2 Sliding angle (°) Sliding angle (°) (After 480 hours (Initial) of UV irradiation) Example 1 Sample 1 16 37 Example 2 Sample 2 28 48 Example 3 Sample 3 24 45 Example 4 Sample 4 20 42 Example 5 Sample 5 19 35 Example 6 Sample 6 20 35 Example 7 Sample 7 24 41 Example 8 Sample 8 22 36 Example 9 Sample 9 16 33 Comparative Sample 10 10 >90 Example 1

Surface-Treating Agent Preparation 2

[0310] The compound (A2) and the compound (B1) were dissolved in ethanol in predetermined proportions so as to be 30 wt % in total. Then, 0.01 N hydrochloric acid was added to each of these solutions in a mass ratio of 0.15 to prepare surface-treating agents 11 to 17. The proportions (molar ratios) of each compound is shown in Table 3 below. The surface-treating agent 11 has a molar ratio (A2)/(B1) of 0, meaning that it contains the compound (B1) only.

Surface-Treated Sample Preparation 2 and Evaluation

[0311] The surface-treating agents 11 to 17 prepared above were used to prepare surface-treated samples 11 to 17 according to the method of the above surface-treated sample preparation 1. Concerning the resulting surface-treated samples 11 to 17, sliding angle measurement and an accelerated UV resistance test were performed in the same manner as above. The results are shown in Table 3 below. The surface-treated sample 11 is Comparative Example 2, and the surface-treated samples 12 to 17 are Examples 10 to 15.

TABLE-US-00003 TABLE 3 Sliding angle (°) (A2)/(B1) Sliding angle (°) (After 480 hours Molar ratio (Initial) of UV irradiation) Comparative Sample 11 0 25 >90 Example 2 Example 10 Sample 12 1 26 35 Example 11 Sample 13 5 19 39 Example 12 Sample 14 10 17 40 Example 13 Sample 15 20 18 42 Example 14 Sample 16 40 20 49 Example 15 Sample 17 50 22 51

Adhesion Test

[0312] Adhesion of each surface-treating agent to glass was evaluated by a cross-cut test. Specifically, 11 cuts reaching the substrate were made in the test surface with a cutter to create a grid of 100 squares with 1 mm intervals between the cuts, an adhesive tape was firmly applied to the grid, and the edge of the tape was pulled at a an angle of 45°. Concerning peeling of the coating, the grid after removal of the tape received a marker pen, and portions that were stained without repelling the marker ink were regarded as defective portions. Adhesion was numerically evaluated according to the following criteria. [0313] 10 points: No squares had peeling. [0314] 8 points: Slightly peeled at the intersections of the cuts, and the area of defective portions was within 5% of the total area of the squares. [0315] 6 points: Peeled on both sides and at the intersections of the cuts, and the area of defective portions was 5% or more and less than 15% of the total area of the squares. [0316] 4 points: Partially or entirely peeled along the cuts, and the area of defective portions was 15% or more and less than 35% of the total area of the squares. [0317] 2 points: Partially or entirely peeled along the cuts, and the area of defective portions was 35% or more and less than 65% of the total area of the squares. [0318] 0 points: The area of defective portions of the cuts was 65% or more of the total area of the squares.

TABLE-US-00004 TABLE 4 Number of Compound Compound Compound Compound defective (A1) (A2) (B1) (B2) portions Score Example 4 0 10 1 0 5/100 8 points Example 9 0 10 0 1 0/100 10 points Comparative 10 0 1 0 70/100 0 points Example 1

Evaluation of Surface Hardness

[0319] The surface hardness of each surface-treated sample was measured in accordance with ERICHSEN Hardness Test Pencil Model 318S (ISO1518). A table in which the results of this test are compared to approximate values of pencil hardness is as follows.

TABLE-US-00005 TABLE 5 318 Pencil hardness Test bar Approximate value 0.5N 2 H-3 H 1.0N 3 H 2.0N 3 H-4 H 4.0N 6 H-7 H

TABLE-US-00006 TABLE 6 Duration of Compound Compound Compound Compound hydrolysis (A1) (A2) (B1) (B2) (h) Example 4 0 10 1 0 6 18 24 Example 9 0 10 0 1 6 18 24 Comparative 10 0 1 0 6 Example 1 18 24 0.5 N 1.0 N 2.0 N 4.0 N Judgement Example 4 ◯ ◯ X 3 H ◯ ◯ X 3 H ◯ X X 2 H-3 H Example 9 ◯ ◯ ◯ X 5 H-6 H ◯ ◯ ◯ X 5 H-6 H ◯ X X 2 H-3 H Comparative X 1 H or less Example 1 X 1 H or less X 1 H or less ◯: Not damaged X: damaged

INDUSTRIAL APPLICABILITY

[0320] The surface-treating agent of the present disclosure can be suitably used in various applications.