SURFACE TREATMENT AGENT

Abstract

The present invention provides a compound represented by general formula (A1) or (A2):

R.sup.1(PE.sup.1-Y).sub.nPE.sup.2-X(SiR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m).sub.(A1)

(R.sup.c.sub.mR.sup.b.sub.lR.sup.a.sub.kSi).sub.X(PE.sup.1-Y).sub.nPE.sup.2-X(SiR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m).sub.(A2)

wherein each of symbols is as defined in the description.

Claims

1. A compound of the following formula (A1) or (A2):
R.sup.1(PE.sup.1-Y).sub.nPE.sup.2-X(SiR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m).sub.(A1)
(R.sup.c.sub.mR.sup.b.sub.lR.sup.a.sub.kSi).sub.X(PE.sup.1-Y).sub.nPE.sup.2-X(SiR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m).sub.(A2) wherein: R.sup.1 is OR.sup.4; R.sup.4 is a hydrogen atom or an alkyl group having 1-20 carbon atoms; PE.sup.1 is each independently at each occurrence a group of the formula:
(C.sub.aH.sub.2aO).sub.b wherein: a is an integer of 1-6 independently per a unit in parentheses with the subscript b; in formula (A1) or (A2), is 4 in at least one unit; (C.sub.4H.sub.8O) unit is (CH.sub.2CH.sub.2CH.sub.2CH.sub.2O); b is each independently at each occurrence an integer of 1-200; Y is each independently at each occurrence a single bond or CONHR.sup.5NHCOO; R.sup.5 is each independently at each occurrence a divalent organic group; n is an integer of 1-50; PE.sup.2 is a single bond or the above (C.sub.aH.sub.2aO).sub.b group; X is each independently a single bond or a 2-10 valent organic group; R.sup.a is each independently at each occurrence ZSiR.sup.71.sub.pR.sup.72.sub.qR.sup.73.sub.r; Z is each independently at each occurrence an oxygen atom or a divalent organic group; R.sup.71 is each independently at each occurrence R.sup.a; R.sup.a has the same definition as that of R.sup.a; in R.sup.a, the number of Si atoms which are straightly linked via the Z group is up to five; R.sup.72 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.73 is each independently at each occurrence a hydrogen atom or a lower alkyl group; p is each independently at each occurrence an integer of 0-3; q is each independently at each occurrence an integer of 0-3; r is each independently at each occurrence an integer of 0-3; in one R.sup.a, the sum of p, q and r is 3; R.sup.b is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.c is each independently at each occurrence a hydrogen atom or a lower alkyl group; k is each independently at each occurrence an integer of 0-3; l is each independently at each occurrence an integer of 0-3; m is each independently at each occurrence an integer of 0-3; in a unit in parentheses with the subscript , the sum of k, l and m is 3; is each independently an integer of 1-9; and at least one R.sup.72 or R.sup.b is present in the formula.

2. The compound according to claim 1 which is a compound of the formula (A1):
R.sup.1(PE.sup.1-Y).sub.nPE.sup.2-X(SiR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m).sub.(A1) wherein R.sup.1, PE.sup.1, PE.sup.2, X, Y, R.sup.a, R.sup.b, R.sup.c, k, l, m, n and are as defined in claim 1.

3. The compound according to claim 1 wherein (C.sub.aH.sub.2aO).sub.b in PE.sup.1 and PE.sup.2 are each independently a group of the formula:
(C.sub.4H.sub.2aO).sub.c(C.sub.3H.sub.6O).sub.d(C.sub.2H.sub.4O).sub.e wherein: c, d and e are each independently an integer of 0-200; the sum of c, d and e is 1-200; and the occurrence order of the respective repeating units in parentheses with the subscript c, d or e is not limited in the formula.

4. The compound according to claim 1 wherein (C.sub.aH.sub.2aO).sub.b in PE.sup.1 and PE.sup.2 are a group of the formula:
(C.sub.4H.sub.8O).sub.c(C.sub.3H.sub.6O).sub.d wherein: c and d are an integer of 0-200; the sum of c and d is 1-200; and the occurrence order of the respective repeating units in parentheses with the subscript c or d is not limited in the formula.

5. The compound according to claim 1 wherein PE.sup.1 and PE.sup.2 are each independently at each occurrence a group selected from;
(C.sub.4H.sub.8O).sub.c
(C.sub.3H.sub.6O).sub.d, and
(C.sub.2H.sub.4O).sub.e wherein c, d and e are each independently an integer of 1-200.

6. The compound according to claim 1 wherein PE.sup.1 and PE.sup.2 are each independently at each occurrence a group of the formulae:
(C.sub.4H.sub.8O).sub.c, and
(C.sub.3H.sub.6O).sub.d wherein c, d and e are each independently an integer of 1-200.

7. The compound according to claim 1 wherein PE.sup.1 and PE.sup.2 are each independently at each occurrence a group of:
(C.sub.4H.sub.8O).sub.c wherein c is an integer of 1-200.

8. The compound according to claim 3 wherein C.sub.3H.sub.6O is CH.sub.2CH.sub.2CH.sub.3O; and C.sub.2H.sub.4O is CH.sub.2CH.sub.2O.

9. The compound according to claim 1 wherein Y is a group of the following formula:
CONHR.sup.5NHCOO wherein R.sup.5 is a group of
(CH.sub.2).sub.x wherein x is an integer of 1-6; ##STR00019## wherein x and y are each independently an integer of 0-6; and z is an integer of 0-10; or ##STR00020## wherein x and y are each independently an integer of 0-6; and z is an integer of 0-4.

10. The compound according to claim 1 wherein X is CONHC.sub.1-20 alkylene group.

11. The compound according to claim 1 wherein a number average molecular weight of PE.sup.1 is 500-10,000.

12. The compound according to claim 1 wherein glass transition temperature is within the range of 70 C. to 40 C.

13. A surface-treating agent comprising at least one compound of the formula (A1) or the formula (A2) according to claim 1.

14. The surface-treating agent according to claim 13 further comprising a solvent.

15. The surface-treating agent according to claim 13 further comprising a polyol of the following formula:
HO(C.sub.aH.sub.2aO).sub.bOH wherein: a is an integer of 1-6 each independently per a unit in parentheses with the subscript b; and b is each independently at each occurrence an integer of 1-300.

16. The surface-treating agent according to claim 13 which is able to form a surface treating layer having a contact angle to n-hexadecane of 40 or less.

17. The surface-treating agent according to claim 13 which is able to form a surface treating layer having a coefficient of kinetic friction of 0.30 or less.

18. An article comprising a base material and a layer which is formed on a surface of the base material from the surface-treating agent according to claim 13.

19. The article according to claim 18 wherein the article is an optical member.

20. The article according to claim 18 wherein the article is a display or a touch panel.

Description

EXAMPLES

[0241] The surface-treating agent of the present invention will be described in detail through Examples, although the present invention is not limited to Examples. It is noted that in Examples, all chemical formulae described below mean an average composition.

Synthesis of Compound

Example 1

[0242] To a four-necked flask provided with a dropping funnel, a stirrer, and a thermometer, polytetramethyleneglycol (molecular weight: 650, 8.56 g) and ethyl acetate (10.0 g) were added, and then stirred and mixed to homogenize in the system. Then, a mixture of isophorone diisocyanate (1.45 g) and di-n-butyl tin dilaurate (0.05 g) as a catalyst was added dropwise from the dropping funnel such that [OH]/[NCO] is 2/1, and then stirred and reacted at 12 hours at a room temperature. After confirming disappearance of a peak at 2260 cm.sup.1 of isocyanate by FT-IR, 3-(triethoxysilyl)propylisocyanate (1.63 g) was added dropwise and reacted until a peak of isocyanate is completely disappear to Composition 1 as a mixture of compounds of the following formula.

##STR00014##

wherein R is each independently OH or CONH(CH.sub.2).sub.3Si(OEt).sub.3.

Example 2

[0243] To a four-necked flask provided with a dropping funnel, a stirrer, and a thermometer, polytetramethyleneglycol (molecular weight: 650, 7.8 g) and ethyl acetate (10.0 g) were added, and then stirred and mixed to homogenize in the system. Then, a mixture of isophorone diisocyanate (2.2 g) and di-n-butyl tin dilaurate (0.05 g) as a catalyst was added dropwise from the dropping funnel such that [OH]/[NCO] is 6/5, and then stirred and reacted at 12 hours at a room temperature. After confirming disappearance of a peak at 2260 cm.sup.1 of isocyanate by FT-IR, 3-(triethoxysilyl)propylisocyanate (0.5 g) was added dropwise and reacted until a peak of isocyanate is completely disappear to Composition 2 as a mixture of compounds of the following formula.

##STR00015##

wherein R is each independently OH or CONH(CH.sub.2).sub.3Si(OEt).sub.3.

Example 3

[0244] To a four-necked flask provided with a dropping funnel, a stirrer, and a thermometer, polytetramethyleneglycol (molecular weight: 2000, 9.5 g) and ethyl acetate (10.0 g) were added, and then stirred and mixed to homogenize in the system. Then, a mixture of isophorone diisocyanate (0.52 g) and di-n-butyl tin dilaurate (0.05 g) as a catalyst was added dropwise from the dropping funnel such that [OH]/[NCO] is 2/1, and then stirred and reacted at 12 hours at a room temperature. After confirming disappearance of a peak at 2260 cm.sup.1 of isocyanate by FT-IR, 3-(triethoxysilyl)propylisocyanate (0.59 g) was added dropwise and reacted until a peak of isocyanate is completely disappear to Composition 3 as a mixture of compounds of the following formula.

##STR00016##

wherein R is each independently OH or CONH(CH.sub.2).sub.3Si(OEt).sub.3.

Comparative Example 1

[0245] To a four-necked flask provided with a dropping funnel, a stirrer, and a thermometer, polypropyleneglycol (molecular weight: 1000, 9.0 g) and ethyl acetate (10.0 g) were added, and then stirred and mixed to homogenize in the system. Then, a mixture of isophorone diisocyanate (0.99 g) and di-n-butyl tin dilaurate (0.05 g) as a catalyst was added dropwise from the dropping funnel such that [OH]/[NCO] is 2/1, and then stirred and reacted at 12 hours at a room temperature. After confirming disappearance of a peak at 2260 cm.sup.1 of isocyanate by FT-IR, 3-(triethoxysilyl)propylisocyanate (1.11 g) was added dropwise and reacted until a peak of isocyanate is completely disappear to Composition 4 as a mixture of compounds of the following formula.

##STR00017##

wherein R is each independently OH or CONH(CH.sub.2).sub.3Si(OEt).sub.3.

Comparative Example 2

[0246] To a four-necked flask provided with a dropping funnel, a stirrer, and a thermometer, polybutyleneglycol ((OCH(CH.sub.3)CH.sub.2CH.sub.2).sub.n) (molecular weight: 700, 8.64 g) and ethyl acetate (10.0 g) were added, and then stirred and mixed to homogenize in the system. Then, a mixture of isophorone diisocyanate (1.36 g) and di-n-butyl tin dilaurate (0.05 g) as a catalyst was added dropwise from the dropping funnel such that [OH]/[NCO] is 2/1, and then stirred and reacted at 12 hours at a room temperature. After confirming disappearance of a peak at 2260 cm.sup.1 of isocyanate by FT-IR, 3-(triethoxysilyl)propylisocyanate (1.44 g) was added dropwise and reacted until a peak of isocyanate is completely disappear to Composition 5 as a mixture of compounds of the following formula.

##STR00018##

wherein R is each independently OH or CONH(CH.sub.2).sub.3Si(OEt).sub.a.

Formation of Surface Treating Layer

Example 4

[0247] Composition 1 obtained in Example 1 was dissolved in ethyl acetate so as to obtain an ethyl acetate solution having a concentration of 20 wt % to prepare a surface treating agent. The surface treating agent was vacuum deposited (pressure 3.010.sup.3 Pa) on a chemical strengthening glass (Gorilla glass manufactured by Corning Incorporated; thickness: 0.7 mm). The surface-treating agent of 2 mg (that is, it contained of 0.4 mg of Compound 1 of Example 1) was vacuum-deposited per one plate of the chemical strengthening glass (55 mm100 mm). Then, the chemical strengthening glass having the deposited layer was stood under a temperature of 20 C. and a humidity of 65% for 24 hours. As a result, the deposited layer was hardened and the surface treating layer was formed.

Example 5

[0248] Similarly to Example 4 except Composition 2 of Example 2 was used in place of Composition 1 of Example 1, the surface-treating agent was prepared and the surface treating layer was formed.

Example 6

[0249] Similarly to Example 4 except Composition 3 of Example 3 was used in place of Composition 1 of Example 1, the surface-treating agent was prepared and the surface treating layer was formed.

Example 7

[0250] In place of the using of Composition 1 of Example 1, Composition 1 of Example 1 and Composition 4 of Comparative Example 1 are mixed such that a solid ratio is 50/50. Then, a surface treating composition is prepared to form a surface treating layer similarly to Example 4.

Example 8

[0251] In place of the using of Composition 1 of Example 1, Composition 1 of Example 1 and Composition 4 of Comparative Example 1 are mixed such that a solid ratio is 25/75. Then, a surface treating composition is prepared to form a surface treating layer similarly to Example 4.

Comparative Example 3

[0252] Similarly to Example 4 except Composition 4 of Comparative Example 1 was used in place of Composition 1 of Example 1, the surface-treating agent was prepared and the surface treating layer was formed.

Comparative Example 4

[0253] Similarly to Example 4 except Composition 5 of Comparative Example 2 was used in place of Composition 1 of Example 1, the surface-treating agent was prepared and the surface treating layer was formed.

Experiment 1

[0254] Evaluation of Surface Slip Property (Measurement of Coefficient of Dynamic Friction)

[0255] Coefficient of dynamic friction of the surface-treating layers formed on the surface of the base material in the above Examples 4-8 and Comparative Examples 3-4 was measured. Specifically, the coefficient of dynamic friction () was measured by using a surface texture measurement instrument (FPT-1 manufactured by Labthink Co., Ltd.) using a paper as a friction probe according to ASTM D4917. Specifically, the base material on which the surface-treating layer was formed was horizontally arranged, and then, a friction paper (2 cm2 cm) was contacted to an exposed surface of the surface-treating layer and a load of 200 gf was applied thereon. Then, the friction paper was parallely moved at a speed of 500 mm/second while applying the load and the coefficient of dynamic friction was measured. The results are shown in Table 1.

[0256] Evaluation of Visibility

[0257] For the surface-treating layers formed on the surface of the base material in the above Examples 4-8 and Comparative Examples 3-4, visibility and wiping property of adhered fingerprint were evaluated. Specifically, the treated base material to which fingerprint was adhered was placed on an aluminum metal plate, and was exposed to light of a fluorescent lamp at an incident angel of 60 degrees in a dark room, and then appearance of fingerprint adhered to the base material was visually observed at 60 degrees from the opposite side to the light source. The evaluation was performed according to the following three criteria.

[0258] 1: Adhered fingerprint was not visible.

[0259] 2: Adhered fingerprint was slightly visible.

[0260] 3: Adhered fingerprint was clearly visible.

[0261] Evaluation of Wiping Fingerprint

[0262] For the base material after the fingerprint adhering test, the fingerprint was wiped using Kimwipe with a load of 100 gf, and condition after wiping fingerprint was evaluated visually. The evaluation was performed according to the following 3 criteria.

[0263] 1: Adhered fingerprint disappeared by the wiping of two or less shuttles.

[0264] 2: Adhered fingerprint disappeared by the wiping of 3-5 shuttles.

[0265] 3: Adhered fingerprint remained even after the wiping of 5 shuttles.

[0266] Evaluation of Contact Angle

[0267] The static contact angle to water and n-hexadecane (degree) was measured for 1 L of water by using a contact angle measuring instrument (DropMaster manufactured by KYOWA INTERFACE. SCIENCE Co., LTD.). The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Example Example Example Example 4 5 6 7 COF 0.09 0.07 0.11 0.12 Adhesion property 1 1 1 1 of fingerprint Wiping property of 1 1 1 1 fingerprint Contact water 1 1 1 1 angle hexadecane 40 39 71 39 () Comparative Comparative Example Example Example 8 3 4 COF 0.12 0.17 0.19 Adhesion property 1 1 1 of fingerprint Wiping property of 2 3 3 fingerprint Contact water 38 35 33 angle hexadecane 7 12 11 ()

[0268] As understood from the above results, it was confirmed that in the surface-treating layer formed from the surface-treating agent containing the compound of the present invention, even when fingerprint is adhered, visibility of fingerprint is low and adhered fingerprints can easily become invisible.

INDUSTRIAL APPLICABILITY

[0269] The present invention is suitably applied for forming a surface-treating layer on a surface of various base materials, in particular, an optical member in which transparency is required.