Surface treatment composition

Abstract

A composition including a compound containing a carbon-carbon double bond obtained by reacting (A) a polyisocyanate which is a trimer of diisocyanate, with (B) a compound having an active hydrogen, wherein component (B) includes: (B1) a perfluoropolyether having an active hydrogen, (B2) a silane compound having an active hydrogen, and (B3) a monomer having an active hydrogen and a carbon-carbon double bond. Further, a molar amount of an isocyanate group in component (A) is equal to a total molar amount of component (B), and a molar amount of component (B1), component (B2) and component (B3) per 9 moles of the isocyanate group in component (A) are component (B1) 0.1-2 moles, component (B2) 0.05-2 moles, and component (B3) 5-8.85 moles, respectively.

Claims

1. A composition comprising a reaction product containing a carbon-carbon double bond obtained by reacting (A) a polyisocyanate which is a trimer of diisocyanate, with (B) a compound having an active hydrogen, wherein component (B) comprises: (B1) a perfluoropolyether having an active hydrogen, (B2) a silane compound or a siloxane compound having an active hydrogen, and (B3) a monomer having an active hydrogen and a carbon-carbon double bond a molar amount of an isocyanate group in component (A) is equal to a total molar amount of component (B), and a molar amount of component (B1), component (B2) and component (B3) per 9 moles of the isocyanate group in component (A) are component (B1) 0.1-2 moles, component (B2) 0.05-2 moles, and component (B3) 5-8.85 moles, respectively, and a ratio of a number average molecular weight of component (B1) to (B2) is 1:3-3:1.

2. The composition according to claim 1 wherein component (A) is an isocyanurate type polyisocyanate.

3. The composition according to claim 1 wherein component (B1) is at least one compound of any one of the following general formulae (B1-i) and (B1-ii):
RfPFPE-R.sup.1CH.sub.2OH(B1-i)
HOCH.sub.2R.sup.1PFPE-R.sup.1CH.sub.2OH(B1-ii) wherein Rf is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; PFPE is a group of the general formula:
(OC.sub.4F.sub.8).sub.a(OC.sub.3F.sub.6).sub.b(OC.sub.2F.sub.4).sub.c(OCF.sub.2).sub.d wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is at least one, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula; and R.sup.1 is each independently a group of the following formula:
(Y).sub.f(CF.sub.2).sub.g(CH.sub.2).sub.h wherein Y is an oxygen atom or a divalent polar group, f, g and h are each independently an integer of 0-50, the sum of f, g and h is at least one, and the occurrence order of the respective repeating units in parentheses is not limited in the formula.

4. The composition according to claim 3 wherein component (B1) is at least one compound of the general formula (B1-i).

5. The composition according to claim 3 wherein PFPE is a group of any one of the formulae (i)-(iii):
(OCF.sub.2CF.sub.2CF.sub.2).sub.b(i) wherein b is an integer of 1-200,
(OCF(CF.sub.3)CF.sub.2).sub.b(ii) wherein b is an integer of 1-200,
(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.a(OCF.sub.2CF.sub.2CF.sub.2).sub.b(OCF.sub.2CF.sub.2).sub.c(OCF.sub.2).sub.d(iii) wherein a and b are each independently 0 or an integer of 1-30, c and d are each independently an integer of 1-200, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula.

6. The composition according to claim 1 wherein component (B2) is at least one compound for the general formula: ##STR00007## wherein R.sup.11, R.sup.12, R.sup.13, R.sup.14 and R.sup.15 are each independently an alkyl group or an aryl group; R.sup.16 is a divalent organic group; l and n are each independently 0 or 1; m is an integer of 1-500; o is an integer of 0-20; and p is 0 or 1.

7. The composition according to claim 1 wherein component (B3) is a compound containing a (meth)acrylate group.

8. The composition according to claim 1 wherein component (B3) is at least one compound selected from the group consisting of
HO(CH.sub.2CH.sub.2).sub.iOCO(R)CCH.sub.2 wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom, and i is 2-10;
CH.sub.3CH(OH)CH.sub.2OCO(R)CCH.sub.2 wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or n alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
CH.sub.3CH.sub.2CH(OH)CH.sub.2OCO(R)CCH.sub.2 wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
C.sub.6H.sub.5OCH.sub.2CH(OH)CH.sub.2OCO(R)CCH.sub.2 wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
HOCH.sub.2C(CH.sub.2OCO(R)CCH.sub.2).sub.3 wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
C(CH.sub.2OCO(R)CCH.sub.2).sub.3CH.sub.2OCH.sub.2C(CH.sub.2OCO(R)CCH.sub.2).sub.2CH.sub.2OH wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
HOCH.sub.2CH.sub.2OCOC.sub.6H.sub.5OCOCH.sub.2CH.sub.2OCO(R)CCH.sub.2 wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
H(OCH.sub.2CH.sub.2).sub.nOCO(R)CCH.sub.2 wherein n is 1-30, and R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
H(OCH(CH.sub.3)CH.sub.2).sub.nOCO(R)CCH.sub.2 wherein n is 1-30, and R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom; an allylalcohol;
HO(CH.sub.2).sub.kCHCH.sub.2 wherein k is 2-20;
(CH.sub.3).sub.3SiCH(OH)CHCH.sub.2; and styrylphenol.

9. The composition according to claim 1 wherein the reaction of component (A) with component (B) is conducted by reacting a portion of the isocyanate group component (A) with component (B1) and component (B2), and then the rest of the isocyanate group with component (B3).

10. The composition according to claim 1, obtained by reacting component (A) with component (B1) and (B3) to provide the first composition, reacting component (A) with component (B2) and (B3) to provide the second composition, and then, mixing the first composition and the second composition.

11. The composition according to claim 10, obtained by reacting component (A) with component (B1) followed by component (B3) to provide the first composition, by reaction component (A) with component (B2) and then component (B3) to provide the second composition.

12. The composition according to claim 1, comprising at least one fluorine-containing oil of the following general formula (C):
Rf.sup.1PFPE-Rf.sup.2(C) wherein: Rf.sup.1 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; Rf.sup.2 is a hydrogen atom, a fluorine atom, or an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; and PFPE is a group of the general formula:
(OC.sub.4F.sub.8).sub.a(OC.sub.3F.sub.6).sub.b(OC.sub.2F.sub.4).sub.c(OCF.sub.2).sub.d wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is at least one, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula.

13. A surface treatment composition comprising one or more compositions according to claim 1.

14. The surface treatment composition according to claim 13, comprising a solvent of 5-10,000 parts by mass with respect to the total 100 parts by mass of the composition according to claim 1.

15. The surface treatment composition according to claim 14 wherein the solvent is a fluorine-free organic solvent.

16. The surface treatment composition according to claim 14 wherein the solvent is a mixed solvent of a fluorine-free organic solvent and a fluorine-containing organic solvent.

17. The surface treatment composition according to claim 13, comprising an active energy curing initiator.

18. A curable composition comprising a composition according to claim 1; and a matrix forming composition.

19. The curable composition according to claim 18 comprising a solvent of 0-19,900 parts by mass with respect to the total 100 parts by mass of the composition.

20. The curable composition according to claim 19 wherein the solvent is a fluorine-free organic solvent.

21. The curable composition according to claim 19 wherein the solvent is a mixed solvent of a fluorine-free organic solvent and a fluorine-containing organic solvent.

22. The curable composition according to claim 18 comprising an active energy curing initiator.

23. The curable composition according to claim 18 comprising the composition according to claim 1 of 0.01-10% by mass with respect to the total of the matrix forming composition and the composition according to claim 1.

24. An article comprising a base material and a layer which is formed on a surface of the base material from the surface treatment composition according to claim 13.

25. The article according to claim 24 which is an optical member.

26. An article comprising a base material and a layer which is formed on a surface of the base material from the curable composition according to claim 18.

Description

EXAMPLE

Example 1

(1) In 1 L of a four-necked flask equipped with a dropping funnel, a condenser, a thermometer and a stirrer, SUMIDUR (registered trademark) N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd., the content of the NCO group: 21.8%, 36.6 g) was dissolved in HCFC 225 (219.4 g), and dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., 0.30 g) was added. A solution in which an alcohol having a perfluoropolyether of an average composition: CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.14CF.sub.2CF.sub.2CH.sub.2OH (hereinafter, referred to as a PFPE alcohol, 30.0 g) was dissolved in HCFC 225 (30.0 g) was dropped into the mixture under nitrogen flowing with stirring at 40 C. for 1 hour, and the mixture was stirred for 1 hour. A solution in which SILAPLANE (registered trademark) FM-0411 (manufactured by JNC Corporation, the molecular weight: 1,000, 10.5 g) was dissolved in HCFC 225 (10.5 g) was dropped into the mixture for 1 hour, and the mixture was stirred for 1 hour. Light ester (trade name) HOA (manufactured by Kyoeisha Chemical Co., Ltd., 19.6 g) was dropped for 30 minutes, and the mixture was stirred for 4 hours. It was confirmed that absorption of NCO in IR (Infrared Spectroscopy) was completely disappeared. Dibutyl hydroxy toluene (0.05 g) was added, and HCFC 225 was completely removed by an evaporator.

(2) component (B1)=2,658

(3) component (B2)=1,000

(4) component (B1)/component (B2)/component (B3)=0.5/0.5/8

Examples 2-11

(5) The compositions of Examples 2-11 were prepared similarly to Example 1 except that the use amount of agents was changed as shown in the following table.

Example 2

(6) TABLE-US-00001 TABLE 1 SUMIDUR N3300 30.5 g HCFC225 (for dissolving SUMIDUR) 182.8 g dibutyltin dilaurate 0.03 g PFPE alcohol 50.0 g HCFC225 (for dissolving PFPE alcohol) 50.0 g SILAPLANE FM-0411 8.8 g HCFC225 (for dissolving SILAPLANE) 8.8 g Light ester HOA 15.3 g dibutyl hydroxy toluene 0.05 g

Example 3

(7) TABLE-US-00002 TABLE 2 SUMIDUR N3300 30.5 g HCFC225 (for dissolving SUMIDUR) 182.8 g dibutyltin dilaurate 0.03 g PFPE alcohol 50.0 g HCFC225 (for dissolving PFPE alcohol) 50.0 g SILAPLANE FM-0411 17.6 g HCFC225 (for dissolving SILAPLANE) 17.6 g Light ester HOA 14.3 g dibutyl hydroxy toluene 0.05 g

Example 4

(8) TABLE-US-00003 TABLE 3 SUMIDUR N3300 36.6 g HCFC225 (for dissolving SUMIDUR) 219.4 g dibutyltin dilaurate 0.03 g PFPE alcohol 30.0 g HCFC225 (for dissolving PFPE alcohol) 30.0 g X-22-170BX in place of SILAPLANE 29.5 g HCFC225 (for dissolving X-22-170BX) 29.5 g Light ester HOA 19.6 g dibutyl hydroxy toluene 0.05 g *X-22-170BX (product name); manufactured by Shin-Etsu Chemical Co., Ltd. (molecular weight: 2,800)

Example 5

(9) TABLE-US-00004 TABLE 4 SUMIDUR N3300 30.5 g HCFC225 (for dissolving SUMIDUR) 182.8 g dibutyltin dilaurate 0.03 g PFPE alcohol 50.0 g HCFC225 (for dissolving PFPE alcohol) 50.0 g X-22-170BX in place of SILAPLANE 24.6 g HCFC225 (for dissolving X-22-170BX) 24.6 g Light ester HOA 15.3 g dibutyl hydroxy toluene 0.05 g

Example 6

(10) TABLE-US-00005 TABLE 5 SUMIDUR N3300 24.4 g HCFC225 (for dissolving SUMIDUR) 146.3 g dibutyltin dilaurate 0.03 g PFPE alcohol 40.0 g HCFC225 (for dissolving PFPE alcohol) 40.0 g X-22-170BX in place of SILAPLANE 39.4 g HCFC225 (for dissolving X-22-170BX) 39.4 g Light ester HOA 11.4 g dibutyl hydroxy toluene 0.05 g

Example 7

(11) TABLE-US-00006 TABLE 6 SUMIDUR N3300 42.7 g HCFC225 (for dissolving SUMIDUR) 256.0 g dibutyltin dilaurate 0.03 g PFPE alcohol 35.0 g HCFC225 (for dissolving PFPE alcohol) 35.0 g SILAPLANE FM-0421 12.3 g HCFC225 (for dissolving SILAPLANE) 12.3 g Light ester HOA 24.0 g dibutyl hydroxy toluene 0.05 g *SILAPLANE (registered trademark) FM-0421; manufactured by JNC Corporation (Molecular weight: 5,000)

Example 8

(12) TABLE-US-00007 TABLE 7 SUMIDUR N3300 30.2 g HCFC225 (for dissolving SUMIDUR) 181.2 g dibutyltin dilaurate 0.03 g PFPE alcohol 40.0 g HCFC225 (for dissolving PFPE alcohol) 40.0 g X-22-170BX in place of SILAPLANE 24.4 g HCFC225 (for dissolving X-22-170BX) 24.4 g Light ester HOA 16.2 g dibutyl hydroxy toluene 0.05 g

Example 9

(13) TABLE-US-00008 TABLE 8 SUMIDUR N3300 42.7 g HCFC225 (for dissolving SUMIDUR) 256.0 g dibutyltin dilaurate 0.03 g PFPE alcohol 35.0 g HCFC225 (for dissolving PFPE alcohol) 35.0 g SILAPLANEFM-0425 12.3 g HCFC225 (for dissolving SILAPLANE) 12.3 g Light ester HOA 24.1 g dibutyl hydroxy toluene 0.05 g *SILAPLANE (registered trademark) FM-0425; manufactured by JNC Corporation (Molecular weight: 10,000)

Example 10

(14) TABLE-US-00009 TABLE 9 SUMIDUR N3300 22.2 g HCFC225 (for dissolving SUMIDUR) 230.0 g dibutyltin dilaurate 0.03 g PFPE alcohol 15.0 g HCFC225 (for dissolving PFPE alcohol) 15.0 g X-22-170BX in place of SILAPLANE FM- 17.9 g 0411 HCFC225 (for dissolving X-22-170BX) 17.9 g A-TMM-3LM-N (trade name) 61.3 g (manufactured by Shin-Nakamura Chemical Co., Ltd.) in place of Light ester HOA dibutyl hydroxy toluene 0.05 g

Example 11

(15) TABLE-US-00010 TABLE 10 SUMIDUR N3300 14.8 g HCFC225 (for dissolving SUMIDUR) 170.0 g dibutyltin dilaurate 0.03 g PFPE alcohol 10.0 g HCFC225 (for dissolving PFPE alcohol) 10.0 g X-22-170BX in place of SILAPLANE FM- 12.0 g 0411 HCFC225 (for dissolving X-22-170BX) 12.0 g A-9570W (trade name) (manufactured by 48.7 g Shin-Nakamura Chemical Co., Ltd.) in place of Light ester HOA dibutyl hydroxy toluene 0.05 g

Example 12

(16) Preparation of the First Composition

(17) In 5 L of a four-necked flask equipped with a dropping funnel, a condenser, a thermometer and a stirrer, SUMIDUR (registered trademark) N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd., the content of the NCO group: 21.8%, 304.5 g) was dissolved in ZEORORA H (manufactured by Nippon ZEON Corporation, 1760 g), and dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., 0.3 g) was added. A solution in which an alcohol having a perfluoropolyether of an average composition: CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.14CF.sub.2CF.sub.2CH.sub.2CH(PFPE alcohol, 500 g) was dissolved in ZEORORA H (500 g) was dropped into the mixture under nitrogen flowing with stirring at 40 C. for 1 hour, and the mixture was stirred for 1 hour. Light ester HOA (196 g) was dropped for 30 minutes, and the mixture was stirred for 4 hours. After confirming that absorption of NCO in IR (Infrared Spectroscopy) was completely disappeared, dibutyl hydroxy toluene (0.5 g) was added, and the mixture was stirred for 15 minutes. The mixture was diluted with propylene glycol monomethylether (PGME) such that the concentration of the polymer solid in the solution was 20% to provide 20 wt % of the perfluoropolyether urethane acrylate compound solution in ZECRORA H/PGME.

(18) Preparation of the Second Composition

(19) In 1 L of a four-necked flask equipped with a dropping funnel, a condenser, a thermometer and a stirrer, SUMIDUR (registered trademark) N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd., the content of the NCO group: 21.8%, 52.6 g) was dissolved in methyl ethyl ketone (295 g), and dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., 0.053 g) was added. A solution in which SILAPLANE (registered trademark) FM-0411 (manufactured by JNC Corporation, the molecular weight: 1,000, 100 g) was dissolved in methyl ethyl ketone (100 g) was dropped into the mixture under nitrogen flowing with stirring at 40 C. for 1 hour, and the mixture was stirred for 1 hour. Light ester HOA (manufactured by Kyoeisha Chemical Co., Ltd., 25.3 g) was dropped for 30 minutes, and the mixture was stirred for 4 hours. It was confirmed that absorption of NCO in IR (Infrared Spectroscopy) was completely disappeared. Dibutyl hydroxy toluene (0.16 g) was added and the mixture was stirred for 15 minutes, and diluted with methyl ethyl ketone such that the concentration of the solid in the solution was 20% by mass to provide 20% of the desired compound solution in methyl ethyl ketone.

(20) Preparation of the Composition of the Present Invention

(21) To 5 L of a four-necked flask equipped with a dropping funnel, a thermometer and a stirrer, the first composition obtained above (2004 g) and methyl ethyl ketone (998 g) were added and stirred for 30 minutes. The second composition obtained above (715 g) was dropped by using a dropping funnel and mixed to provide the composition of the present invention.

Example 13

(22) With respect to the first composition, the similar process to that of Example 12 described above was performed.

(23) With respect to the second composition, the similar process to that of Example 12 described above was performed except the use amount of the agents were changed as shown in the following table.

(24) TABLE-US-00011 TABLE 11 SUMIDUR N3300 17.3 g methyl ethyl ketone (for dissolving SUMIDUR) 240 g dibutyltin dilaurate 0.05 g SILAPLANEFM-0421 in place of SILAPLANE FM- 150 g 0411 methyl ethyl ketone (for dissolving 150 g SILAPLANE) Light ester HOA 8.4 g dibutyl hydroxy toluene 0.15 g

(25) Preparation of the Composition of the Present Invention

(26) To 5 L of a four-necked flask equipped with a dropping funnel, a thermometer and a stirrer, the first composition obtained above (2427 g) and methyl ethyl ketone (976 g) were added and stirred for 30 minutes. The second composition obtained above (500 g) was dropped by using a dropping funnel and mixed to provide the composition of the present invention.

Example 14

(27) With respect to the first composition, the similar process to that of Example 12 described above was performed.

(28) With respect to the second composition, the similar process to that of Example 12 described above was performed except the use amount of the agents were changed as shown in the following table.

(29) TABLE-US-00012 TABLE 12 SUMIDUR N3300 20.6 g methyl ethyl ketone (for dissolving SUMIDUR) 262 g dibutyltin dilaurate 0.05 g X-22-170BX in place of SILAPLANE FM-0411 100 g methyl ethyl ketone (for dissolving X-22- 100 g 170BX) A-TMM-3LM-N (trade name) (manufactured by 42 g Shin-Nakamura Chemical Co. Ltd.) dibutyl hydroxy toluene 0.08 g

(30) Preparation of the Composition of the Present Invention

(31) To 5 L of a four-necked flask equipped with a dropping funnel, a thermometer and a stirrer, the first composition obtained above (1098 g) and methyl ethyl ketone (532 g) were added and stirred for 30 minutes. The second composition obtained above (500 g) was dropped by using a dropping funnel and mixed to provide the composition of the present invention.

Example 15

(32) With respect to the first composition, the similar process to that of Example 12 described above was performed.

(33) With respect to the second composition, the similar process to that of Example 12 described above was performed except the use amount of the agents were changed as shown in the following table.

(34) TABLE-US-00013 TABLE 13 SUMIDUR N3300 20.6 g methyl ethyl ketone (for dissolving SUMIDUR) 281 g dibutyltin dilaurate 0.05 g X-22-170BX in place of SILAPLANE FM-0411 100 g methyl ethyl ketone 100 g (for dissolving X-22-170BX) A-9570W (trade name) (manufactured by Shin- 51 g Nakamura Chemical Co., Ltd.) dibutyl hydroxy toluene 0.1 g

(35) Preparation of the Composition of the Present Invention

(36) To 5 L of a four-necked flask equipped with a dropping funnel, a thermometer and a stirrer, the first composition obtained above (1048 g) and methyl ethyl ketone (516 g) were added and stirred for 30 minutes. The second composition obtained above (500 g) was dropped by using a dropping funnel and mixed to provide the composition of the present invention.

(37) The number average molecular weight of component (B1) and (B2) and a ratio (a molar ratio) of component (B1), component (B2) and component (B3) with respect to 9 moles of the isocyanate group in component (A) in Examples 1-15 are shown in the following table.

(38) TABLE-US-00014 TABLE 14 Number average molecular weight Component Component B1/B2/B3 (B1) (B2) (molar ratio) Example 1 2,658 1,000 0.5/0.5/8 Example 2 2,658 1,000 1/0.5/7.5 Example 3 2,658 1,000 1/1/7 Example 4 2,658 2,800 0.5/0.5/8 Example 5 2,658 2,800 1/0.5/7.5 Example 6 2,658 2,800 1/1/7 Example 7 2,658 5,000 0.5/0.1/8.4 Example 8 4,290 2,800 0.5/0.5/8 Example 9 2,658 10,000 0.5/0.05/8.45 Example 10 2,658 2,800 0.5/0.5/8 Example 11 2,658 2,800 0.5/0.5/8 Example 12 2,658 1,000 0.75/0.75/7.5 Example 13 2,658 5,000 0.94/0.18/7.88 Example 14 2,658 2,800 0.85/0.45/7.7 Example 15 2,658 2,800 0.85/0.45/7.7

Comparative Example 1

(39) In 1 L of a four-necked flask equipped with a dropping funnel, a condenser, a thermometer and a stirrer, SUMIDUR (registered trademark) N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd., the content of the NCO group: 21.8%, 36.6 g) was dissolved in HCFC 225 (219.4 g), and dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., 0.30 g) was added. A solution in which an alcohol having a perfluoropolyether of an average composition: CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.14CF.sub.2CF.sub.2CH.sub.2OH(PFPE alcohol, 60.0 g) was dissolved in HCFC 225 (60.0 g) was dropped into the mixture under nitrogen flowing with stirring at 40 C. for 1 hour, and the mixture was stirred for 1 hour. Light ester (trade name) HOA (manufactured by Kyoeisha Chemical Co., Ltd., 19.6 g) was dropped for 30 minutes, and the mixture was stirred for 4 hours. It was confirmed that absorption of NCO in IR was completely disappeared. Dibutyl hydroxy toluene (0.05 g) was added, and HCFC 225 was completely removed by an evaporator.

Comparative Examples 2-3

(40) The compositions of Comparative Examples 2-3 were prepared similarly to Example 1 except that the use amount of the agents was changed as shown in the following table.

Comparative Example 2

(41) TABLE-US-00015 TABLE 15 SUMIDUR N3300 14.2 g HCFC225 (for dissolving SUMIDUR) 85.3 g dibutyltin dilaurate 0.03 g PFPE alcohol 70.0 g HCFC225 (for dissolving PFPE alcohol) 70.0 g X-22-170BX in place of SILAPLANE 23.0 g HCFC225 (for dissolving X-22-170BX) 23.0 g Light ester HOA 4.8 g dibutyl hydroxy toluene 0.05 g

Comparative Example 3

(42) TABLE-US-00016 TABLE 16 SUMIDUR N3300 18.3 g HCFC225 (for dissolving SUMIDUR) 109.7 g dibutyltin dilaurate 0.04 g PFPE alcohol 15.0 g HCFC225 (for dissolving PFPE alcohol) 15.0 g X-22-170BX 88.6 g HCFC225 (for dissolving X-22-170BX) 88.6 g Light ester HOA 6.7 g dibutyl hydroxy toluene 0.05 g

(43) The number average molecular weight of component (B1) and (B2) and a ratio (a molar ratio) of component (B1), component (B2) and component (B3) with respect to 9 moles of the isocyanate group in component (A) in Comparative Examples 1-3 are shown in the following table.

(44) TABLE-US-00017 TABLE 17 B1/B2/B3 Number average molecular weight (molar Component (B1) Component (B2) ratio) Comparative 2,658 none 1/0/8 Example 1 Comparative 2,658 2,800 3/1/5 Example 2 Comparative 2,658 2,800 0.5/3/5.5 Example 3

Text Example 1

Solubility Examination

(45) Each of the compositions obtained in Examples 1-11 and Comparative Examples 1-3 was added to methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethyl acetate and butyl acetate such that the concentration of the solid was 20% by mass, and stirred at 25 C. for 60 minutes.

(46) The obtained solutions were observed, and solubility was determined based on the following criteria.

(47) clear and colorless

(48) dissolved, but slightly cloudy

(49) producing precipitate

(50) TABLE-US-00018 TABLE 18 Esther solvent Ketone solvent Ethyl Butyl Acetone MEK MIBK acetate acetate Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative X X X X X Example 1 Comparative X X X X X Example 2 Comparative X X X X X Example 3

Text Example 2

Function Examination

(51) Formation of Surface Treating Layer

(52) Each of the compositions (0.05 g) obtained in Examples 1-15 was added to a hard coating agent (Beam set 575CB (trade name), Arakawa Chemical Industry Co., Ltd., 9.95 g) and dissolved in methyl isobutyl ketone (15 g) to obtain 40% by mass of the curable composition. A polycarbonate substrate (Stella, manufactured by Nippon Testpanel Co., Ltd) was immersed in the obtained curable composition, and dried at 70 C. for 5 minutes. Then, 500 mJ/cm.sup.2 of ultraviolet was irradiated to form the surface treatment layer.

(53) The composition (2 g) obtained in Comparative Example 1 was dissolved in ZEORORA (registered trademark) H (manufactured by Nippon ZEON Corporation, 5 g) and propylene glycol monomethylether (3 g). The solution (0.5 g) was added to a hard coating agent (Beam set 575CB (trade name), Arakawa Chemical Industry Co., Ltd., 9.9 g), and dissolved in propylene glycol monomethylether (14.6 g) to obtain 40% by mass of the curable composition.

(54) Evaluation

(55) Evaluation of Contact Angle

(56) Static contact angles of water and n-hexadecane (water contact angle and n-hexadecane contact angle) were measured for 1 L or 2 L respectively by using a contact angle measuring instrument (manufactured by KYOWA INTERFACE SCIENCE Co., Ltd., DropMaster). The results are shown in Table 20 below.

(57) Evaluation of Friction Durability

(58) A cotton friction durability evaluation was performed as a friction durability evaluation. Specifically, the base material on which the surface treating layer was formed was horizontally arranged, and then, a cotton (BEMCOT (registered trademark) M3-II) was contacted with the exposed surface of the surface treating layer and a load of 500 g/cm.sup.2 was applied thereon. Then, the cotton was shuttled at a rate of 140 mm/second while applying the load. The static contact angle of water (water contact angle) was measured every 100 shuttles. The number of friction times was decided as the durable times for friction at the point that the measured value of the contact angle became to be 100 degree or less. The results are shown in Table 20 below.

(59) Evaluation of Surface Slip Property

(60) Coefficient of dynamic friction was measured by using a surface texture measurement instrument (FPT-F1; manufactured by Labthink Instrument Co. Ltd.) using a paper as a friction probe according to ASTM D4917. The results are shown in Table 20 below.

(61) Evaluation of Transparency

(62) Total light transmittance and haze were measured by using HAZE-GARDII (manufactured by Toyo Seiki Seisaku-Sho, Ltd.). The results are shown in Table 20 below.

(63) Evaluation of Repelling Property and Wiping Property of an Oil-based Ink

(64) A line was drawn on the surface-treating layer with an oil pen (Mckee (trade name), manufactured by Zebra Co., Ltd.), and the repelling property and the state of the surface-treating layer after allowing the surface-treating layer to stand for one minute and wiping the adhered ink three times with Kimwipe (trade name, manufactured by Jujo-Kimberly Co., Ltd) were visually evaluated.

(65) Evaluation criteria are as follows.

(66) TABLE-US-00019 TABLE 19 Repelling property Wiping property extremely repel easily wipeable repel wipeable X not repel not wipeable

(67) The above results are shown in Table 20.

(68) TABLE-US-00020 TABLE 20 Total Contact angle Coefficient Oil-based ink light n- of dynamic Repelling Wiping transmittance Haze water hexadecane friction property property Durability Example 1 92.5 0.31 107 64 0.052 15,000 Example 2 92.4 0.31 109 64 0.063 13,000 Example 3 92.5 0.35 107 64 0.073 13,000 Example 4 92.3 0.32 106 61 0.053 14,000 Example 5 92.4 0.31 107 65 0.063 18,000 Example 6 92.6 0.40 109 65 0.075 12,000 Example 7 92.6 0.31 110 65 0.045 15,000 Example 8 92.3 0.41 106 63 0.060 14,000 Example 9 92.5 0.55 110 65 0.045 15,000 Example 10 92.2 0.32 108 63 0.051 18,000 Example 11 92.6 0.35 109 63 0.058 20,000 Example 12 92.3 0.41 109 66 0.074 14,000 Example 13 92.3 0.37 109 62 0.023 12,000 Example 14 92.7 0.31 106 62 0.070 15,000 Example 15 92.1 0.29 107 64 0.062 18,000 Comparative 92.5 0.35 107 65 0.120 4,000 Example 1

(69) As seen from Table 18 and Table 20, Examples 1-11 in which the molar amounts of component (B1), component (B2) and component (B3) were within the following range:

(70) component (B1) 0.1-2 moles,

(71) component (B2) 0.05-2 moles, and

(72) component (B3) 5-8.85 moles

(73) with respect to 9 moles of the isocyanate group in component (A) were dissolved in the ketone solvent and the ester solvent. In particular, it was confirmed that Examples 1, 2, 4-7 and 11 were completely dissolved. On the other hand, it was confirmed that Comparative Examples 1-3 in which the ratio was not within the above range were not dissolved in the ketone solvent and the ester solvent. Similarly, in the evaluation of wiping property of an oil-based ink, Examples 1-15 showed good wiping property while Comparative Examples showed less wiping property in comparison with Examples.

Industrial Applicability

(74) The present invention is suitably applied for forming a surface treating layer on a surface of various base materials.

(75) The present invention includes the following embodiments: Embodiment 1. A composition comprising a compound containing a carbon-carbon double bond obtained by reacting (A) a polyisocyanate which is a trimer of diisocyanate, with (B) a compound having an active hydrogen,
wherein component (B) comprises: (B1) a perfluoropolyether having an active hydrogen, (B2) a silane compound having an active hydrogen, and (B3) a monomer having an active hydrogen and a carbon-carbon double bond a molar amount of an isocyanate group in component (A) is equal to a total molar amount of component (B), and a molar amount of component (B1), component (B2) and component (B3) per 9 moles of the isocyanate group in component (A) are component (B1) 0.1-2 moles, component (B2) 0.05-2 moles, and component (B3) 5-8.85 moles, respectively. Embodiment 2. The composition according to Embodiment 1 wherein component (A) is an isocyanurate type polyisocyanate. Embodiment 3. The composition according to Embodiment 1 or 2 wherein component (B1) is at least one compound of any one of the following general formulae (B1-i) and (B1-ii):
RfPFPE-R.sup.1CH.sub.2OH(B1-i)
HOCH.sub.2R.sup.1PFPE-R.sup.1CH.sub.2OH(B1-ii)
wherein Rf is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; PFPE is a group of the general formula:
(OC.sub.4F.sub.8).sub.a(OC.sub.3F.sub.6).sub.b(OC.sub.2F.sub.4).sub.c(OCF.sub.2).sub.d wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is at least one, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula; and R.sup.1 is each independently a group of the following formula:
(Y).sub.f(CF.sub.2).sub.g(CH.sub.2).sub.h wherein Y is an oxygen atom or a divalent polar group, f, g and h are each independently an integer of 0-50, the sum of f, g and h is at least one, and the occurrence order of the respective repeating units in parentheses is not limited in the formula. Embodiment 4. The composition according to Embodiment 3 wherein component (B1) is at least one compound of the general formula (B1-i). Embodiment 5. The composition according to Embodiment 3 or 4 wherein PFPE is a group of any one of the formulae (i)-(iii):
(OCF.sub.2CF.sub.2CF.sub.2).sub.b(i)
wherein b is an integer of 1-200,
(OCF(CF.sub.3)CF.sub.2).sub.b(ii)
wherein b is an integer of 1-200,
(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.a(OCF.sub.2CF.sub.2CF.sub.2).sub.b(OCF.sub.2CF.sub.2).sub.c(OCF.sub.2).sub.d(iii)
wherein a and b are each independently 0 or an integer of 1-30, c and d are each independently an integer of 1-200, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula. Embodiment 6. The composition according to any one of Embodiments 1-5 wherein component (B2) is at least one compound for the general formula:

(76) ##STR00006##
wherein R.sup.11, R.sup.12, R.sup.13, R.sup.14 and R.sup.15 are each independently an alkyl group or an aryl group; R.sup.16 is a divalent organic group; l and n are each independently 0 or 1; m is an integer of 1-500; o is an integer of 0-20; and p is 0 or 1. Embodiment 7. The composition according to any one of Embodiments 1-6 wherein component (B3) is a compound containing a (meth)acrylate group. Embodiment 8. The composition according to any one of Embodiments 1-7 wherein component (B3) is at least one compound selected from the group consisting of
HO(CH.sub.2CH.sub.2).sub.iOCO(R)CCH.sub.2 wherein a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom, and i is 2-10, for example, 2-2-hydroxyethyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate;
CH.sub.3CH(OH)CH.sub.2OCO(R)CCH.sub.2 wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or n alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
CH.sub.3CH.sub.2CH(OH)CH.sub.2OCO(R)CCH.sub.2 wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
C.sub.6H.sub.5OCH.sub.2CH(OH)CH.sub.2OCO(R)CCH.sub.2 wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
HOCH.sub.2C(CH.sub.2OCO(R)CCH.sub.2).sub.3 wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
C(CH.sub.2OCO(R)CCH.sub.2).sub.3CH.sub.2OCH.sub.2C(CH.sub.2OCO(R)CCH.sub.2).sub.2CH.sub.2OH wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
HOCH.sub.2CH.sub.2OCOC.sub.6H.sub.5OCOCH.sub.2CH.sub.2OCO(R)CCH.sub.2 wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
H(OCH.sub.2CH.sub.2).sub.nOCO(R)CCH.sub.2 wherein n is 1-30, and R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
H(OCH(CH.sub.3)CH.sub.2).sub.nOCO(R)CCH.sub.2 wherein n is 1-30, and R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom; an allylalcohol;
HO(CH.sub.2).sub.kCHCH.sub.2 wherein k is 2-20;
(CH.sub.3).sub.3SiCH(OH)CHCH.sub.2; and styrylphenol. Embodiment 9. The composition according to any one of Emboidments 1-8 wherein the reaction of component (A) with component (B) is conducted by reacting a portion of the isocyanate group component (A) with component (B1) and component (B2), and then the rest of the isocyanate group with component (B3). Embodiment 10. The composition according to any one of Embodiments 1-8, obtained by reacting component (A) with component (B1) and (B3) to provide the first composition, reacting component (A) with component (B2) and (B3) to provide the second composition, and then, mixing the first composition and the second composition. Embodiment 11. The composition according to Embodiment 10, obtained by reacting component (A) with component (B1) followed by component (B3) to provide the first composition, by reaction component (A) with component (B2) and then component (B3) to provide the second composition. Embodiment 12. The composition according to any one of Embodiments 1-11, comprising at least one fluorine-containing oil of the following general formula (C):
Rf.sup.1PFPE-Rf.sup.2(C)
wherein: Rf.sup.1 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; Rf.sup.2 is a hydrogen atom, a fluorine atom, or an alkyl group (for example, straight or branched) having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; and PFPE is a group of the general formula:
(OC.sub.4F.sub.8).sub.a(OC.sub.3F.sub.6).sub.b(OC.sub.2F.sub.4).sub.c(OCF.sub.2).sub.d
wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is at least one, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula. Embodiment 13. A surface treatment composition comprising one or more compositions according to any one of Embodiments 1-12. Embodiment 14. The surface treatment composition according to Embodiment 13, comprising a solvent of 5-10,000 parts by mass with respect to the total 100 parts by mass of the composition according to any one of claims 1-12. Embodiment 15. The surface treatment composition according to Embodiment 14 wherein the solvent is a fluorine-free organic solvent. Embodiment 16. The surface treatment composition according to Embodiment 14 wherein the solvent is a mixed solvent of a fluorine-free organic solvent and a fluorine-containing organic solvent. Embodiment 17. The surface treatment composition according to any one of Embodiments 13-16, comprising an active energy curing initiator. Embodiment 18. A curable composition comprising one or more compositions according to any one of Embodiments 1-12; and a matrix forming composition. Embodiment 19. The curable composition according to claim 18 comprising a solvent of 0-19,900 parts by mass with respect to the total 100 parts by mass of the composition according to any one of Embodiments 1-12 and the matrix forming composition. Embodiment 20. The curable composition according to Embodiment 19 wherein the solvent is a fluorine-free organic solvent. Embodiment 21. The curable composition according to Embodiment 19 wherein the solvent is a mixed solvent of a fluorine-free organic solvent and a fluorine-containing organic solvent. Embodiment 22. The curable composition according to any one of Embodiments 18-21 comprising an active energy curing initiator. Embodiment 23. The curable composition according to any one of Embodiments 18-22 comprising the composition according to any one of claims 1-12 of 0.01-10% by mass with respect to the total of the matrix forming composition and the composition according to any one of claims 1-12. Embodiment 24. An article comprising a base material and a layer which is formed on a surface of the base material from the surface treatment composition according to any one of claims 13-17 or the curable composition according to any one of Embodiments 18-23. Embodiment 25. The article according to Embodiment 24 which is an optical member.