Surface treatment agent

Abstract

wherein, each of symbols is as defined in the specification, wherein a proportion of the perfluoro(poly)ether group containing silane compound having a molecular weight of 3,000 or less in the perfluoro(poly)ether group containing silane compounds of any of the above general formulae is 9 mol % or less.

1 . A surface-treating agent comprising at least one perfluoro(poly)ether group containing silane compound of any of the formulae (A1), (A2), (B1), (B2), (C1) and (C2): 
       
         
           
           
               
               
           
         
       
       wherein:
 PFPE is each independently at each occurrence a group of the formula:
   —(OC 4 F 8 ) a —(OC 3 F 6 ) b —(OC 2 F 4 ) c —(OCF 2 ) d —
 
 wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is 1 or more, 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; 
 
 Rf is each independently at each occurrence an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; 
 R 1  is each independently at each occurrence a hydrogen atom or an alkyl group having 1-22 carbon atoms; 
 R 2  is each independently at each occurrence a hydroxyl group or a hydrolyzable group; 
 R 11  is each independently at each occurrence a hydrogen atom or a halogen atom; 
 R 12  is each independently at each occurrence a hydrogen atom or a lower alkyl group; 
 n is, independently per a unit (—SiR 1   n R 2   3-n ), an integer of 0-3; 
 there is at least one R 2  in the formulae (A1), (A2), (B1) and (B2); 
 X 1  is each independently a single bond or a 2-10 valent organic group; 
 X 2  is each independently at each occurrence a single bond or a divalent organic group; 
 t is each independently at each occurrence an integer of 1-10; 
 α is each independently an integer of 1-9; 
 α′ is each independently an integer of 1-9; 
 X 5  is each independently a single bond or a 2-10 valent organic group; 
 β is each independently an integer of 1-9; 
 β′ is each independently an integer of 1-9; 
 X 7  is each independently a single bond or a 2-10 valent organic group; 
 γ is each independently an integer of 1-9; 
 γ′ is each independently an integer of 1-9; 
 R a  is each independently at each occurrence —Z—SiR 71   p R 72   q R 73   r ; 
 Z is each independently at each occurrence an oxygen atom or a divalent organic group; 
 R 71  is each independently at each occurrence R a′ ; 
 R a′  has the same definition as that of R a ; 
 in R a , the number of Si atoms which are straightly linked via the Z group is up to five; 
 R 72  is each independently at each occurrence a hydroxyl group or a hydrolyzable group; 
 R 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 a , the sum of p, q and r is 3, and there is at least one R 72  in the formula (C1) and (C2); 
 R b  is each independently at each occurrence a hydroxyl group or a hydrolyzable group; 
 R 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 1-3; 
 1 is each independently at each occurrence an integer of 0-2; 
 m is each independently at each occurrence an integer of 0-2; and 
 the sum of k, l and m is 3 in each unit in parentheses with the subscript γ, 
 
       wherein a proportion of the perfluoro(poly)ether group containing silane compound having a molecular weight of 3,000 or less in the perfluoro(poly)ether group containing silane compounds of any of the above general formulae is 9 mol % or less. 
     
     
         2 . The surface-treating agent according to  claim 1  wherein the proportion of the perfluoro(poly)ether group containing silane compound having a molecular weight of 3,000 or less in the perfluoro(poly)ether group containing silane compounds of any of the above general formulae is 7 mol % or less. 
     
     
         3 . The surface-treating agent according to  claim 1  wherein the proportion of the perfluoro(poly)ether group containing silane compound having a molecular weight of 3,000 or less in the perfluoro(poly)ether group containing silane compounds of any of the above general formulae is 5 mol % or less. 
     
     
         4 . The surface-treating agent according to  claim 1  wherein Rf is a perfluoroalkyl group having 1-16 carbon atoms. 
     
     
         5 . The surface-treating agent according to  claim 1  wherein PFPE is a group of any of the following formulas (i) to (iv):
   —(OCF 2 CF 2 CF 2 ) b —  (i)
 
 wherein b is an integer of 1-200;
   —(OCF(CF 3 )CF 2 ) b —  (ii)
 
 
 wherein b is an integer of 1-200;
   —(OCF 2 CF 2 CF 2 CF 2 ) a —(OCF 2 CF 2 CF 2 ) b —(OCF 2 CF 2 ) c —(OCF 2 ) 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; 
 or
   —(OC 2 F 4 —R 8 ) f —  (iv)
 
 
 wherein R 8  is a group selected from OC 2 F 4 , OC 3 F 6  and OC 4 F 8 ; and
 f is an integer of 2-100. 
 
 
     
     
         6 . The surface-treating agent according to  claim 1  wherein X 1 , X 5  and X 7  are each independently a 2-4 valent organic group, α, β and γ are each independently 1-3, and α′, β′ and γ′ are 1. 
     
     
         7 . The surface-treating agent according to  claim 1  wherein X 1 , X 5  and X 7  are a divalent organic group, α, β and γ are 1, and a′, β′ and γ′ are 1. 
     
     
         8 . The surface-treating agent according to  claim 7  wherein X 1 , X 5  and X 7  are each independently —(R 31 ) p′ —(X a ) q′ —
 wherein:
 R 31  is a single bond, —(CH 2 ) s′ — (wherein s′ is an integer of 1-20) or a o-, m- or p-phenylene group; 
 X a  is —(X b ) 1′ — (wherein 1′ is an integer of 1-10); 
 X b  is each independently at each occurrence selected from the group consisting of —O—, —S—, an o-, m- or p-phenylene group, —C(O)O—, —Si(R 33 ) 2 —, —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 — (wherein m′ is an integer of 1-100), —CONR 34 —, —O—CONR 34 —, —NR 34 — and —(CH 2 ) n′ — (wherein n′ is an integer of 1-20); 
 R 33  is each independently at each occurrence a phenyl group, a C 1-6  alkyl group or a C 1-6  alkoxy group; 
 R 34  is each independently at each occurrence a hydrogen atom, a phenyl group or a C 1-6  alkyl group; 
 p′ is 0 or 1; 
 q′ is 0 or 1; 
 at least one of p′ and q′ is 1, 
 the occurrence order of the respective repeating units in parentheses with the subscript p′ or q′ is not limited in the formula; and 
 R 31  and X a  is may be substituted with one or more substituents selected from a fluorine atom, a C 1-3  alkyl group and a C 1-3  fluoroalkyl group. 
 
 
     
     
         9 . The surface-treating agent according to  claim 7  wherein X 1 , X 5  and X 7  are each independently selected from the group consisting of:
 —CH 2 O(CH 2 ) 2 —, 
 —CH 2 O(CH 2 ) 3 —, 
 —CH 2 O(CH 2 ) 6 —, 
 —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, 
 —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, 
 —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —, 
 —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —, 
 —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —, 
 —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —, 
 —CH 2 OCF 2 CHFOCF 2 —, 
 —CH 2 OCF 2 CHFOCF 2 CF 2 —, 
 —CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —, 
 —CH 2 OCH 2 CF 2 CF 2 OCF 2 —, 
 —CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 —, 
 —CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2 —, 
 —CH 2 OCH 2 CF 2 CF 2 OCF(CF 3 )CF 2 OCF 2 —, 
 —CH 2 OCH 2 CF 2 CF 2 OCF(CF 3 )CF 2 OCF 2 CF 2 —, 
 —CH 2 OCH 2 CF 2 CF 2 OCF(CF 3 )CF 2 OCF 2 CF 2 CF 2 —, 
 —CH 2 OCH 2 CHFCF 2 OCF 2 —, 
 —CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 —, 
 —CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2 —, 
 —CH 2 OCH 2 CHFCF 2 OCF(CF 3 )CF 2 OCF 2 —, 
 —CH 2 OCH 2 CHFCF 2 OCF(CF 3 )CF 2 OCF 2 CF 2 —, 
 —CH 2 OCH 2 CHFCF 2 OCF(CF 3 )CF 2 OCF 2 CF 2 CF 2 — 
 —CH 2 OCH 2 (CH 2 ) 7 CH 2 Si(OCH 3 ) 2 OSi(OCH 3 ) 2 (CH 2 ) 2 Si(OCH 3 ) 2 OSi(OCH 3 ) 2 (CH 2 ) 2 —, 
 —CH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 2 OSi(OCH 3 ) 2 (CH 2 ) 3 —, 
 —CH 2 OCH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 2 OSi(OCH 2 CH 3 ) 2 (CH 2 ) 3 —, 
 —CH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 2 OSi(OCH 3 ) 2 (CH 2 ) 2 —, 
 —CH 2 OCH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 2 OSi(OCH 2 CH 3 ) 2 (CH 2 ) 2 —, 
 —(CH 2 ) 2 —, 
 —(CH 2 ) 3 —, 
 —(CH 2 ) 4 —, 
 —(CH 2 ) 6 —, 
 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 — 
 —CONH—(CH 2 ) 3 —, 
 —CON(CH 3 )—(CH 2 ) 3 —, 
 —CON(Ph)-(CH 2 ) 3 — (wherein Ph is a phenyl group), 
 —CONH—(CH 2 ) 6 —, 
 —CON(CH 3 )—(CH 2 ) 6 —, 
 —CON(Ph)-(CH 2 ) 6 — (wherein Ph is a phenyl group), 
 —CONH—(CH 2 ) 2 NH(CH 2 ) 3 —, 
 —CONH—(CH 2 ) 6 NH(CH 2 ) 3 —, 
 —CH 2 O—CONH—(CH 2 ) 3 —, 
 —CH 2 O—CONH—(CH 2 ) 6 —, 
 —S—(CH 2 ) 3 —, 
 —(CH 2 ) 2 S(CH 2 ) 3 —, 
 —CONH—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, 
 —CONH—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, 
 —CONH—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —, 
 —CONH—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —, 
 —CONH—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —, 
 —CONH—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 — 
 —C(O)O—(CH 2 ) 3 —, 
 —C(O)O—(CH 2 ) 6 —, 
 —CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —, 
 —CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—, 
 —CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 3 —, 
 —CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—CH 2 —, 
 
       
         
           
           
               
               
           
         
       
     
     
         10 . The surface-treating agent according to  claim 1  wherein
 X 1  is —O—CFR 13 —(CF 2 ) e —, 
 R 13  is a fluorine atom or a lower fluoroalkyl group, and 
 e is 0 or 1. 
 
     
     
         11 . The surface-treating agent according to  claim 1  wherein
 X 2  is —(CH 2 ) s —, and 
 s is an integer of 0-2. 
 
     
     
         12 . The surface-treating agent according to  claim 1  wherein k is 3, and q is 3 in R a . 
     
     
         13 . The surface-treating agent according to  claim 1  wherein X 1 , X 5  and X 7  are each independently a 3-10 valent organic group. 
     
     
         14 . The surface-treating agent according to  claim 13  wherein X 1 , X 5  and X 7  are each independently selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein in each group, at least one of T is the following group attached to PFPE in the formulae (A1), (A2), (B1), (B2), (C1) and (C2): 
         —CH 2 O(CH 2 ) 2 —, 
         —CH 2 O(CH 2 ) 3 —, 
         —CF 2 O(CH 2 ) 3 —, 
         —(CH 2 ) 2 —, 
         —(CH 2 ) 3 —, 
         —(CH 2 ) 4 —, 
         —CONH—(CH 2 ) 3 —, 
         —CON(CH 3 )—(CH 2 ) 3 —, 
         —CON(Ph)-(CH 2 ) 3 — (wherein Ph is a phenyl group), and 
       
       
         
           
           
               
               
           
         
         
           at least one of the other T is —(CH 2 ) n — (wherein n is an integer of 2-6) attached to the carbon atom or the Si atom in the formulae (A1), (A2), (B1), (B2), (C1) and (C2) and the others are each independently a methyl group, a phenyl group, a alkoxy having 1-6 carbon atoms, or a radical scavenger group or an ultraviolet ray absorbing group, 
           R 41  is each independently a hydrogen atom, a phenyl group, an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and 
           R 42  is each independently a hydrogen atom, a C 1-6  alkyl group or a C 1-6  alkoxy group. 
         
       
     
     
         15 . The surface-treating agent according to  claim 1  wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any of the formulae (A1) and (A2). 
     
     
         16 . The surface-treating agent according to  claim 1  wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any of the formulae (B1) and (B2). 
     
     
         17 . The surface-treating agent a  claim 1  wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any of the formulae (C1) and (C2). 
     
     
         18 . The surface-treating agent according to  claim 1  further comprising one or more components selected form a fluorine-containing oil, a silicone oil and a catalyst. 
     
     
         19 . The surface-treating agent according to  claim 18  wherein the fluorine-containing oil is one or more compounds of the formula (3):
   R 21 —(OC 4 F 8 ) a′ —(OC 3 F 6 ) b′ —(OC 2 F 4 ) c′ —(OCF 2 ) d′ —R 22   (3)
 
 wherein:
 R 21  is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; 
 R 22  is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; and 
 a′, b′, c′ and d′ are the repeating number of each of four repeating units of perfluoro(poly)ether which constitute a main backbone of the polymer, and are each independently an integer of 0 or more and 300 or less, the sum of a′, b′, c′ and d′ is 1 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a′, b′, c′ and d′ is not limited in the formula. 
 
 
     
     
         20 . The surface-treating agent according to  claim 18  wherein the fluorine-containing oil is one or more compounds of the formula (3a) or (3b):
   R 21 —(OCF 2 CF 2 CF 2 ) b″ —R 22   (3a)
 
   R 21 —(OCF 2 CF 2 CF 2 CF 2 ) a″ —(OCF 2 CF 2 CF 2 ) b″ —(OCF 2 CF 2 ) c″ —(OCF 2 ) d″ —R 22   (3b)
 
 wherein:
 R 21  is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; 
 R 22  is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; 
 in the formula (3a), b″ is an integer of 1 or more and 100 or less; 
 in the formula (3b), a″ and b″ are each independently an integer of 0 or more and 30 or less, and c″ and d″ are each independently an integer of 1 or more and 300 or less; 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. 
 
 
     
     
         21 . The surface-treating agent according to  claim 20  wherein a mass ratio of the perfluoro(poly)ether group containing silane compound and the compound of the formula (3b) is 10:1-1:10. 
     
     
         22 . The surface-treating agent according to  claim 20  wherein a mass ratio of the perfluoro(poly)ether group containing silane compound and the compound of the formula (3b) is 4:1-1:4. 
     
     
         23 . The surface-treating agent according to  claim 20  wherein the compound of the formula (3a) has a number average molecular weight of 2,000-8,000. 
     
     
         24 . The surface-treating agent according to  claim 20  wherein the compound of the formula (3b) has a number average molecular weight of 8,000-30,000. 
     
     
         25 . The surface-treating agent according to  claim 20  wherein the compound of the formula (3b) has a number average molecular weight of 3,000-8,000. 
     
     
         26 . The surface-treating agent according to  claim 1  further comprising a solvent. 
     
     
         27 . The surface-treating agent according to  claim 1  which is used as an antifouling-coating agent or a water-proof coating agent. 
     
     
         28 . The surface-treating agent according to  claim 1  for vacuum deposition. 
     
     
         29 . A pellet comprising the surface-treating agent according to  claim 1 . 
     
     
         30 . 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 1 . 
     
     
         31 . The article according to  claim 30  wherein the base material is a glass or a sapphire glass. 
     
     
         32 . The article according to  claim 31  wherein the glass is a glass selected from the group consisting of a soda-lime glass, an alkali aluminosilicate glass, a borosilicate glass, a non-alkaline glass, a crystal glass, and a quartz glass. 
     
     
         33 . The article according to  claim 30  wherein the article is an optical member. 
     
     
         34 . The article according to  claim 30  wherein the article is a display.