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CN-115803362-B - Curable composition

CN115803362BCN 115803362 BCN115803362 BCN 115803362BCN-115803362-B

Abstract

The invention provides a fluorinated polyether group-containing silane compound represented by the formula (I) [ the meanings of each symbol are as described in the specification ].

Inventors

  • Maru Kazuki
  • HONDA YOSHIAKI
  • MITSUHASHI HISASHI

Assignees

  • 大金工业株式会社

Dates

Publication Date
20260512
Application Date
20210701
Priority Date
20200702

Claims (15)

  1. 1. A fluorinated polyether group-containing silane compound represented by the following formula (I), In the formula, R 3 is independently at each occurrence a hydrogen atom or a 1-valent organic group, R 4 is independently at each occurrence a hydroxyl or a hydrolyzable group, P is an integer of 0 to 3 independently at each occurrence; Wherein (in SiR 3 p R 4 3－p ) j , p in at least 1 SiR 3 p R 4 3－p is an integer of 0 to 2, Q is an integer of 0 to 3 independently for each occurrence; wherein q in at least 1 SiR 3 q R 4 3 － q is an integer of 0 to 2 in (SiR 3 q R 4 3 － q ) j ), R 5 is independently at each occurrence a j+1 valent organic group, R 6 is independently at each occurrence-R 16 －R 15 －R 17 -, R 15 is independently at each occurrence a cycloalkylene-containing group, R 16 is independently at each occurrence a single bond or a C 1－6 alkylene group, R 17 is independently at each occurrence a single bond or a C 1－6 alkylene group, R 7 is independently at each occurrence a hydrogen atom or a C 1－20 alkyl group, PFPE 1 is independently at each occurrence-R F －R FE -, R F is- (C f F 2f ) -, F is an integer of 1 to 10, R FE is a 2-valent fluoropolyether group represented by formula ：－(OCF 2 ) a1 －(OC 2 F 4 ) a2 －(OC 3 X 10 6 ) a3 －(OC 4 F 8 ) a4 －(OC 5 F 10 ) a5 －(OC 6 F 12 ) a6 －(OC 7 F 14 ) a7 －(OC 8 F 16 ) a8 －, Wherein a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer of 0 to 200, the sum of a1, a2, a3, a4, a5, a6, a7 and a8 is at least 5, The order of the presence of the repeating units denoted by the subscripts a1, a2, a3, a4, a5, a6, a7, or a8 and bracketed is arbitrary in the formula, X 10 is independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom, wherein when all X 10 is a hydrogen atom or a chlorine atom, at least 1 of a1, a2, a4, a5, a6, a7 and a8 is an integer of 1 or more, J is independently at each occurrence an integer of 1 to 9, K is an integer of 1 or more.
  2. 2. The fluoropolyether-based silane compound according to claim 1, R 15 is independently a group containing a monocyclic, bicyclic or tricyclic cycloalkylene group having 5 to 12 carbon atoms, R 16 is independently at each occurrence a single bond or a C 1－6 alkylene group, R 17 is independently a single bond or C 1－6 alkylene at each occurrence.
  3. 3. The fluoropolyether-based silane compound according to claim 1 or 2, R 6 is a group selected from the group consisting of a hydrogen atom on a ring which may be substituted, In the formula, R 16 is independently at each occurrence a single bond or a C 1－6 alkylene group, R 17 is independently at each occurrence a single bond or a C 1－6 alkylene group, R 18 is independently at each occurrence C 1－6 alkylene.
  4. 4. The fluoropolyether-based silane compound according to claim 1 or 2, wherein X 10 is a fluorine atom.
  5. 5. The fluoropolyether-based silane compound according to claim 1 or 2, R FE is independently at each occurrence a group of the formula (f 1), (f 2), (f 3), (f 4) or (f 5), -(OC 3 F 6 ) a3 －(OC 2 F 4 ) a2 - (f1) In the formula (f 1), a3 is an integer of 5 to 200, a2 is 0 or 1, －(OC 4 F 8 ) a4 －(OC 3 F 6 ) a3 －(OC 2 F 4 ) a2 －(OCF 2 ) a1 － (f2) In the formula (f 2), a3 and a4 are each independently an integer of 0 to 30; a1 and a2 are each independently an integer of 1 to 200; The sum of a1, a2, a3 and a4 is an integer of 10 to 200; The order of the presence of the repeating units indicated by the subscripts a1, a2, a3, or a4 and bracketed is arbitrary in the formula, -(R 16 －R 17 ) g - (f3) In the formula (f 3), R 16 is OCF 2 or OC 2 F 4 ; R 17 is a group selected from OC 2 F 4 、OC 3 F 6 、OC 4 F 8 、OC 5 F 10 and OC 6 F 12 , or a combination of 2 or 3 groups selected from these groups; g is an integer of 2 to 100, －(OC 6 F 12 ) a6 －(OC 5 F 10 ) a5 －(OC 4 F 8 ) a4 －(OC 3 F 6 ) a3 －(OC 2 F 4 ) a2 －(OCF 2 ) a1 － (f4) In the formula (f 4), a2 is an integer of 1 to 200, a1, a3, a4, a5 and a6 are each independently an integer of 0 to 200, the sum of a1, a2, a3, a4, a5 and a6 is at least 5, and the order of the presence of the repeating units denoted by a1, a2, a3, a4, a5 or a6 and bracketed is arbitrary in the formula, －(OC 6 F 12 ) a6 －(OC 5 F 10 ) a5 －(OC 4 F 8 ) a4 －(OC 3 F 6 ) a3 －(OC 2 F 4 ) a2 －(OCF 2 ) a1 － (f5) In the formula (f 5), a1 is an integer of 1 to 200, a2, a3, a4, a5 and a6 are each independently an integer of 0 to 200, the sum of a1, a2, a3, a4, a5 and a6 is at least 5, and the order of the presence of the repeating units denoted by a1, a2, a3, a4, a5 or a6 and bracketed is arbitrary in the formula.
  6. 6. The fluoropolyether-based silane compound according to claim 1 or 2, wherein R 7 is a hydrogen atom.
  7. 7. The fluoropolyether-based silane compound according to claim 1 or 2, wherein R 5 is a divalent organic group and j is 1.
  8. 8. The fluoropolyether-based silane compound according to claim 1 or 2, wherein R 5 is C 1－6 alkylene and j is 1.
  9. 9. The fluoropolyether-based silane compound according to claim 1 or 2, wherein the compound is represented by formula (A), (B), (C) or (D), In the formula, R 11 and R 11″ are each independently at each occurrence a hydrogen atom or a halogen atom, R 12 and R 12″ are each independently at each occurrence a hydrogen atom or a lower alkyl group, R 13 and R 13″ are each independently at each occurrence a hydroxyl or a hydrolyzable group, R 14 and R 14″ are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, X 2 is independently a single bond or a 2-valent organic group at each occurrence, N1 is independently an integer of 0 to 3 in each (-SiR 13 n1 R 14 3－n1 ) unit or each (-SiR 13″ n1 R 14″ 3－n1 ) unit, X 1 is independently a single bond or a 2-10-valent organic group connected with an amide bond, T is an integer of 1 to 10 independently, Alpha 1 is an integer of 1 to 9, X 3 is each independently a 2-10 valent organic group, Beta 1 is an integer of 1 to 9, X 5 is each independently a 2-10 valent organic group, Gamma 1 is an integer of 1 to 9, R a is independently at each occurrence-Z 3 －SiR 71 p1 R 72 q1 R 73 r1 , Z 3 is independently at each occurrence an oxygen atom or a 2-valent organic group, R 71 is independently at each occurrence R a′ , R a′ has the same meaning as R a , In R a , at most 5 Si are linked in a straight chain through Z 3 group, R 72 is independently at each occurrence a hydroxyl or a hydrolyzable group, R 73 is independently at each occurrence a hydrogen atom or lower alkyl, P1 is an integer of 0 to 3 independently at each occurrence, Q1 is an integer of 0 to 3 independently for each occurrence, R1 is an integer of 0 to 3 independently at each occurrence, Wherein in each (-Z 3 －SiR 71 p1 R 72 q1 R 73 r1 ), the sum of p1, q1 and r1 is 3, R a″ is independently at each occurrence-Z 3 －SiR 71 p1 R 72″ q1 R 73 r1 , Z 3 、R 71 、R 73 , p1, q1 and r1 have the meaning given above, R 72″ has the same meaning as R 72 , R b and R b″ are each independently at each occurrence a hydroxyl or a hydrolyzable group, R c and R c″ are each independently at each occurrence a hydrogen atom or a lower alkyl group, K1 is independently an integer of 0 to 3 at each occurrence, L1 is an integer of 0 to 3 independently at each occurrence, M1 is an integer of 0 to 3 independently at each occurrence, Wherein in each (SiR a k1 R b l1 R c m1 ) or each (SiR a″ k1 R b″ l1 R c″ m1 ), the sum of k1, l1 and m1 is 3, X 7 is each independently a 2-10 valent organic group, Δ1 is an integer of 1 to 9, R d is independently at each occurrence-Z 4 －CR 81 p2 R 82 q2 R 83 r2 , Z 4 is independently at each occurrence an oxygen atom or a 2-valent organic group, R 81 is independently at each occurrence R d′ , R d′ has the same meaning as R d , R 82 is independently at each occurrence-Y-SiR 85 n2 R 86 3－n2 , Y is independently at each occurrence a 2-valent organic group, R 85 is independently at each occurrence a hydroxyl or a hydrolyzable group, R 86 is independently at each occurrence a hydrogen atom or lower alkyl, N2 is independently an integer of 0 to 3 in each (-Y-SiR 85 n2 R 86 3－n2 ) unit or each (-Y-SiR 85″ n2 R 86″ 3 － n2 ) unit, R 83 is independently at each occurrence a hydrogen atom, hydroxy or lower alkyl, P2 is independently an integer of 0 to 3 at each occurrence, Q2 is an integer of 0 to 3 independently for each occurrence, R2 is independently an integer of 0 to 3 at each occurrence, Wherein, in each (-Z 4 －CR 81 p2 R 82 q2 R 83 r2 ) or each (-Z 4 －CR 81 p2 R 82″ q2 R 83 r2 ), the sum of p2, q2 and r2 is 3, R d″ is independently at each occurrence-Z 4 －CR 81 p2 R 82″ q2 R 83 r2 , R 82″ is independently at each occurrence-Y-SiR 85″ n2 R 86″ 3－n2 , R 85″ and R 86 ″ have the same meaning as R 85 and R 86 , respectively, R e is independently at each occurrence-Y-SiR 85 n2 R 86 3－n2 , R e″ is independently at each occurrence-Y-SiR 85″ n2 R 86″ 3－n2 , R f and R f″ are each independently at each occurrence a hydrogen atom, a hydroxy group or a lower alkyl group, Each occurrence of k2 is an integer of 0 to 3, L2 is independently an integer of 0 to 3 at each occurrence, M2 is an integer of 0 to 3 independently at each occurrence, Wherein the sum of k2, l2 and m2 is 3, R 6 is independently at each occurrence-R 16 －R 15 －R 17 -, R 15 is independently at each occurrence a cycloalkylene-containing group, R 16 is independently at each occurrence a single bond or a C 1－6 alkylene group, R 17 is independently at each occurrence a single bond or a C 1－6 alkylene group, R 7 is independently at each occurrence a hydrogen atom or a C 1－20 alkyl group, PFPE 1 is independently at each occurrence-R F －R FE -, R F is- (C f F 2f ) -, F is an integer of 1 to 10, R FE is a 2-valent fluoropolyether group represented by formula ：－(OCF 2 ) a1 －(OC 2 F 4 ) a2 －(OC 3 X 10 6 ) a3 －(OC 4 F 8 ) a4 －(OC 5 F 10 ) a5 －(OC 6 F 12 ) a6 －(OC 7 F 14 ) a7 －(OC 8 F 16 ) a8 －, In the formula, A1, a2, a3, a4, a5, a6, a7 and a8 are each independently integers from 0 to 200, the sum of a1, a2, a3, a4, a5, a6, a7 and a8 being at least 5, The order of the presence of the repeating units denoted by the subscripts a1, a2, a3, a4, a5, a6, a7, or a8 and bracketed is arbitrary in the formula, X 10 is independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom, wherein when all X 10 is a hydrogen atom or a chlorine atom, at least 1 of a1, a2, a4, a5, a6, a7 and a8 is an integer of 1 or more, R is an integer of 1 or more.
  10. 10. A surface treatment agent, which is characterized in that, A silane compound containing a fluoropolyether group according to any one of claims 1 to 9.
  11. 11. The surface treatment agent according to claim 10, Further comprises 1 or more other components selected from fluorine-containing oil, silicone oil and catalyst.
  12. 12. The surface treatment agent according to claim 10 or 11, wherein, And further comprises a solvent.
  13. 13. The surface treatment agent according to claim 10 or 11, wherein, As an antifouling coating agent or a water-repellent coating agent.
  14. 14. An article, comprising: Substrate and method for producing the same A layer formed of the fluorinated polyether-based silane compound according to any one of claims 1 to 9 or the surface treatment agent according to any one of claims 10 to 13 on the surface of the substrate.
  15. 15. The article of claim 14, wherein the article is an optical component.

Description

Curable composition Technical Field The present invention relates to a surface treatment agent. Background It is known that certain types of fluorosilane compounds are capable of providing excellent water repellency, oil repellency, stain resistance, and the like when used for the surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorosilane compound (hereinafter also referred to as "surface treatment layer") is applied as a so-called functional film to various substrates such as glass, plastic, fiber, building material, and the like. As such fluorine-containing compounds, perfluoropolyether group-containing silane compounds having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part are known (patent documents 1 and 2). Prior art literature Patent literature Patent document 1 Japanese patent application laid-open No. 2014-218639 Patent document 2 Japanese patent application laid-open No. 2017-08284 Disclosure of Invention Technical problem to be solved by the invention The layer obtained from the surface treatment agent containing the perfluoropolyether group-containing silane compound is suitable for use in optical parts such as spectacles and touch panels, where light transmittance and transparency are required, because it can exhibit functions such as water repellency, oil repellency, and stain resistance even in the case of a film. In particular, in these applications, friction durability is required in order to maintain the function even when repeatedly rubbed. The purpose of the present invention is to provide a fluorinated polyether-based silane compound capable of forming a layer having high friction durability. Technical scheme for solving technical problems The present invention includes the following means. [1] A fluorinated polyether group-containing silane compound represented by the following formula (I). [ In the above-mentioned, a method for producing a semiconductor device, R 3 is independently at each occurrence a hydrogen atom or a 1-valent organic group, R 4 is independently at each occurrence a hydroxyl or a hydrolyzable group, P is an integer of 0 to 3 independently at each occurrence; Wherein (in SiR 3pR43-p)j, p in at least 1 SiR 3pR43-p is an integer of 0 to 2, Q is an integer of 0 to 3 independently for each occurrence; Wherein q in at least 1 SiR 3qR43-q is an integer of 0 to 2 in (SiR 3qR43-q)j), R 5 is independently at each occurrence a j+1 valent organic group, R 6 is independently at each occurrence-R 16－R15－R17 -, R 15 is independently at each occurrence a cycloalkylene-containing group, R 16 is independently at each occurrence a single bond or a divalent organic group, R 17 is independently at each occurrence a single bond or a divalent organic group, R 7 is independently at each occurrence a hydrogen atom or a C 1-20 alkyl group, PFPE 1 is independently at each occurrence-R F－RFE -, R F is- (C fF2f) -, F is an integer of 1 to 10, R FE is a 2-valent fluoropolyether group represented by formula ：－(OCF2)a1－(OC2F4)a2－(OC3X106)a3－(OC4F8)a4－(OC5F10)a5－(OC6F12)a6－(OC7F14)a7－(OC8F16)a8－, (In the formula (I), A1, a2, a3, a4, a5, a6, a7 and a8 are each independently integers from 0 to 200, the sum of a1, a2, a3, a4, a5, a6, a7 and a8 being at least 5, The order of the presence of the repeating units denoted by the subscripts a1, a2, a3, a4, a5, a6, a7, or a8 and bracketed is arbitrary in the formula, Each occurrence of X 10 is independently a hydrogen atom, a fluorine atom, or a chlorine atom, wherein when all X 10 are a hydrogen atom or a chlorine atom, at least 1 of a1, a2, a4, a5, a6, a7, and a8 is an integer of 1 or more. ) J is independently at each occurrence an integer of 1 to 9, K is an integer of 1 or more. ] [2] The fluoropolyether-group-containing silane compound according to [1] above, wherein R 15 is independently a group containing a monocyclic, bicyclic or tricyclic cycloalkylene group having 5 to 12 carbon atoms at each occurrence, R 16 is independently at each occurrence a single bond or a C 1-6 alkylene group, R 17 is independently a single bond or C 1-6 alkylene at each occurrence. [3] The fluoropolyether group-containing silane compound according to [1] or [2] above, wherein R 6 is a group selected from the group consisting of a hydrogen atom on the ring, which may be substituted. [ In the above-mentioned, a method for producing a semiconductor device, R 16 is independently at each occurrence a single bond or a C 1-6 alkylene group, R 17 is independently at each occurrence a single bond or a C 1-6 alkylene group, R 18 is independently at each occurrence C 1-6 alkylene. ] [4] A fluorinated polyether-based silane compound according to any one of the above [1] to [3], wherein X 10 is a fluorine atom. [5] The fluoropolyether-based silane compound according to any one of the above [1] to [4], wherein R FE is each independently a group