CN116694203A - Surface treating agent - Google Patents
Surface treating agent Download PDFInfo
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- CN116694203A CN116694203A CN202310175852.3A CN202310175852A CN116694203A CN 116694203 A CN116694203 A CN 116694203A CN 202310175852 A CN202310175852 A CN 202310175852A CN 116694203 A CN116694203 A CN 116694203A
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- 239000000203 mixture Substances 0.000 claims abstract description 142
- 150000001875 compounds Chemical class 0.000 claims abstract description 99
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 58
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011737 fluorine Substances 0.000 claims abstract description 41
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- 125000000962 organic group Chemical group 0.000 claims description 185
- 125000000217 alkyl group Chemical group 0.000 claims description 117
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 62
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- 239000000758 substrate Substances 0.000 claims description 32
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- 238000001514 detection method Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- 229950011087 perflunafene Drugs 0.000 description 1
- LOQGSOTUHASIHI-UHFFFAOYSA-N perfluoro-1,3-dimethylcyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)C1(F)F LOQGSOTUHASIHI-UHFFFAOYSA-N 0.000 description 1
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Abstract
The present invention addresses the problem of providing a composition capable of forming a layer that has excellent liquid repellency and also has excellent slip properties. The present invention provides a composition comprising (A): crosslinkable compound and component (B): a composition comprising a fluorine-containing liquid-repellent compound, wherein the formula is satisfied: p (P) b －P c > 0[ in the formula: p (P) b P is a value of a polar component ratio in a surface free energy of a layer formed of the fluorine-containing liquid-repellent compound c The value of the polar component ratio in the free energy of the surface of the layer formed from the above composition.]。
Description
Technical Field
The present invention relates to a surface treatment agent.
Background
As compositions for surface treatment of a substrate, there are known a composition containing a fluorine-containing alkoxysilane and a difunctional or higher alkoxysilane (patent document 1) and a composition containing a silane coupling agent and a tetrafunctional alkoxysilane (patent document 2).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2017-186495
Patent document 2: japanese patent laid-open No. 2013-213181
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a composition which can form a layer that has excellent liquid repellency and also has excellent slip properties.
Means for solving the problems
The present invention includes the following embodiments.
[1] A composition comprising:
component (A): crosslinkable compound, and
component (B): a fluorine-containing liquid-repellent compound,
the above composition satisfies the following formula:
P b －P c ＞0
[ formula:
P b the polar component ratio in the surface free energy of the layer formed of the fluorine-containing liquid-repellent compound is set to be a value,
P c the value of the polar component ratio in the free energy of the surface of the layer formed from the above composition.]。
[2] The composition of [1], which satisfies the following formula:
P b －P c ≥3.0。
[3] the composition according to [1] or [2], wherein,
P c is 20.0 or less.
[4] The composition according to any one of [1] to [3], wherein,
the crosslinkable compound has a metal alkoxide group.
[5] The composition according to any one of [1] to [4], wherein,
the crosslinkable compound is a compound represented by the following formula (A1) or (A2):
A[Z a1 －M 1 (OR a1 ) n1 (R a2 ) n2－n1 ] m1 [Z a2 －R a3 ] m2 (A1)
[ formula:
a is an organic group having a valence of 1 to 10,
Z a1 each independently a single bond or a 2-valent organic group,
M 1 al, ca, fe, ge, hf, in, si, ta, ti, sn, zr or Zn;
R a1 each independently is a hydrogen atom or C 1－6 An alkyl group, a hydroxyl group,
R a2 each independently is a hydrogen atom or a hydrocarbon group,
n1 is 1 or more and (M) 1 The valence of (2) is less than-1),
n2 is each independently (M) 1 Valence number-1) of (c) is set to be equal to or lower than the valence number-1),
Z a2 each independently a single bond or a 2-valent organic group,
R a3 each independently a reactive organic group,
m1 is an integer of 1 to 10,
m2 is an integer of 0 to 10,
the sum of m1 and m2 is the valence of A. ]
[ formula:
M 2 al, ca, fe, ge, hf, in, si, ta, ti, sn, zr or Zn;
R a4 are each independently a hydrogen atom, C 1－6 Alkyl or R a6 －CO－；
R a6 A hydrocarbon group having a valence of 1;
R a5 each independently is C 1－3 Alkyl or C 1－3 An alkoxy group;
n3 is M as described above 2 Valence of (2);
n4 is 0 or more and M is as described above 2 Below the valence number of (c).]。
[6] The composition according to [5], wherein,
n1 is 2 or more.
[7] The composition according to [5] or [6], wherein,
r is as described above a1 Is C 1－4 An alkyl group.
[8] The composition according to any one of [5] to [7], wherein,
a is an alkylene group or a group of the formula:
[ formula:
X a each independently a single bond or a 2-valent organic group.]。
[9] The composition according to any one of [5] to [8], wherein,
the reactive organic group is an isocyanate group, an epoxy group or a vinyl group.
[10] The composition according to any one of [1] to [9], wherein,
the fluorine-containing liquid-repellent compound has a fluoroalkyl group or a fluoropolyether group.
[11] The composition according to [10], wherein,
The fluoropolyether group is a group represented by the following formula:
－(OC 6 F 12 ) a －(OC 5 F 10 ) b －(OC 4 F 8 ) c －(OC 3 R Fa 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f －
[ formula, R Fa Each occurrence of which is independently a hydrogen atom, a fluorine atom or a chlorine atom,
a. b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f being 1 or more, the order of presence of the repeating units denoted by a, b, c, d, e or f and bracketed in the formula is arbitrary, wherein, in all R Fa In the case of a hydrogen atom or a chlorine atom, at least 1 of a, b, c, e and f is 1 or more.]。
[12] The composition according to any one of [1] to [11], wherein,
the fluorine-containing liquid-repellent compound is a fluorinated polyether group-containing silane compound represented by the following formula (1) or (2):
R F1 α -X A -R Si β (1)
R Si γ -X A -R F2 -X A -R Si γ (2)
[ in the above-mentioned, a method for producing a semiconductor device,
R F1 each occurrence is independently Rf 1 -or Rf 1 -R F -O q -；
R F2 is-Rf 2 -or-Rf 2 p -R F -O q -；
Rf 1 Each occurrence is independently C which may be substituted with 1 or more fluorine atoms 1-16 An alkyl group;
Rf 2 for C which may be substituted by 1 or more fluorine atoms 1-6 An alkylene group;
R F each occurrence is independently a 2-valent fluoropolyether group;
p is 0 or 1;
q is independently 0 or 1 at each occurrence;
R Si each occurrence is independently a 1-valent group comprising a Si atom to which a hydroxyl group, a hydrolyzable group, or a 1-valent organic group is bonded, or a 1-valent group comprising a reactive organic group;
At least 1R Si A 1-valent group comprising a Si atom to which a hydroxyl group or a hydrolyzable group is bonded, or a 1-valent group comprising a reactive organic group;
X A each independently is a single bond or an organic group having a valence of 2 to 10;
alpha is an integer of 1 to 9;
beta is an integer of 1 to 9;
gamma is an integer of 1 to 9. ].
[13] The composition according to [12], wherein,
R F each occurrence is independently a group of the formula:
-(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 R Fa 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -
[ formula, R Fa Each occurrence is independently a hydrogen atom, a fluorine atom or a chlorine atom, each of a, b, c, d, e and f is independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more, and the order of presence of the repeating units denoted by a, b, c, d, e or f and bracketed in the formula is arbitrary, wherein, in all R Fa In the case of a hydrogen atom or a chlorine atom, at least 1 of a, b, c, e and f is 1 or more.]。
[14] The composition according to [12] or [13], wherein,
R F each occurrence is independently a group represented by the following formula (f 1), formula (f 2), formula (f 3), formula (f 4), formula (f 5) or formula (f 6):
－(OC 3 F 6 ) d －(OC 2 F 4 ) e －(f1)
[ wherein d is an integer of 1 to 200, and e is 0 or 1.],
－(OC 4 F 8 ) c －(OC 3 F 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f －(f2)
[ wherein c and d are each independently an integer of 0 to 30;
e and f are each independently integers from 1 to 200;
c. d, e and f are integers from 10 to 200;
the order of the presence of the repeat units denoted by the subscripts c, d, e, or f and bracketed is arbitrary in the formula. ],
－(R 6 －R 7 ) g －(f3)
[ formula, R 6 Is OCF 2 Or OC (alpha) 2 F 4 ；
R 7 Is 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. ],
－(R 6 －R 7 ) g －R r －(R 7′ －R 6′ ) g′ －(f4)
[ formula, R 6 Is OCF 2 Or OC (alpha) 2 F 4 ，
R 7 Is 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 independently selected from these groups,
R 6′ is OCF 2 Or OC (alpha) 2 F 4 ，
R 7′ Is 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 independently selected from these groups,
g is an integer of 2 to 100,
g' is an integer of 2 to 100,
R r is that
(wherein, the term "represents a binding site"). The ];
－(OC 6 F 12 ) a －(OC 5 F 10 ) b －(OC 4 F 8 ) c －(OC 3 F 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f －(f5)
[ wherein e is an integer of 1 to 200, a, b, c, d and f are each independently an integer of 0 to 200, and the order of the presence of the repeating units indicated by a, b, c, d, e or f and bracketed is arbitrary in the formula. ]
－(OC 6 F 12 ) a －(OC 5 F 10 ) b －(OC 4 F 8 ) c －(OC 3 F 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f －(f6)
[ wherein f is an integer of 1 to 200, a, b, c, d and e are each independently an integer of 0 to 200, and the order of the presence of the repeating units denoted by a, b, c, d, e or f and bracketed by brackets is arbitrary in the formula. ].
[15] The composition according to any one of [12] to [14], wherein,
the reactive organic group is an isocyanate group, an epoxy group or a vinyl group.
[16] The composition according to any one of [12] to [15], wherein,
R Si is a group represented by the following formula (S1), formula (S2), formula (S3), formula (S4) or formula (S5):
-SiR 11 n1 R 12 3-n1 (S2)
-SiR a1 k1 R b1 11 R c1 m1 (S3)
-CR d1 12 R e1 12 R f1 n2 (S4)
-NR g1 R h1 (S5)
[ formula:
R 11 each occurrence is independently a hydroxyl group or a hydrolyzable group;
R 12 organic groups each independently at each occurrence being 1 valent;
n1 is defined in each (SiR 11 n1 R 12 3-n1 ) Each of the units is independently an integer of 0 to 3;
X 11 an organic group independently at each occurrence being a single bond or a 2-valent organic group;
R 13 an organic group which is independently a hydrogen atom or a valence 1 at each occurrence;
t is an integer of 2 or more independently at each occurrence;
R 14 each occurrence is independently a hydrogen atom, a halogen atom or-X 11 -SiR 11 n1 R 12 3-n1 ；
R 15 Each occurrence is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms;
R a1 are each independently-Z at each occurrence 1 -SiR 21 p1 R 22 q1 R 23 r1 ；
Z 1 An oxygen atom or a 2-valent organic group independently at each occurrence;
R 21 are each independently-Z at each occurrence 1′ -SiR 21′ p1′ ，R 22′ q1′ R 232 r1′ ；
R 22 Each occurrence is independently a hydroxyl group or a hydrolyzable group;
R 23 Organic groups each independently at each occurrence being 1 valent;
p1 is independently an integer from 0 to 3 at each occurrence;
q1 is independently an integer from 0 to 3 at each occurrence;
r1 is independently an integer from 0 to 3 at each occurrence;
the sum of p1, q1 and r1 is in (SiR 21 p1 R 22 q1 R 23 r1 ) 3 in the unit;
Z 1′ an oxygen atom or a 2-valent organic group independently at each occurrence;
R 21′ are each independently-Z at each occurrence 1" －SiR 22" q1" R 23" r1" ；
R 22′ Each occurrence is independently a hydroxyl group or a hydrolyzable group;
R 23′ organic groups each independently at each occurrence being 1 valent;
p1' is independently an integer from 0 to 3 at each occurrence;
q1' is independently an integer from 0 to 3 at each occurrence;
r1' is independently an integer from 0 to 3 at each occurrence;
the sum of p1', q1' and r1' is in (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ) 3 in the unit;
Z 1" an oxygen atom or a 2-valent organic group independently at each occurrence;
R 22" each occurrence is independently a hydroxyl group or a hydrolyzable group;
R 23" organic groups each independently at each occurrence being 1 valent;
q1 "is independently an integer from 0 to 3 at each occurrence;
r1 "is independently an integer from 0 to 3 at each occurrence;
the sum of q1 'and r1' is in (SiR 22" q1" R 23" r1" ) 3 in the unit;
R b1 each occurrence is independently a hydroxyl group or a hydrolyzable group;
R c1 organic groups each independently at each occurrence being 1 valent;
k1 is independently an integer of 0 to 3 at each occurrence;
l1 is independently an integer from 0 to 3 at each occurrence;
m1 is independently an integer of 0 to 3 at each occurrence;
the sum of k1, l1 and m1 is in (SiR a1 k1 R b1 l1 R c1 m1 ) 3 in the unit;
R d1 are each independently-Z at each occurrence 2 －CR 31 p2 R 32 q2 R 33 r2 ；
Z 2 An organic group independently at each occurrence being a single bond, an oxygen atom, or a valence 2;
R 31 are each independently-Z at each occurrence 2′ －CR 32′ q2′ R 33′ r2′ ；
R 32 Are each independently-Z at each occurrence 3 －SiR 34 n2 R 35 3－n2 ；
R 33 An organic group which is independently a hydrogen atom, a hydroxyl group, or a valence 1 at each occurrence;
p2 is independently an integer from 0 to 3 at each occurrence;
q2 is independently an integer from 0 to 3 at each occurrence;
r2 is independently an integer from 0 to 3 at each occurrence;
the sum of p2, q2 and r2 is in (CR 31 p2 R 32 q2 R 33 r2 ) 3 in the unit;
Z 2′ an organic group independently at each occurrence being a single bond, an oxygen atom, or a valence 2;
R 32′ are each independently-Z at each occurrence 3 －SiR 34 n2 R 35 3－n2 ；
R 33′ An organic group which is independently a hydrogen atom, a hydroxyl group, or a valence 1 at each occurrence;
q2' is independently an integer from 0 to 3 at each occurrence;
r2' is independently an integer from 0 to 3 at each occurrence;
the sum of q2 'and r2' is equal to (CR 32′ q2′ R 33′ r2′ ) 3 in the unit;
Z 3 an organic group independently at each occurrence being a single bond, an oxygen atom, or a valence 2;
R 34 each occurrence is independently a hydroxyl group or a hydrolyzable group;
R 35 organic groups each independently at each occurrence being 1 valent;
n2 is independently an integer from 0 to 3 at each occurrence;
R e1 are each independently-Z at each occurrence 3 －SiR 34 n2 R 35 3－n2 ；
R f1 An organic group which is independently a hydrogen atom, a hydroxyl group, or a valence 1 at each occurrence;
k2 is independently an integer of 0 to 3 at each occurrence;
l2 is independently an integer from 0 to 3 at each occurrence;
m2 is independently an integer from 0 to 3 at each occurrence;
the sum of k2, l2 and m2 is in (CR d1 k2 R e1 l2 R f1 m2 ) 3 in the unit;
R g1 and R is h1 Are each independently-Z at each occurrence 4 －SiR 11 n1 R 12 3－n1 、－Z 4 －SiR a1 k1 R b1 l1 R c1 m1 、－Z 4 －CR d1 k2 R e1 l2 R f1 m2 ；
Z 4 An organic group independently at each occurrence being a single bond, an oxygen atom, or a valence 2;
wherein at least one Si atom having a hydroxyl group or a hydrolyzable group bonded thereto is present in the formulae (S1), (S2), (S3), (S4) and (S5). ].
[17] The composition according to any one of [12] to [16], wherein,
X A is a single bond or a 2-valent organic group represented by the following formula:
－(R 51 ) p5 －(X 51 ) q5 －
[ formula:
R 51 is a single bond, - (CH) 2 ) s5 Either ortho-, meta-or para-phenylene,
s5 is an integer of 1 to 20,
X 51 is- (X) 52 ) l5 －，
X 52 At each occurrence is independently selected from the group consisting of-O-, -S-, O-phenylene m-or p-phenylene, -C (O) O-, -Si (R) 53 ) 2 －、－(Si(R 53 ) 2 O) m5 －Si(R 53 ) 2 －、－CONR 54 －、－O－CONR 54 －、－NR 54 -and- (CH) 2 ) n5 A group which is a radical of the formula,
R 53 at each occurrence is independently phenyl, C 1－6 Alkyl or C 1－6 An alkoxy group, an amino group,
R 54 each occurrence is independently a hydrogen atom, phenyl or C 1－6 An alkyl group, a hydroxyl group,
m5 is each independently an integer of 1 to 100,
n5 is each independently an integer of 1 to 20,
l5 is an integer of 1 to 10,
p5 is either 0 or 1 and,
q5 is either 0 or 1 and,
wherein at least one of p5 and q5 is 1, and the order in which the repeating units, denoted by p5 or q5 and bracketed, are present is arbitrary. ].
[18] The composition according to any one of [12] to [16], wherein,
X A is a group of the formula:
[ wherein X is a Is a single bond or a 2-valent organic group.]。
[19] The composition according to any one of [12] to [18], wherein,
the fluorine-containing liquid repellent compound is a fluorinated polyether silane compound represented by the formula (1).
[20] The composition according to any one of [1] to [19], wherein,
the content of the fluorine-containing liquid-repellent compound is 0.1 to 90.0% by mass based on the total of the crosslinkable compound and the fluorine-containing liquid-repellent compound.
[21] The composition according to any one of [1] to [20], wherein,
the F/Si ratio of the surface of the layer formed by the composition is more than 5.0.
[22] The composition according to any one of [1] to [21], wherein,
the water falling angle of the layer formed by the composition is below 25 degrees.
[23] The composition according to any one of [1] to [22], wherein,
and further comprises other components selected from the group consisting of organic solvents, water and catalysts.
[24] The composition according to any one of [1] to [23], which is a surface treatment agent.
[25] An article comprising a substrate and a layer formed of the composition of [24] above on the substrate.
[26] An article comprising a substrate and a composition comprising (a): crosslinkable compound and component (B): a layer formed from a composition comprising a fluorine-containing liquid-repellent compound,
the above composition satisfies the following formula:
P b －P c ＞0
[ formula:
P b the polar component ratio in the surface free energy of the layer formed of the fluorine-containing liquid-repellent compound is set to be a value,
P c the value of the polar component ratio in the free energy of the surface of the layer formed from the above composition.]。
[27] An article comprising a substrate and a composition comprising (a): crosslinkable compound and component (B): a layer formed from a composition containing a fluorine-containing liquid-repellent compound, wherein the polar component ratio in the surface free energy of the layer is 20.0% or less.
[28] The article according to [26] or [27], wherein,
the F/Si ratio of the surface of the layer is 5.0 or more.
[29] The article according to any one of [26] to [28], wherein,
the water falling angle of the layer is below 25 degrees.
[30] The article according to any one of [26] to [29], wherein,
the thickness of the layer is 0.01 μm or more.
Effects of the invention
According to the present invention, a composition capable of forming a layer excellent in liquid repellency and slip properties can be provided.
Detailed Description
As used in this specification, "1-valent organic group" refers to a 1-valent group containing carbon. The 1-valent organic group is not particularly limited, and may be a hydrocarbon group or a derivative thereof. The derivative of the hydrocarbon group means a group having 1 or more than 1 of N, O, S, si, amide group, sulfonyl group, siloxane group, carbonyl group, carbonyloxy group, etc. at the end of the hydrocarbon group or in the molecular chain. In the case of being merely referred to as an "organic group", the term "organic group" means an organic group having a valence of 1. The "2-valent organic group" to "10-valent organic group" refer to a group having 2 to 10 valences, respectively, of carbon. The 2-valent organic group is not particularly limited, and examples thereof include 2 to 10-valent groups having 1 to 9 hydrogen atoms further separated from the organic group.
As used herein, "hydrocarbyl" is a carbon and hydrogen containing group, meaning a group that has been stripped of 1 hydrogen atom from a hydrocarbon. The hydrocarbon group is not particularly limited, and examples thereof include a hydrocarbon group having 1 or more substituentsSubstituted C 1－20 Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The "aliphatic hydrocarbon group" may be any of linear, branched, and cyclic, or may be any of saturated or unsaturated. In addition, the hydrocarbon group may contain 1 or more ring structures.
In the case of use in the present specification, the substituent for the "hydrocarbon group" is not particularly limited, and examples thereof include C selected from halogen atoms and optionally substituted with 1 or more halogen atoms 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, 5-10 membered unsaturated heterocyclic group, C 6－10 Aryl and 1 or more than 1 group in 5-10 membered heteroaryl.
The composition of the present invention is a composition comprising components (A) and (B),
component (A): crosslinkable compound, and
component (B): a fluorine-containing liquid-repellent compound,
the above composition satisfies the following formula:
P b －P c ＞0
[ formula:
P b The polar component ratio in the surface free energy of the layer formed of the fluorine-containing liquid-repellent compound is set to be a value,
P c the value of the polar component ratio in the free energy of the surface of the layer formed from the above composition.]。
The composition of the invention satisfies P b －P c The layer obtained from the composition (hereinafter, also referred to as "surface-treated layer") has liquid repellency and excellent slip properties, > 0.
(polar component ratio)
The value of the above polar component ratio means that the polar component (γ s p ) Relative to the dispersion component (gamma) s d ) And polar component (gamma) s p ) The total ratio (%) of (a) can be obtained by the following formula:
polar component ratio (%) =γ s p /(γ s d +γ s p )×100。
The dispersion component (gamma) of the surface free energy s d ) And polar component (gamma) s p ) The following can be obtained: using 2 liquids, the static contact angle (θ) measured for the layer obtained from each liquid and the known parameters of the 2 liquids (surface free energy of liquid (γ L ) Dispersion component (gamma) of the surface free energy of the liquid L d ) And the polar component (gamma) of the surface free energy of the liquid 1 L p ) Based on the following formula of Kaelble-Uy.
[ formula:
γ L1 is the surface free energy of the liquid 1,
γ L1 d is the dispersive component of the surface free energy of the liquid 1,
γ L1 p is the polar component of the surface free energy of the liquid 1,
γ L2 Is the surface free energy of the liquid 2,
γ L2 d is the dispersive component of the surface free energy of the liquid 2,
γ L2 p is the polar component of the surface free energy of the liquid 2,
γ s d as a dispersive component of the surface of the layer,
γ s p as a polar component of the layer,
θ 1 is the static contact angle of the liquid 1,
θ 2 is the static contact angle of the liquid 2.]
The liquid used for the liquid 1 and the liquid 2 is preferably 2 kinds selected from water, hexadecane and formamide.
Surface free energy (gamma) of the above liquid L ) Dispersion component of surface free energy (gamma L d ) And the polar component of the surface free energy (gamma L p ) Shown in the table below.
TABLE 1
| Water and its preparation method | Hexadecane | Formamide | |
| γ L | 72.8 | 27.6 | 58.2 |
| γ L d | 21.8 | 27.6 | 39.5 |
| γ L p | 51.0 | 0 | 18.7 |
The static contact angle of the layer can be measured as followsAnd (5) setting. The static contact angle θ of the liquid 1 1 And static contact angle theta of liquid 2 2 The layers formed under the same conditions were measured.
(method for measuring static contact Angle)
The static contact angle can be determined as follows: 2. Mu.L of liquid was dropped on a horizontally placed surface-treated substrate by a micro-syringe using a full-automatic contact angle meter DropMaster501 (manufactured by Kyowa interface science Co., ltd.), and a still image was taken after 1 second of the drop was taken by a video microscope.
The composition of the present invention satisfies the following conditions.
P b －P c ＞0
[ formula:
P b the polar component ratio in the surface free energy of the layer formed of the fluorine-containing liquid-repellent compound is set to be a value,
P c The value of the polar component ratio in the free energy of the surface of the layer formed from the above composition.]
P b －P c The value of (2) is preferably 3.0 or more, more preferably 3.6 or more, still more preferably 5.0 or more, and still more preferably 8.0 or more. By making P b －P c Within this range, the liquid repellency and the liquid repellency of the layer are improved.
P c Preferably 20.0 or less, more preferably 10.0 or less, still more preferably 8.0 or less, and still more preferably 5.0 or less. By making P c Within this range, the liquid repellency and the liquid repellency of the layer are improved.
The thickness of the layer formed from the composition of the present invention is, for example, 0.05 μm or more, preferably 0.10 μm or more, more preferably 0.50 μm or more, and still more preferably 1.0 μm or more. The thickness of the above layer is, for example, 0.05 to 10.0. Mu.m, 0.50 to 5.0. Mu.m, 1.0 to 3.0. Mu.m.
Component (A) crosslinkable compound
The crosslinkable compound preferably has a metal alkoxide group.
The alkoxy group in the above metal alkoxide group is preferably C 1－6 Alkoxy groups, more preferablyIs C 1－3 Alkoxy, more preferably methoxy or ethoxy.
In a preferred embodiment, the crosslinkable compound is a compound represented by the following formula (A1) or a compound represented by the following formula (A2):
A[Z a1 －M 1 (OR a1 ) n1 (R a2 ) n2－n1 ] m1 [Z a2 －R a3 ] m2 (A1)
[ formula:
a is an organic group having a valence of 1 to 10,
Z a1 each independently a single bond or a 2-valent organic group,
M 1 al, ca, fe, ge, hf, in, si, ta, ti, sn, zr or Zn;
R a1 each independently is a hydrogen atom or C 1－6 An alkyl group, a hydroxyl group,
R a2 each independently is a hydrogen atom or a hydrocarbon group,
n1 is 1 or more and (M) 1 The valence of (2) is less than-1),
n2 is each independently (M) 1 Valence number-1) of (c) is set to be equal to or lower than the valence number-1),
Z a2 each independently a single bond or a 2-valent organic group,
R a3 each independently a reactive organic group,
m1 is an integer of 1 to 10,
m2 is an integer of 0 to 10,
the sum of m1 and m2 is the valence of A. ]
[ formula:
M 2 al, ca, fe, ge, hf, in, si, ta, ti, sn, zr or Zn;
R a4 are each independently a hydrogen atom, C 1－6 Alkyl or R a6 －CO－；
R a6 Is 1 priceIs a hydrocarbon group of (2);
R a5 each independently is C 1－3 Alkyl or C 1－3 An alkoxy group;
n3 is M as described above 2 Valence of (2);
n4 is 0 or more and M is as described above 2 Below the valence number of (c).]。
(Compound represented by the formula (A1))
A[Z a1 －M 1 (OR a1 ) n1 (R a2 ) n2－n1 ] m1 [Z a2 －R a3 ] m2 (A1)
A is an organic group having a valence of 1 to 10, preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 to 3, particularly preferably 2 or 3.
In one embodiment, a is a 2 valent organic group.
The above-mentioned 2-valent organic group is preferably a group represented by the following formula:
－[(R A1 ) a1 －(R A2 ) a2 －(R A3 ) a3 ]－
[ formula:
R A1 each independently is alkylene, preferably C 1－20 Alkylene, more preferably C 1－10 Alkylene, more preferably C 1－6 Alkylene groups, even more preferably C 1－4 An alkylene group,
R A2 each independently is cycloalkylene, preferably C 3－20 Cycloalkylene group, more preferably C 3－10 Cycloalkylene radicals, more preferably C 5－8 Cycloalkylene radicals, even more preferably C 5－7 A cycloalkylene group, a cyclic alkylene group,
R A3 respectively and independently arylene, preferably C 6－20 Arylene groups, more preferably C 6－10 Arylene groups, more preferably C 6－8 Arylene is particularly preferably phenylene,
a1 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 1 or 2,
a2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1,
a3 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1,
the total of a1, a2 and a3 is 1 or more, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
the order in which the repeating units denoted by a1, a2 and a3 and bracketed is present is arbitrary. ].
In one embodiment, A is R A1 。
R is as described above A1 The alkylene group in (a) may be linear or branched, and is preferably linear.
In further embodiments, a is a3 valent organic group.
The above 3-valent organic group is preferably a group represented by the following formula:
[ formula:
X a each independently a single bond or a 2-valent organic group.]。
In one embodiment, X a Is a single bond.
In a further embodiment, X a An organic group having a valence of 2.
X a The organic group having a valence of 2 in (a) is preferably an alkylene group or a group having a valence of 2 containing at least one bond selected from the group consisting of an ether bond and an ester bond, more preferably a single bond, C 1－10 An alkylene group or a hydrocarbon group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond and an ester bond.
In a preferred embodiment, X a The organic group having a valence of 2 is a group represented by the following formula:
－(CX 121 X 122 ) x1 －(X a1 ) y1 －(CX 123 X 124 ) z1 －
(wherein X is 121 ～X 124 H, F, OH OR-OSi (OR) 121 ) 3 (wherein 3R' s 121 Independently alkyl groups having 1 to 4 carbon atoms),
above X a1 is-C (=O) NH-, -NHC (=O) -, -O-, -C (=O) O-, -OC (=O) O-, or-NHC (=O) NH- (left side of each bond and CX 121 X 122 Binding),
x1 is an integer of 0 to 10, y1 is 0 or 1, and z1 is an integer of 1 to 10. ).
The left side of the above group is bonded to an isocyanuric ring.
X a1 preferably-O-or C (=O) O-.
X a The organic group having a valence of 2 in (b) is particularly preferably a group represented by the following formula:
－(CF 2 ) m11 －(CH 2 ) m12 －O－(CH 2 ) m13 The group indicated is chosen from the group indicated,
(wherein m11 is an integer of 1 to 3, m12 is an integer of 1 to 3, and m13 is an integer of 1 to 3.)
－(CF 2 ) m14 －(CH 2 ) m15 －O－CH 2 CH(OH)－(CH 2 ) m16 The group indicated is chosen from the group indicated,
(wherein m14 is an integer of 1 to 3, m15 is an integer of 1 to 3, and m16 is an integer of 1 to 3.)
－(CF 2 ) m17 －(CH 2 ) m18 The group indicated is chosen from the group indicated,
(wherein m17 is an integer of 1 to 3, and m18 is an integer of 1 to 3.)
－(CF 2 ) m19 －(CH 2 ) m20 －O－CH 2 CH(OSi(OCH 3 ) 3 )－(CH 2 ) m21 The group indicated is chosen from the group indicated,
(wherein m19 is an integer of 1 to 3, m20 is an integer of 1 to 3, and m21 is an integer of 1 to 3), or
－(CH 2 ) m22 -the group shown
(wherein m22 is an integer of 1 to 3).
As X a The organic group having a valence of 2 in (3) is not particularly limited, and specifically, may be-CH 2 －、－C 2 H 4 －、－C 3 H 6 －、－C 4 H 8 －、－C 4 H 8 －O－CH 2 －、－CO－O－CH 2 －CH(OH)－CH 2 －、－(CF 2 ) n5 - (n 5 is an integer of 0 to 4)), and- (CF 2 ) n5 －(CH 2 ) m5 - (n 5 and m5 are each independently an integer of 0 to 4), -CF 2 CF 2 CH 2 OCH 2 CH(OH)CH 2 －、－CF 2 CF 2 CH 2 OCH 2 CH(OSi(OCH 3 ) 3 )CH 2 -and the like.
Z a1 Each independently a single bond or a 2-valent organic group.
In one embodiment, Z a1 Is a single bond.
In further embodiments, Z a1 Each independently a 2-valent organic group.
The above Z a1 The organic radicals of the valences 2 in (a) are each independently alkylene, preferably C 1－20 Alkylene, more preferably C 1－10 Alkylene, more preferably C 1－6 Alkylene groups, even more preferably C 1－4 An alkylene group.
M 1 Al, ca, fe, ge, hf, in, si, ta, ti, sn, zr or Zn.
M 1 Si, ti or Zr is preferable, and Si is more preferable.
R a1 Each independently is a hydrogen atom or C 1－6 An alkyl group.
In a preferred embodiment, R a1 Each independently is C 1－6 Alkyl, preferably C 1－4 Alkyl, more preferably C 1－2 An alkyl group.
R a2 Each independently is a hydrogen atom or a hydrocarbyl group.
R a2 Each independently is a hydrocarbyl group.
R a2 The hydrocarbon radical in (C) is preferably 1－6 Alkyl, preferably C 1－3 Alkyl, more preferably C 1－2 An alkyl group.
n1 is 1 or more and (M) 1 Valence number-1) or less, n2 is (M) 1 Valence number-1).
n1 is preferably 2 or more and (M) 1 Valence of (2) is not more than-1), more preferably not less than 3 and (M) 1 The valence of (2) is not more than-1), more preferably (M) 1 Valence number-1).
Z a2 Each independently a single bond or a 2-valent organic group.
In one embodiment, Z a2 Is a single bond.
In further embodiments, Z a2 Each independently a 2-valent organic group.
The above Z a2 The organic radical of valency 2 in (2) is preferably C 1－6 Alkylene, - (CH) 2 ) z1 －O－(CH 2 ) z2 - (wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6) or- (CH) 2 ) z3 -phenylene- (CH) 2 ) z4 - (wherein z3 is an integer of 0 to 6, for example, an integer of 1 to 6), and z4 is an integer of 0 to 6, for example, an integer of 1 to 6). The C is 1－6 The alkylene group may be linear or branched, and is preferably linear. These groups may be selected, for example, from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 1 or more substituents in the alkynyl group are substituted, preferably unsubstituted.
In a preferred embodiment, Z a2 Is C 1－6 Alkylene or- (CH) 2 ) z1 －O－(CH 2 ) z2 - (wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6).
R a3 Each independently a reactive organic group.
R is as described above a3 The reactive organic groups in (a) being isocyanate groups, ringsOxy or vinyl.
In one embodiment, the reactive organic group is an isocyanate group.
In another embodiment, the reactive organic group is an epoxy group.
In another embodiment, the reactive organic group is a vinyl group.
m1 is an integer of 1 to 10, m2 is an integer of 0 to 10, and the sum of m1 and m2 is the valence of A.
In one embodiment, m1 is an integer from 1 to 10 and m2 is 0.
In another embodiment, m1 is an integer from 1 to 10 and m2 is an integer from 1 to 10.
In a preferred embodiment, m1 is 1 or 2, m2 is 0 or 1, preferably m1 is 1 and m2 is 1.
(Compound represented by the formula (A2))
M 2 Al, ca, fe, ge, hf, in, si, ta, ti, sn, zr or Zn.
M 2 Si, ti or Zr is preferable, and Si is more preferable.
R a3 Are each independently a hydrogen atom, C 1－6 Alkyl or R a6 －CO－。
R a3 Are each independently preferably C 1－6 Alkyl, more preferably C 1－3 Alkyl, more preferably C 1－2 An alkyl group.
R a4 Each independently is C 1－3 Alkyl or C 1－3 An alkoxy group.
R is as described above a4 The alkyl group in (a) is preferably methyl or ethyl, more preferably methyl.
R is as described above a4 The alkoxy group in (a) is preferably methoxy or ethoxy, more preferably ethoxy.
n3 is M as described above 2 Valence of n4 is 0 or more and M is as described above 2 Below the valence number of (c).
In one embodiment, n4 is the valence of M.
In other embodiments, (n 3-n 4) is 1.
In one embodiment, the composition of the present invention contains a compound represented by formula (A1).
In one embodiment, the composition of the present invention contains a compound represented by formula (A2).
In another embodiment, the composition of the present invention contains a compound represented by formula (A1) and a compound represented by formula (A2).
< component (B): fluorine-containing liquid-repellent Compound ]
The fluorine-containing liquid-repellent compound preferably has a fluoroalkyl group or a fluoropolyether group.
The above-mentioned fluoropolyether group is preferably a group represented by the following formula:
-(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 R Fa 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -
[ formula, R Fa Each occurrence of which is independently a hydrogen atom, a fluorine atom or a chlorine atom,
a. b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f being 1 or more, the order of presence of the repeating units denoted by a, b, c, d, e or f and bracketed in the formula is arbitrary, wherein, in all R Fa In the case of a hydrogen atom or a chlorine atom, at least 1 of a, b, c, e and f is 1 or more.]。
In a preferred embodiment, the fluorine-containing liquid repellent compound is a fluorinated polyether silane compound represented by the following formula (1) or formula (2):
R F1 α -X A -R Si β (1)
R Si γ -X A -R F2 -X A -R Si γ (2)
[ formula:
R F1 each occurrence is independently Rf 1 -or Rf 1 -R F -O q -；
R F2 is-Rf 2 -or-Rf 2 p -R F -O q -；
Rf 1 Each occurrence is independently C which may be substituted with 1 or more fluorine atoms 1-16 An alkyl group;
Rf 2 for C which may be substituted by 1 or more fluorine atoms 1-6 An alkylene group;
R F each occurrence is independently a 2-valent fluoropolyether group;
p is 0 or 1;
q is independently 0 or 1 at each occurrence;
R Si each occurrence is independently a 1-valent group comprising a Si atom to which a hydroxyl group, a hydrolyzable group, or a 1-valent organic group is bonded, or a 1-valent group comprising a reactive organic group;
at least 1R Si A 1-valent group comprising a Si atom to which a hydroxyl group or a hydrolyzable group is bonded, or a 1-valent group comprising a reactive organic group;
X A each independently is a single bond or an organic group having a valence of 2 to 10;
alpha is an integer of 1 to 9;
beta is an integer of 1 to 9;
gamma is an integer of 1 to 9. ].
In the above formula (1), R F1 Each occurrence is independently Rf 1 －R F －O q －。
In the above formula (2), R F2 is-Rf 2 p －R F －O q －。
In the above formula, rf 1 Each occurrence is independently C which may be substituted with 1 or more fluorine atoms 1－16 An alkyl group.
The above may be substituted with 1 or 1C of more than one fluorine atom 1－16 "C" in alkyl 1－16 The alkyl group "may be linear or branched, and is preferably linear or branched C 1－6 Alkyl, especially C 1－3 Alkyl, more preferably C in straight chain form 1－6 Alkyl, especially C 1－3 An alkyl group.
The Rf described above 1 Preferably C substituted with 1 or more fluorine atoms 1－16 Alkyl, more preferably CF 2 H－C 1－15 Perfluoroalkylene groups, more preferably C 1－16 Perfluoroalkyl groups.
The above C 1－16 The perfluoroalkyl group may be linear or branched, and is preferably linear or branched C 1－6 Perfluoroalkyl group, especially C 1－3 Perfluoroalkyl group, more preferably straight-chain C 1－6 Perfluoroalkyl group, especially C 1－3 Perfluoroalkyl, in particular-CF 3 、－CF 2 CF 3 or-CF 2 CF 2 CF 3 。
In the above formula, rf 2 For C which may be substituted by 1 or more fluorine atoms 1－6 An alkylene group.
The above C may be substituted with 1 or more fluorine atoms 1－6 "C" in alkylene 1－6 The alkylene group "may be linear or branched, and is preferably linear or branched C 1－3 Alkylene group, more preferably C in straight chain 1－3 An alkylene group.
The Rf described above 2 Preferably C substituted with 1 or more fluorine atoms 1－6 Alkylene, more preferably C 1－6 Perfluoroalkylene groups, more preferably C 1－3 A perfluoroalkylene group.
The above C 1－6 The perfluoroalkylene group may be linear or branched, and preferably linear or branched C 1－3 Perfluoroalkylene groups, more preferably linear C 1－3 Perfluoroalkylene radicals, in particular-CF 2 －、－CF 2 CF 2 -or-CF 2 CF 2 CF 2 －。
In the above formula, p is 0 or 1. In one embodiment, p is 0. In further embodiments, p is 1.
In the above formula, q is independently 0 or 1 at each occurrence. In one embodiment, q is 0. In other embodiments, q is 1.
In the above formulae (1) and (2), R F Each occurrence is independently 2-valent fluoropolyether group.
R F Preferably comprises a group of the formula:
－(OC h1 R Fa 2h1 ) h3 －(OC h2 R Fa 2h2-2 ) h4 －
[ formula:
R Fa each occurrence of which is independently a hydrogen atom, a fluorine atom or a chlorine atom,
h1 is an integer of 1 to 6,
h2 is an integer of 4 to 8,
h3 is an integer of 0 or more,
h4 is an integer of 0 or more,
wherein the total of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order of the presence of the repeating units denoted by h3 and h4 and bracketed is arbitrary in the formula. ].
In one embodiment, R F Can be straight-chain or branched. R is R F Preferred are groups of the formula:
－(OC 6 F 12 ) a －(OC 5 F 10 ) b －(OC 4 F 8 ) c －(OC 3 R Fa 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f －
[ formula:
R Fa each occurrence of which is independently a hydrogen atom, a fluorine atom or a chlorine atom,
a. b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of presence of the repeating units denoted a, b, c, d, e or f and bracketed is arbitrary in the formula. Wherein, at all R Fa In the case of a hydrogen atom or a chlorine atom, at least 1 of a, b, c, e and f is 1 or more.]。
R Fa Preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. Wherein, at all R Fa In the case of a hydrogen atom or a chlorine atom, at least 1 of a, b, c, e and f is 1 or more.
a. b, c, d, e and f are preferably each independently integers from 0 to 100.
a. The sum of b, c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be 15 or more or 20 or more, for example. a. The sum of b, c, d, e and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be 50 or 30 or less, for example.
These repeating units may be linear or branched. For example- (OC) 6 F 12 ) Can be- (OCF) 2 CF 2 CF 2 CF 2 CF 2 CF 2 )－、－(OCF(CF 3 )CF 2 CF 2 CF 2 CF 2 )－、－(OCF 2 CF(CF 3 )CF 2 CF 2 CF 2 )－、－(OCF 2 CF 2 CF(CF 3 )CF 2 CF 2 )－、－(OCF 2 CF 2 CF 2 CF(CF 3 )CF 2 )－、－(OCF 2 CF 2 CF 2 CF 2 CF(CF 3 ) -and the like. - (OC) 5 F 10 ) Can be- (OCF) 2 CF 2 CF 2 CF 2 CF 2 )－、－(OCF(CF 3 )CF 2 CF 2 CF 2 )－、－(OCF 2 CF(CF 3 )CF 2 CF 2 )－、－(OCF 2 CF 2 CF(CF 3 )CF 2 )－、－(OCF 2 CF 2 CF 2 CF(CF 3 ) -and the like. - (OC) 4 F 8 ) Can be- (OCF) 2 CF 2 CF 2 CF 2 )－、－(OCF(CF 3 )CF 2 CF 2 )－、－(OCF 2 CF(CF 3 )CF 2 )－、－(OCF 2 CF 2 CF(CF 3 ))－、－(OC(CF 3 ) 2 CF 2 )－、－(OCF 2 C(CF 3 ) 2 )－、－(OCF(CF 3 )CF(CF 3 ))－、－(OCF(C 2 F 5 )CF 2 ) -and- (OCF) 2 CF(C 2 F 5 ) Any case of (c) x. - (OC) 3 F 6 ) - (i.e. R in the above formula) Fa Is a fluorine atom) may be- (OCF) 2 CF 2 CF 2 )－、－(OCF(CF 3 )CF 2 ) -and- (OCF) 2 CF(CF 3 ) Any case of (c) x. - (OC) 2 F 4 ) Can be- (OCF) 2 CF 2 ) -and- (OCF (CF) 3 ) Any case of (c) x.
In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface slidability, wear durability, and the like of the surface treatment layer can be improved.
In one embodiment, the repeating unit is branched. By forming the repeating unit into a branched chain, the coefficient of dynamic friction of the surface treatment layer can be increased.
In one embodiment, R F May comprise a ring structure.
The above-mentioned ring structure may be a three-membered ring, a four-membered ring, a five-membered ring or a six-membered ring as described below.
[ formula (I) is the binding site. ]
The above-mentioned ring structure is preferably a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.
The repeating unit having a ring structure may preferably be a unit described later.
[ formula (I) is the binding site. ]
In one embodiment, R F Each occurrence is independently a group represented by any one of the following formulas (f 1) to (f 6).
－(OC 3 F 6 ) d －(OC 2 F 4 ) e －(f1)
[ wherein d is an integer of 1 to 200, and e is 0 or 1. The ];
－(OC 4 F 8 ) c －(OC 3 F 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f －(f2)
[ wherein c and d are each independently an integer of 0 to 30, e and f are each independently an integer of 1 to 200,
c. d, e and f are added to 2 or more,
the order of the presence of the repeat units denoted by the subscripts c, d, e, or f and bracketed is arbitrary in the formula. The ];
－(R 6 －R 7 ) g －(f3)
[ formula, R 6 Is OCF 2 Or OC (alpha) 2 F 4 ，
R 7 Is 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. The ];
－(R 6 －R 7 ) g －R r －(R 7′ －R 6′ ) g′ －(f4)
[ formula, R 6 Is OCF 2 Or OC (alpha) 2 F 4 ，
R 7 Is 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,
R 6′ is OCF 2 Or OC (alpha) 2 F 4 ，
R 7′ Is 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 independently selected from these groups,
g is an integer of 2 to 100,
g' is an integer of 2 to 100,
R r is that
(wherein, the term "represents a binding site"). The ];
－(OC 6 F 12 ) a －(OC 5 F 10 ) b －(OC 4 F 8 ) c －(OC 3 F 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f －(f5)
[ wherein e is an integer of 1 to 200, a, b, c, d and f are each independently an integer of 0 to 200, and the order of the presence of the repeating units indicated by a, b, c, d, e or f and bracketed is arbitrary in the formula. ]
－(OC 6 F 12 ) a －(OC 5 F 10 ) b －(OC 4 F 8 ) c －(OC 3 F 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f －(f6)
[ wherein f is an integer of 1 to 200, a, b, c, d and e are each independently an integer of 0 to 200, and the order of the presence of the repeating units denoted by a, b, c, d, e or f and bracketed by brackets is arbitrary in the formula. ]
In the above formula (f 1), d is preferably an integer of from 5 to 200, more preferably from 10 to 100, still more preferably from 15 to 50, for example from 25 to 35. OC in the above formula (f 1) 3 F 6 Preferably (OCF) 2 CF 2 CF 2 )、(OCF(CF 3 )CF 2 ) Or (OCF) 2 CF(CF 3 ) More preferably (OCF) 2 CF 2 CF 2 ). In one embodiment, e is 0. In other embodiments, e is 1. (OC) in the above formula (f 1) 2 F 4 ) Preferably (OCF) 2 CF 2 ) Or (OCF (CF) 3 ) More preferably (OCF) 2 CF 2 )。
In the above formula (f 2), e and f are each independently preferably an integer of 5 to 200, more preferably 10 to 200. The sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be 15 or more or 20 or more, for example. In one embodiment, the above formula (f 2) is preferably- (OCF) 2 CF 2 CF 2 CF 2 ) c －(OCF 2 CF 2 CF 2 ) d －(OCF 2 CF 2 ) e －(OCF 2 ) f -the group shown. In further embodiments, formula (f 2) may be- (OC) 2 F 4 ) e －(OCF 2 ) f -the group shown.
In the above formula (f 3), R 6 Preferably OC 2 F 4 . In the above (f 3), R 7 Preferably selected from OC 2 F 4 、OC 3 F 6 And OC 4 F 8 Or a combination of 2 or 3 groups independently selected from these groups, more preferably selected from OC 3 F 6 And OC 4 F 8 Is a group of (2). As being independently selected from OC 2 F 4 、OC 3 F 6 And OC 4 F 8 The combination of 2 or 3 groups of (C) is not particularly limited, and examples thereof include-OC 2 F 4 OC 3 F 6 －、－OC 2 F 4 OC 4 F 8 －、－OC 3 F 6 OC 2 F 4 －、－OC 3 F 6 OC 3 F 6 －、－OC 3 F 6 OC 4 F 8 －、－OC 4 F 8 OC 4 F 8 －、－OC 4 F 8 OC 3 F 6 －、－OC 4 F 8 OC 2 F 4 －、－OC 2 F 4 OC 2 F 4 OC 3 F 6 －、－OC 2 F 4 OC 2 F 4 OC 4 F 8 －、－OC 2 F 4 OC 3 F 6 OC 2 F 4 －、－OC 2 F 4 OC 3 F 6 OC 3 F 6 －、－OC 2 F 4 OC 4 F 8 OC 2 F 4 －、－OC 3 F 6 OC 2 F 4 OC 2 F 4 －、－OC 3 F 6 OC 2 F 4 OC 3 F 6 －、－OC 3 F 6 OC 3 F 6 OC 2 F 4 -and-OC 4 F 8 OC 2 F 4 OC 2 F 4 -and the like. In the above formula (f 3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f 3), OC 2 F 4 、OC 3 F 6 、OC 4 F 8 、OC 5 F 10 And OC 6 F 12 The chain may be linear or branched, and is preferably linear. In this embodiment, the above formula (f 3) is preferably the form- (OC) 2 F 4 －OC 3 F 6 ) g -or- (OC) 2 F 4 －OC 4 F 8 ) g －。
In the above formula (f 4), R 6 、R 7 And g has the same meaning as described in the above formula (f 3), and has the same embodiment. R is R 6′ 、R 7′ And g' is independently the same as R described in the above formula (f 3) 6 、R 7 The same as g, the same embodiment. R is R r Preferably is
[ formula (I) is the binding site. ],
more preferably
[ formula (I) is the binding site. ].
In the above formula (f 5), e is preferably an integer of 1 to 100, more preferably 5 to 100. a. The sum of b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.
In the above formula (f 6), f is preferably an integer of 1 to 100, more preferably 5 to 100. a. The sum of b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.
In one embodiment, R is as defined above F Is a group represented by the above formula (f 1).
In one embodiment, R is as defined above F Is a group represented by the above formula (f 2).
In one embodiment, R is as defined above F Is a group represented by the above formula (f 3).
In one embodiment, R is as defined above F Is a group represented by the above formula (f 4).
In one embodiment, R is as defined above F Is a group represented by the above formula (f 5).
In one embodiment, R is as defined above F Is a group represented by the above formula (f 6).
The above R F The ratio of e to f (hereinafter referred to as "e/f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and still more preferably 0.2 to 0.85. By setting the e/f ratio to 10 or less, the abrasion durability of the layer obtained from the compound is further improved. The smaller the e/f ratio, the less grinding of the resulting layerThe more the damage durability is improved. On the other hand, by setting the e/f ratio to 0.1 or more, the stability of the compound can be further improved. The greater the e/f ratio, the further improved the stability of the compound.
In the above-mentioned fluoropolyether group-containing compound, R F1 And R is F2 The number average molecular weight of the fraction is not particularly limited, and is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. In the present specification, R F1 And R is F2 The number average molecular weight of (2) is determined by 19 F-NMR measured values.
In another embodiment, R F1 And R is F2 The number average molecular weight of the fraction is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, still more preferably 2,000 to 10,000, and may be 3,000 to 6,000, for example.
In further embodiments, R F1 And R is F2 The number average molecular weight of the fraction is 4,000 to 30,000, preferably 5,000 to 10,000, more preferably 6,000 to 10,000.
In the above formulae (1) and (2), R Si At each occurrence is independently a 1-valent group comprising a Si atom to which a hydroxyl group, a hydrolyzable group, or a 1-valent organic group is bonded, or a 1-valent group comprising a reactive organic group, at least 1R Si Is a 1-valent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded, or a 1-valent group containing an isocyanate group, an epoxy group, or a vinyl group.
Here, "hydrolyzable group" means a group capable of undergoing a hydrolysis reaction, that is, a group capable of being detached from the main skeleton of the compound by a hydrolysis reaction. As examples of hydrolyzable groups, mention may be made of-OR j 、－OCOR j 、－O－N＝CR j 2 、－NR j 2 、－NHR j -NCO, halogen (in these formulae, R j Represents substituted or unsubstituted C 1－4 Alkyl), and the like.
"reactive organic group" refers to a group that is reactive with a substrate or with other compounds.
In one embodiment, R Si Each occurrence is independently a reactive organic group, preferably a 1-valent group comprising an isocyanate group, an epoxy group, or a vinyl group.
In a preferred embodiment, R Si Each occurrence is independently an isocyanate group, an epoxy group, or a vinyl group.
In further embodiments, R Si Each occurrence is independently a 1-valent group comprising a Si atom to which a hydroxyl group, a hydrolyzable group, or a 1-valent organic group is bonded.
In a preferred embodiment, R Si Each occurrence is independently a 1-valent group comprising a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.
In a preferred embodiment, R Si Each occurrence is independently a group represented by the following formula (S1), formula (S2), formula (S3), formula (S4) or formula (S5):
-SiR 11 n1 R 12 3-n1 (S2)
-SiR a1 k1 R b1 11 R c1 m1 (S3)
-CR d1 k2 R e1 12 R f1 m2 (S4)
-NR g1 R h1 (S5)。
in the above formula, R 11 Each occurrence is independently a hydroxyl group or a hydrolyzable group.
R 11 Preferably, each occurrence is independently a hydrolyzable group.
R 11 Preferably, each occurrence is independently-OR j 、-OCOR j 、-O-N＝CR j 2 、-NR j 2 、-NHR j -NCO or halogen (in these formulae, R j Representing substitution or non-extractionSubstituted C 1-4 Alkyl), more preferably-OR j (i.e., alkoxy). As R j Examples of the method include: unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.; substituted alkyl groups such as chloromethyl. Of these, alkyl groups, particularly unsubstituted alkyl groups, are preferable, and methyl or ethyl groups are more preferable. In one embodiment, R j Methyl, in another embodiment, R j Is ethyl.
In the above formula, R 12 Each occurrence is independently a 1-valent organic group. The 1-valent organic group is a 1-valent organic group other than the hydrolyzable group.
At R 12 In which the 1-valent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 Alkyl groups are more preferably methyl groups.
In the above formula, n1 is defined in each (SiR 11 n1 R 12 3－n1 ) The units are independently integers from 0 to 3. Wherein R is Si In the case of the group represented by the formula (S1) or the formula (S2), R is at the end of the formula (1) or the formula (2) Si At least 1 (SiR) having n1 of 1 to 3 is present in a moiety (hereinafter, sometimes simply referred to as "terminal portion" of the formulae (1) and (2) " 11 n1 R 12 3－n1 ) A unit. That is, at this end portion, all n1 are not 0 at the same time. In other words, at least 1 Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present in the terminal portion of the formula (1) and the formula (2).
n1 is defined in each (SiR 11 n1 R 12 3－n1 ) Each unit is independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.
In the above, X 11 Each occurrence is independently a single bond or a 2-valent organic group. The 2-valent organic group is preferably-R 28 －O x －R 29 - (wherein R is 28 And R is 29 Each occurrence is independently a single bond or C 1－20 Alkylene, x is 0 or 1. ). The C is 1－20 The alkylene group may be linear or branched, and is preferably linear. The C is 1－20 Alkylene is preferably C 1－10 Alkylene, more preferably C 1－6 Alkylene, more preferably C 1－3 An alkylene group.
In one embodiment, X 11 Are each independently-C at each occurrence 1－6 alkylene-O-C 1－6 alkylene-or-O-C 1－6 Alkylene-.
In a preferred embodiment, X 11 C independently at each occurrence is a single bond or a straight chain 1－6 Alkylene, preferably C, singly or in linear form 1－3 Alkylene, more preferably C, singly or in straight chain 1－2 Alkylene, more preferably C, which is linear 1－2 An alkylene group.
In the above formula, R 13 Each occurrence is independently a hydrogen atom or a 1-valent organic group. The 1-valent organic group is preferably C 1－20 An alkyl group. The C is 1－20 The alkyl group may be linear or branched, and is preferably linear.
In a preferred embodiment, R 13 C independently at each occurrence being a hydrogen atom or a straight chain 1－6 Alkyl radicals, preferably hydrogen atoms or straight-chain C 1－3 Alkyl groups are preferably hydrogen atoms or methyl groups.
In the above formula, t is an integer of 2 or more independently at each occurrence.
In a preferred embodiment, t is independently an integer from 2 to 10, preferably an integer from 2 to 6, at each occurrence.
In the above formula, R 14 Each occurrence is independently a hydrogen atom, a halogen atom or-X 11 －SiR 11 n1 R 12 3－n1 . The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom. In a preferred mode, R 14 Is a hydrogen atom.
In the above formula, R 15 Each occurrence is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
In one embodiment, R 15 Each occurrence is independently an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
In a preferred embodiment, R 15 Is a single bond.
In one embodiment, formula (S1) is the following formula (S1-a).
[ in the above-mentioned, a method for producing a semiconductor device,
R 11 、R 12 、R 13 、X 11 and n1 has the same meaning as described in the above formula (S1);
t1 and t2 are each independently an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 2 to 10, for example an integer of 1 to 5 or an integer of 2 to 5;
the order of presence of the repeating units denoted by t1 and t2 and bracketed is arbitrary in the formula. ]
In a preferred embodiment, formula (S1) is the following formula (S1-b).
[ formula, R 11 、R 12 、R 13 、X 11 N1 and t have the same meaning as those described in the above formula (S1). ]
In the above formula, R a1 Are each independently-Z at each occurrence 1 －SiR 21 p1 R 22 q1 R 23 r1 。
The above Z 1 Each occurrence is independently an oxygen atom or a 2-valent organic group. In addition, hereinafter referred to as Z 1 Right side of the structure of (1) and (SiR) 21 p1 R 22 q1 R 23 r1 ) And (5) combining.
In a preferred embodiment, Z 1 An organic group having a valence of 2.
In a preferred embodiment, Z 1 Not including with Z 1 The bonded Si atoms form siloxane bonds. Preferably in the formula (S3) (Si-Z 1 -Si) contains no siloxane bonds.
The above Z 1 Preferably C 1－6 Alkylene, - (CH) 2 ) z1 －O－(CH 2 ) z2 - (wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6) or- (CH) 2 ) z3 -phenylene- (CH) 2 ) z4 - (wherein z3 is an integer of 0 to 6, for example, an integer of 1 to 6, and z4 is an integer of 0 to 6, for example, an integer of 1 to 6). The C is 1－6 The alkylene group may be linear or branched, and is preferably linear. These groups may be selected, for example, from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 1 or more substituents in the alkynyl group are substituted, preferably unsubstituted.
In a preferred embodiment, Z 1 Is C 1－6 Alkylene or- (CH) 2 ) z3 -phenylene- (CH) 2 ) z4 -, preferably-phenylene- (CH) 2 ) z4 －。Z 1 In the case of this group, the light resistance, particularly the ultraviolet resistance, is further improved.
In another preferred embodiment, Z is as defined above 1 Is C 1－3 An alkylene group. In one embodiment, Z 1 Can be-CH 2 CH 2 CH 2 -. In another embodiment, Z 1 Can be-CH 2 CH 2 －。
R is as described above 21 Are each independently-Z at each occurrence 1′ －SiR 21′ p1′ R 22′ q1′ R 23′ r1′ 。
The above Z 1′ Each occurrence is independently an oxygen atom or a 2-valent organic group. In addition, hereinafter referred to as Z 1′ Right side of the structure of (1) and (SiR) 21′ p1′ R 22′ q1′ R 23′ r1′ ) And (5) combining.
In a preferred embodiment, Z 1′ An organic group having a valence of 2.
In a preferred embodiment, Z 1′ Not including with Z 1′ The bonded Si atoms form siloxane bonds. Preferably in the formula (S3) (Si-Z 1′ -Si) contains no siloxane bonds.
The above Z 1′ Preferably C 1－6 Alkylene, - (CH) 2 ) z1′ －O－(CH 2 ) z2′ - (wherein z1 'is an integer of 0 to 6, for example, an integer of 1 to 6, and z2' is an integer of 0 to 6, for example, an integer of 1 to 6) or- (CH) 2 ) z3′ -phenylene- (CH) 2 ) z4′ - (wherein z3 'is an integer of 0 to 6, for example, an integer of 1 to 6, and z4' is an integer of 0 to 6, for example, an integer of 1 to 6). The C is 1－6 The alkylene group may be linear or branched, and is preferably linear. These groups may be selected, for example, from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 1 or more substituents in the alkynyl group are substituted, preferably unsubstituted.
In a preferred embodiment, Z 1′ Is C 1－6 Alkylene or- (CH) 2 ) z3′ -phenylene- (CH) 2 ) z4′ -, preferably-phenylene- (CH) 2 ) z4′ －。Z 1′ In the case of this base, the light resistance, particularly the ultraviolet resistance, of the obtained layer is further improved.
In another preferred embodiment, Z is as defined above 1′ Is C 1－3 An alkylene group. In one embodiment, Z 1′ Can be-CH 2 CH 2 CH 2 -. In further embodiments, Z 1′ Can be-CH 2 CH 2 －。
R is as described above 21′ Are each independently-Z at each occurrence 1" －SiR 22" q1" R 23" r1" 。
The above Z 1" Each occurrence is independently an oxygen atom or a 2-valent organic group. In addition, the right side AND (SiR) of the structure hereinafter referred to as Z1 22" q1" R 23" r1" ) And (5) combining.
In a preferred embodiment, Z 1" An organic group having a valence of 2.
In a preferred embodiment, Z 1" Not including with Z 1" The bonded Si atoms form siloxane bonds. Preferably in the formula (S3) (Si-Z 1" -Si) contains no siloxane bonds.
The above Z 1" Preferably C 1－6 Alkylene, - (CH) 2 ) z1" －O－(CH 2 ) z2" - (wherein z1 "is an integer of 0 to 6, for example, an integer of 1 to 6, and z2" is an integer of 0 to 6, for example, an integer of 1 to 6) or- (CH) 2 ) z3" -phenylene- (CH) 2 ) z4" - (wherein z3 "is an integer of 0 to 6, for example, an integer of 1 to 6, and z4" is an integer of 0 to 6, for example, an integer of 1 to 6). The C is 1－6 The alkylene group may be linear or branched, and is preferably linear. These groups may be selected, for example, from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 1 or more substituents in the alkynyl group are substituted, preferably unsubstituted.
In a preferred embodiment, Z 1" Is C 1－6 Alkylene or- (CH) 2 ) z3" -phenylene- (CH) 2 ) z4" -, preferably-phenylene- (CH) 2 ) z4" －。Z 1" In the case of this group, the light resistance, particularly the ultraviolet resistance, of the obtained layer is further improved.
In another preferred embodiment, Z is as defined above 1" Is C 1－3 An alkylene group. In one embodiment, Z 1" Can be-CH 2 CH 2 CH 2 -. In further embodiments, Z 1" Can be-CH 2 CH 2 －。
R is as described above 22" Each occurrence is independently hydroxyOr a hydrolyzable group.
R is as described above 22" Preferably, each occurrence is independently a hydrolyzable group.
R is as described above 22" Preferably, each occurrence is independently-OR j 、－OCOR j 、－O－N＝CR j 2 、－NR j 2 、－NHR j -NCO or halogen (in these formulae, R j Represents substituted or unsubstituted C 1－4 Alkyl), more preferably-OR j (i.e., alkoxy). As R j Examples of the method include: unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl and the like. Of these, alkyl groups, particularly unsubstituted alkyl groups, are preferable, and methyl or ethyl groups are more preferable. In one embodiment, R j Is methyl, in further embodiments, R j Is ethyl.
R is as described above 23" Each occurrence is independently a 1-valent organic group. The 1-valent organic group is a 1-valent organic group other than the hydrolyzable group.
The above R 23" In which the 1-valent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 Alkyl groups are more preferably methyl groups.
The q1 "is an integer of 0 to 3 independently at each occurrence, and the r1" is an integer of 0 to 3 independently at each occurrence. In addition, the sum of q1 'and r 1' is within (SiR 22" q1" R 23" r1" ) The number of the units is 3.
The above q 1' is represented by the formula (SiR) 22" q1" R 23" r1" ) The units are each independently preferably an integer of 1 to 3, more preferably 2 to 3, and even more preferably 3.
R is as described above 22′ Each occurrence is independently a hydroxyl group or a hydrolyzable group.
R 22′ Preferably, each occurrence is independently a hydrolyzable group.
R 22′ Preferably, each occurrence is independently-OR j 、－OCOR j 、－O－N＝CR j 2 、－NR j 2 、－NHR j -NCO or halogen (in these formulae, R j Represents substituted or unsubstituted C 1－4 Alkyl), more preferably-OR j (i.e., alkoxy). As R j Examples of the method include: unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl and the like. Of these, alkyl groups, particularly unsubstituted alkyl groups, are preferable, and methyl or ethyl groups are more preferable. In one embodiment, R j Is methyl, in further embodiments, R j Is ethyl.
R is as described above 23′ Each occurrence is independently a 1-valent organic group. The 1-valent organic group is a 1-valent organic group other than the hydrolyzable group.
At R 23′ In which the 1-valent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 Alkyl groups are more preferably methyl groups.
The above-mentioned p1' is an integer of 0 to 3 independently at each occurrence, q1' is an integer of 0 to 3 independently at each occurrence, and r1' is an integer of 0 to 3 independently at each occurrence. In addition, the sum of p ', q1' and r1' is within (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ) The number of the units is 3.
In one embodiment, p1' is 0.
In one embodiment, p1' is defined at each (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ) The units are each independently an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, p1' is 3.
In one embodiment, q1' is defined at each (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ) The units are independently integers of 1 to 3, preferably 2 to 3, more preferably 3.
In one embodiment, p1 'is 0 and q1' is present at each (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ) The units are independently integers of 1 to 3, preferably 2 to 3, more preferably 3.
R is as described above 22 Each occurrence is independently a hydroxyl group or a hydrolyzable group.
R 22 Preferably, each occurrence is independently a hydrolyzable group.
R 22 Preferably, each occurrence is independently-OR j 、－OCOR j 、－O－N＝CR j 2 、－NR j 2 、－NHR j -NCO or halogen (in these formulae, R j Represents substituted or unsubstituted C 1－4 Alkyl), more preferably-OR j (i.e., alkoxy). As R j Examples of the method include: unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl and the like. Of these, alkyl groups, particularly unsubstituted alkyl groups, are preferable, and methyl or ethyl groups are more preferable. In one embodiment, R j Is methyl, in further embodiments, R j Is ethyl.
R is as described above 23 Each occurrence is independently a 1-valent organic group. The 1-valent organic group is a 1-valent organic group other than the hydrolyzable group.
At R 23 In which the 1-valent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 Alkyl groups are more preferably methyl groups.
The above-mentioned p1 is an integer of 0 to 3 independently at each occurrence, q1 is an integer of 0 to 3 independently at each occurrence, and r1 is an integer of 0 to 3 independently at each occurrence. In addition, the sum of p1, q1 and r1 is within (SiR 21 p1 R 22 q1 R 23 r1 ) The number of the units is 3.
In one embodiment, p1 is 0.
In one embodiment, p1 is present at each (SiR 21 p1 R 22 q1 R 23 r1 ) Each independently being an integer from 1 to 3, from 2 to 3Integer or 3. In a preferred embodiment, p1 is 3.
In one embodiment, q1 is defined in each (SiR 21 p1 R 22 q1 R 23 r1 ) The units are independently integers of 1 to 3, preferably 2 to 3, more preferably 3.
In one embodiment, p1 is 0 and q1 is present in each (SiR 21 p1 R 22 q1 R 23 r1 ) The units are independently integers of 1 to 3, preferably 2 to 3, more preferably 3.
In the above formula, R b1 Each occurrence is independently a hydroxyl group or a hydrolyzable group.
R is as described above b1 Preferably, each occurrence is independently a hydrolyzable group.
R is as described above b1 Preferably, each occurrence is independently-OR j 、－OCOR j 、－O－N＝CR j 2 、－NR j 2 、－NHR j -NCO or halogen (in these formulae, R j Represents substituted or unsubstituted C 1－4 Alkyl), more preferably-OR j (i.e., alkoxy). As R j Examples of the method include: unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl and the like. Of these, alkyl groups, particularly unsubstituted alkyl groups, are preferable, and methyl or ethyl groups are more preferable. In one embodiment, R j Is methyl, in further embodiments, R j Is ethyl.
In the above formula, R c1 Each occurrence is independently a 1-valent organic group. The 1-valent organic group is a 1-valent organic group other than the hydrolyzable group.
The above R c1 In which the 1-valent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 Alkyl groups are more preferably methyl groups.
Wherein k1 is an integer of 0 to 3 independently at each occurrence, l1 is an integer of 0 to 3 independently at each occurrence, and m1 is 0 independently at each occurrenceAn integer of 3. In addition, the sum of k1, l1 and m1 is in (SiR a1 k1 R b1 l1 R c1 m1 ) The number of the units is 3.
In one embodiment, k1 is defined at each (SiR a1 k1 R b1 l1 R c1 m1 ) The units are independently integers of 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.
In the above formula (1) and formula (2), R Si In the case of the group represented by the formula (S3), it is preferable that at least 2 Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal portions of the formulas (1) and (2).
In a preferred embodiment, the group of formula (S3) has the formula-Z 1 －SiR 22 q1 R 23 r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer of 0 to 2), -Z 1′ －SiR 22′ q1′ R 23′ r1′ (wherein q1 'is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1' is an integer of 0 to 2.) or-Z 1" －SiR 22" q1" R 23" r1" (wherein q1 'is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1' is an integer of 0 to 2). Z is Z 1 、Z 1′ 、Z 1" 、R 22 、R 23 、R 22′ 、R 23′ 、R 22" And R is 23" The same meaning as described above.
In a preferred embodiment, R is present in formula (S3) 21′ In the case of at least 1, preferably in total R 21′ Among them, q1 "is an integer of 1 to 3, preferably 2 or 3, more preferably 3.
In a preferred embodiment, R is present in formula (S3) 21 In the case of at least 1, preferably in total R 21 Among these, p1 'is 0, q1' is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.
In a preferred embodiment, R is present in formula (S3) a1 In the case of at least 1, preferablyAt all R a1 Among these, p1 is 0, q1 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.
In a preferred embodiment, in formula (S3), k1 is 2 or 3, preferably 3, p1 is 0, q1 is 2 or 3, preferably 3.
R d1 Are each independently-Z at each occurrence 2 －CR 31 p2 R 32 q2 R 33 r2 。
Z 2 Each occurrence is independently a single bond, an oxygen atom, or a 2-valent organic group. In addition, hereinafter referred to as Z 2 Right side of the structure of (C) and (CR) 31 p2 R 32 q2 R 33 r2 ) And (5) combining.
In a preferred embodiment, Z 2 An organic group having a valence of 2.
The above Z 2 Preferably C 1－6 Alkylene, - (CH) 2 ) z5 －O－(CH 2 ) z6 - (wherein z5 is an integer of 0 to 6, for example, an integer of 1 to 6, and z6 is an integer of 0 to 6, for example, an integer of 1 to 6) or- (CH) 2 ) z7 -phenylene- (CH) 2 ) z8 - (wherein z7 is an integer of 0 to 6, for example, an integer of 1 to 6, and z8 is an integer of 0 to 6, for example, an integer of 1 to 6). The C is 1－6 The alkylene group may be linear or branched, and is preferably linear. These groups may be selected, for example, from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 1 or more substituents in the alkynyl group are substituted, preferably unsubstituted.
In a preferred embodiment, Z 2 Is C 1－6 Alkylene or- (CH) 2 ) z7 -phenylene- (CH) 2 ) z8 -, preferably-phenylene- (CH) 2 ) z8 －。Z 2 In the case of this group, the light resistance, particularly the ultraviolet resistance, of the obtained layer is further improved.
In another preferred embodiment, Z is as defined above 2 Is C 1－3 An alkylene group. In one embodiment of the present invention, in one embodiment,Z 2 can be-CH 2 CH 2 CH 2 -. In further embodiments, Z 2 Can be-CH 2 CH 2 －。
R 31 Are each independently-Z at each occurrence 2′ －CR 32′ q2′ R 33′ r2′ 。
Z 2′ Each occurrence is independently a single bond, an oxygen atom, or a 2-valent organic group. In addition, hereinafter referred to as Z 2′ Right side of the structure of (C) and (CR) 32′ q2′ R 33′ r2′ ) And (5) combining.
The above Z 2′ Preferably C 1－6 Alkylene, - (CH) 2 ) z5′ －O－(CH 2 ) z6′ - (wherein z5 'is an integer of 0 to 6, for example, an integer of 1 to 6, and z6' is an integer of 0 to 6, for example, an integer of 1 to 6) or- (CH) 2 ) z7′ -phenylene- (CH) 2 ) z8′ - (wherein z7 'is an integer of 0 to 6, for example, an integer of 1 to 6, and z8' is an integer of 0 to 6, for example, an integer of 1 to 6). The C is 1－6 The alkylene group may be linear or branched, and is preferably linear. These groups may be selected, for example, from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 1 or more substituents in the alkynyl group are substituted, preferably unsubstituted.
In a preferred embodiment, Z 2′ Is C 1－6 Alkylene or- (CH) 2 ) z7′ -phenylene- (CH) 2 ) z8′ -, preferably-phenylene- (CH) 2 ) z8′ －。Z 2′ In the case of this group, the light resistance, particularly the ultraviolet resistance, is further improved.
In another preferred embodiment, Z is as defined above 2′ Is C 1－3 An alkylene group. In one embodiment, Z 2′ Can be-CH 2 CH 2 CH 2 -. In further embodiments, Z 2′ Can be-CH 2 CH 2 －。
R is as described above 32′ Are each independently-Z at each occurrence 3 －SiR 34 n2 R 35 3－n2 。
The above Z 3 Each occurrence is independently a single bond, an oxygen atom, or a 2-valent organic group. In addition, hereinafter referred to as Z 3 Right side of the structure of (1) and (SiR) 34 n2 R 35 3－n2 ) And (5) combining.
In one embodiment, Z 3 Is an oxygen atom.
In one embodiment, Z 3 An organic group having a valence of 2.
The above Z 3 Preferably C 1－6 Alkylene, - (CH) 2 ) z5" －O－(CH 2 ) z6" - (wherein z5 "is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6) or- (CH) 2 ) z7" -phenylene- (CH) 2 ) z8" - (wherein z7 "is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6). The C is 1－6 The alkylene group may be linear or branched, and is preferably linear. These groups may be selected, for example, from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 1 or more substituents in the alkynyl group are substituted, preferably unsubstituted.
In a preferred embodiment, Z 3 Is C 1－6 Alkylene or- (CH) 2 ) z7" -phenylene- (CH) 2 ) z8" -, preferably-phenylene- (CH) 2 ) z8" －。Z 3 In the case of this group, the light resistance, particularly the ultraviolet resistance, is further improved.
In another preferred embodiment, Z is as defined above 3 Is C 1－3 An alkylene group. In one embodiment, Z 3 Can be-CH 2 CH 2 CH 2 -. In further embodiments, Z 3 Can be-CH 2 CH 2 －。
R is as described above 34 Each occurrence is independently a hydroxyl group or a hydrolyzable group.
R 34 Preferably, each occurrence is independently a hydrolyzable group.
R 34 Preferably, each occurrence is independently-OR j 、－OCOR j 、－O－N＝CR j 2 、－NR j 2 、－NHR j -NCO or halogen (in these formulae, R j Represents substituted or unsubstituted C 1－4 Alkyl), more preferably-OR j (i.e., alkoxy). As R j Examples of the method include: unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl and the like. Of these, alkyl groups, particularly unsubstituted alkyl groups, are preferable, and methyl or ethyl groups are more preferable. In one embodiment, R j Is methyl, in further embodiments, R j Is ethyl.
R is as described above 35 Each occurrence is independently a 1-valent organic group. The 1-valent organic group is a 1-valent organic group other than the hydrolyzable group.
The above R 35 In which the 1-valent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 Alkyl groups are more preferably methyl groups.
In the above formula, n2 is represented by the formula (SiR 34 n2 R 35 3－n2 ) The units are independently integers from 0 to 3. Wherein R is Si In the case of the group represented by the formula (S4), at least 1 (SiR) in which n2 is 1 to 3 is present in the terminal portion of the formulae (1) and (2) 34 n2 R 35 3－n2 ) A unit. That is, at this end portion, all n2 are not 0 at the same time. In other words, at least 1 Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present in the terminal portion of the formula (1) and the formula (2).
n2 is found in each (SiR 34 n2 R 35 3－n2 ) The units are each independently preferably an integer of 1 to 3, more preferably 2 to 3, and even more preferably 3.
R is as described above 33′ Each occurrence is independently a hydrogen atom, a hydroxyl group, or a 1-valent organic group. The 1-valent organic group is a 1-valent organic group other than the hydrolyzable group.
The above R 33′ In which the organic radical of valence 1 is preferably C 1－20 Alkyl or- (C) s H 2s ) t1 －(O－C s H 2s ) t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably C 1－20 Alkyl, more preferably C 1－6 Alkyl is particularly preferably methyl.
In one embodiment, R 33′ Is hydroxyl.
In further embodiments, R 33′ An organic group of valence 1, preferably C 1－20 Alkyl, more preferably C 1－6 An alkyl group.
Q2 'is an integer of 0 to 3 independently at each occurrence, and r2' is an integer of 0 to 3 independently at each occurrence. In addition, the sum of q2 'and r2' is equal to (CR 32′ q2′ R 33′ r2′ ) The number of the units is 3.
q2' is shown at each (CR 32′ q2′ R 33′ r2′ ) The units are each independently preferably an integer of 1 to 3, more preferably 2 to 3, and even more preferably 3.
R 32 Are each independently-Z at each occurrence 3 －SiR 34 n2 R 35 3－n2 . The Z is 3 －SiR 34 n2 R 35 3－n2 And R is as described above 32′ The meaning of the description is the same.
R is as described above 33 Each occurrence is independently a hydrogen atom, a hydroxyl group, or a 1-valent organic group. The 1-valent organic group is a 1-valent organic group other than the hydrolyzable group.
The above R 33 In which the 1-valent organic group is preferably C 1－20 Alkyl or- (C) s H 2s ) t1 －(O－C s H 2s ) t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably C 1－20 Alkyl, more preferably C 1－6 Alkyl is particularly preferably methyl.
In one embodiment, R 33 Is hydroxyl.
In further embodiments, R 33 An organic group of valence 1, preferably C 1－20 Alkyl, more preferably C 1－6 An alkyl group.
P2 is an integer of 0 to 3 independently at each occurrence, q2 is an integer of 0 to 3 independently at each occurrence, and r2 is an integer of 0 to 3 independently at each occurrence. The sum of p2, q2 and r2 is equal to (CR 31 p2 R 32 q2 R 33 r2 ) The number of the units is 3.
In one embodiment, p2 is 0.
In one embodiment, p2 is present at each (CR 31 p2 R 32 q2 R 33 r2 ) The units are each independently an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, p2 is 3.
In one embodiment, q2 is found at each (CR 31 p2 R 32 q2 R 33 r2 ) The units are independently integers of 1 to 3, preferably 2 to 3, more preferably 3.
In one embodiment, p2 is 0 and q2 is present in each (CR 31 p2 R 32 q2 R 33 r2 ) The units are independently integers of 1 to 3, preferably 2 to 3, more preferably 3.
R is as described above e1 Are each independently-Z at each occurrence 3 －SiR 34 n2 R 35 3－n2 . The Z is 3 －SiR 34 n2 R 35 3－n2 And R is as described above 32′ The meaning of the description is the same.
R is as described above f1 Each occurrence is independently a hydrogen atom, a hydroxyl group, or a 1-valent organic group. The 1-valent organic group is a 1-valent organic group other than the hydrolyzable group.
The above R f1 In which the 1-valent organic group is preferably C 1－20 Alkyl or- (C) s H 2s ) t1 －(O－C s H 2s ) t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably C 1－20 Alkyl, more preferably C 1－6 Alkyl is particularly preferably methyl.
In one embodiment, R f1 Is hydroxyl.
In further embodiments, R f1 An organic group of valence 1, preferably C 1－20 Alkyl, more preferably C 1－6 An alkyl group.
Where k2 is an integer of 0 to 3 independently at each occurrence, l2 is an integer of 0 to 3 independently at each occurrence, and m2 is an integer of 0 to 3 independently at each occurrence. In addition, the sum of k2, l2 and m2 is equal to (CR d1 k2 R e1 l2 R f1 m2 ) The number of the units is 3.
In the above formula (1) and formula (2), R Si In the case of the group represented by the formula (S4), it is preferable that at least 2 Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal portions of the formula (1) and the formula (2).
In one embodiment, R Si In the case of the group represented by the formula (S4), n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 34 n2 R 35 3－n2 ) The units are present in the terminal portions of the formulae (1) and (2) in an amount of 2 or more, for example, 2 to 27, preferably 2 to 9, more preferably 2 to 6, still more preferably 2 to 3, and particularly preferably 3.
In a preferred embodiment, R is present in formula (S4) 32′ Is the case of (2)At least 1, preferably at all R 32′ Among them, n2 is an integer of 1 to 3, preferably 2 or 3, more preferably 3.
In a preferred embodiment, R is present in formula (S4) 32 In the case of at least 1, preferably in total R 32 Among them, n2 is an integer of 1 to 3, preferably 2 or 3, more preferably 3.
In a preferred embodiment, R is present in formula (S4) e1 In the case of at least 1, preferably in total R a1 Among them, n2 is an integer of 1 to 3, preferably 2 or 3, more preferably 3.
In a preferred embodiment, in formula (S4), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.
R is as described above g1 And R is h1 Are each independently-Z at each occurrence 4 －SiR 11 n1 R 12 3－n1 、－Z 4 －SiR a1 k1 R b1 l1 R c1 m1 、－Z 4 －CR d1 k2 R e1 l2 R f1 m2 . Wherein R is 11 、R 12 、R a1 、R b2 、R c1 、R d1 、R e1 、R f1 N1, k1, l1, m1, k2, l2 and m2 have the meaning given above.
In a preferred embodiment, R g1 And R is h1 Each independently is-Z 4 －SiR 11 n1 R 12 3－n1 。
The above Z 4 Each occurrence is independently a single bond, an oxygen atom, or a 2-valent organic group. In addition, hereinafter referred to as Z 4 Right side of the structure of (1) and (SiR) 11 n1 R 12 3－n1 ) And (5) combining.
In one embodiment, Z 4 Is an oxygen atom.
In one embodiment, Z 4 An organic group having a valence of 2.
The above Z 4 Preferably C 1－6 Alkylene, - (CH) 2 ) z5" －O－(CH 2 ) z6" - (wherein z5 "is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6) or- (CH) 2 ) z7" -phenylene- (CH) 2 ) z8" - (wherein z7 "is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6). The C is 1－6 The alkylene group may be linear or branched, and is preferably linear. These groups may be selected, for example, from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 1 or more substituents in the alkynyl group are substituted, preferably unsubstituted.
In a preferred embodiment, Z 4 Is C 1－6 Alkylene or- (CH) 2 ) z7" -phenylene- (CH) 2 ) z8" -, preferably-phenylene- (CH) 2 ) z8" －。Z 3 In the case of this group, the light resistance, particularly the ultraviolet resistance, is further improved.
In another preferred embodiment, Z is as defined above 4 Is C 1－3 An alkylene group. In one embodiment, Z 4 Can be-CH 2 CH 2 CH 2 -. In further embodiments, Z 4 Can be-CH 2 CH 2 －。
In one embodiment, R Si Is a group represented by the formula (S2), the formula (S3), the formula (S4) or the formula (S5). These compounds are capable of forming a surface-treated layer having high surface slidability.
In one embodiment, R Si Is a group represented by the formula (S3), the formula (S4) or the formula (S5). These compounds have a plurality of hydrolyzable groups at one end, and therefore can strongly adhere to a substrate, and can form a surface-treated layer having high wear durability.
In one embodiment, R Si Is a group represented by the formula (S3) or the formula (S4). These compounds have a plurality of hydrolyzable groups branching from one Si atom or C atom at one end, and thus can be formed to have higher wear durabilityIs a surface treatment layer of the substrate.
In one embodiment, R Si Is a group represented by the formula (S1).
In one embodiment, R Si Is a group represented by the formula (S2).
In one embodiment, R Si Is a group represented by the formula (S3).
In one embodiment, R Si Is a group represented by the formula (S4).
In one embodiment, R Si Is a group represented by the formula (S5).
In the above formulas (1) and (2), X A It can be understood that the fluorine-containing group (R) mainly provides functions such as liquid repellency and slip property F1 And R is F2 ) And a site (R) providing binding ability to a substrate Si ) And a connecting part for connecting. Accordingly, as long as the compounds represented by the formula (1) and the formula (2) can exist stably, the X A The compound may be a single bond or an arbitrary group.
In the above formula (1), α1 is an integer of 1 to 9, and β1 is an integer of 1 to 9. These α1 and β1 groups can be determined according to X A The valence number of (c) varies. Sum of alpha 1 and beta 1 and X A The valence of (2) is the same. For example, X A In the case of an organic group having a valence of 10, the sum of α1 and β1 is 10, and for example, α1 may be 9 and β1 may be 1, α1 may be 5 and β1 may be 5, or α1 may be 1 and β1 may be 9. In addition, X A In the case of an organic group of valence 2, α1 and β1 are 1.
In the above formula (2), γ1 is an integer of 1 to 9.γ1 can be according to X A The valence number of (c) varies. That is, γ1 is represented by X A A value obtained by subtracting 1 from the valence of (2).
X A Each independently is a single bond or an organic group having a valence of 2 to 10;
above X A The organic group having a valence of 2 to 10 is preferably an organic group having a valence of 2 to 8. In one embodiment, the organic group having a valence of 2 to 10 is preferably an organic group having a valence of 2 to 4, more preferably an organic group having a valence of 2. In other embodiments, the organic group having a valence of 2 to 10 is preferably an organic group having a valence of 3 to 8, more preferably an organic group having a valence of 3 to 6A group.
In one embodiment, X A Is a single bond or a 2-valent organic group, and α1 is 1 and β1 is 1.
In one embodiment, X A Is a single bond or a 2-valent organic group, and γ1 is 1.
In one embodiment, X A An organic group having a valence of 3 to 6, wherein α1 is 1 and β1 is 2 to 5.
In one embodiment, X A Is an organic group with a valence of 3-6, and gamma 1 is 2-5.
In one embodiment, X A Is a 3-valent organic group, and α1 is 1 and β1 is 2.
In one embodiment, X A Is a 3-valent organic group, and γ1 is 2.
X A In the case of a single bond or an organic group having a valence of 2, the formulae (1) and (2) are represented by the following formulae (1 ') and (2').
R F1 -X A -R Si (1’)
R Si -X A -R F2 -X A -R Si (2’)
In one embodiment, X A Is a single bond.
In a further embodiment, X A An organic group having a valence of 2.
In one embodiment, as X A For example, a single bond or a 2-valent organic group represented by the following formula:
-(R 51 ) p5 -(X 51 ) q5 -
[ formula:
R 51 represents a single bond, - (CH) 2 ) s5 -or ortho-, meta-or para-phenylene, preferably- (CH) 2 ) s5 -，
s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, still more preferably 1 or 2,
X 51 representation- (X) 52 ) 15 -，
X 52 Each occurrence is independently selected from the group consisting of-O-, -S-, O-phenylene m-or p-phenylene, -C (O) O-, -Si (R) 53 ) 2 -、-(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 －、－CONR 54 －、－O－CONR 54 －、－NR 54 -and- (CH) 2 ) n5 A group which is a radical of the formula,
R 53 each occurrence is independently phenyl, C 1－6 Alkyl or C 1－6 Alkoxy, preferably phenyl or C 1－6 An alkyl group, more preferably a methyl group,
R 54 each occurrence of which independently represents a hydrogen atom, a phenyl group or a C 1－6 Alkyl (preferably methyl),
m5 is independently an integer from 1 to 100, preferably an integer from 1 to 20,
n5 is independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3,
l5 is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
p5 is either 0 or 1 and,
q5 is either 0 or 1 and,
wherein at least one of p5 and q5 is 1, and the order in which the repeating units, denoted by p5 or q5 and bracketed, are present is arbitrary.
Wherein X is A (typically X A Hydrogen atom of (C) may be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 1 or more substituents of the fluoroalkyl group. In a preferred embodiment, X A Are not substituted with these groups.
In a preferred embodiment, X is as defined above A Each independently is- (R) 51 ) p5 －(X 51 ) q5 －R 52 －。R 52 Represents a single bond, - (CH) 2 ) t5 -or ortho-, meta-or para-phenylene, preferably- (CH) 2 ) t5 -. t5 is an integer from 1 to 20, preferably an integer from 2 to 6,more preferably an integer of 2 to 3. Wherein R is 52 (typically R) 52 Hydrogen atom of (C) may be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 1 or more substituents in the fluoroalkyl group. In a preferred mode, R 56 Are not substituted with these groups.
Preferably X is as defined above A Each independently is:
a single bond,
C 1－20 Alkylene group,
－R 51 －X 53 －R 52 -, or
－X 54 －R 5 －
[ formula, R 51 And R is 52 In the same manner as described above,
X 53 representation of
－O－、
－S－、
－C(O)O－、
－CONR 54 －、
－O－CONR 54 －、
－Si(R 53 ) 2 －、
－(Si(R 53 ) 2 O) m5 －Si(R 53 ) 2 －、
－O－(CH 2 ) u5 －(Si(R 53 ) 2 O) m5 －Si(R 53 ) 2 －、
－O－(CH 2 ) u5 －Si(R 53 ) 2 －O－Si(R 53 ) 2 －CH 2 CH 2 －Si(R 53 ) 2 －O－Si(R 53 ) 2 －、
－O－(CH 2 ) u5 －Si(OCH 3 ) 2 OSi(OCH 3 ) 2 －、
－CONR 54 －(CH 2 ) u5 －(Si(R 53 ) 2 O) m5 －Si(R 53 ) 2 －、
－CONR 54 －(CH 2 ) u5 －N(R 54 ) -or
－CONR 54 - (ortho-phenylene, meta-phenylene or para-phenylene) -Si (R) 53 ) 2 －
(wherein R is 53 、R 54 And m5 is as defined above,
u5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. ) X, X 54 Representation of
－S－、
－C(O)O－、
－CONR 54 －、
－O－CONR 54 －、
－CONR 54 －(CH 2 ) u5 －(Si(R 54 ) 2 O) m5 －Si(R 54 ) 2 －、
－CONR 54 －(CH 2 ) u5 －N(R 54 ) -, or
－CONR 54 - (ortho-phenylene, meta-phenylene or para-phenylene) -Si (R) 54 ) 2 －
(wherein each symbol has the same meaning as described above). ].
More preferably X as described above A Each independently is:
a single bond,
C 1－20 Alkylene group,
－(CH 2 ) s5 －X 53 －、
－(CH 2 ) s5 －X 53 －(CH 2 ) t5 －
－X 54 -, or
－X 54 －(CH 2 ) t5 －
[ wherein X is 53 、X 54 S5 and t5 are as defined above.]。
More preferably X as described above A Each independently is:
a single bond,
C 1－20 Alkylene groupA base group,
－(CH 2 ) s5 －X 53 －(CH 2 ) t5 -, or
－X 54 －(CH 2 ) t5 －
In the formula, each symbol has the same meaning as described above. ].
In a preferred embodiment, X is as defined above A Each independently is:
a single bond,
C 1－20 Alkylene group,
－(CH 2 ) s5 －X 53 -or
－(CH 2 ) s5 －X 53 －(CH 2 ) t5 －
[ in the above-mentioned, a method for producing a semiconductor device,
X 53 is-O-, -CONR 54 -or-O-CONR 54 －，
R 54 Each occurrence of which independently represents a hydrogen atom, a phenyl group or a C 1－6 An alkyl group, a hydroxyl group,
s5 is an integer of 1 to 20,
t5 is an integer of 1 to 20. ].
In a preferred embodiment, X is as defined above A Each independently is:
－(CH 2 ) s5 －O－(CH 2 ) t5 －
－CONR 54 －(CH 2 ) t5 －
[ in the above-mentioned, a method for producing a semiconductor device,
R 54 each occurrence of which independently represents a hydrogen atom, a phenyl group or a C 1－6 An alkyl group, a hydroxyl group,
s5 is an integer of 1 to 20,
t5 is an integer of 1 to 20. ].
In one embodiment, the above X A Each independently is:
a single bond,
C 1－20 Alkylene group,
－(CH 2 ) s5 －O－(CH 2 ) t5 －、
－(CH 2 ) s5 －(Si(R 53 ) 2 O) m5 －Si(R 53 ) 2 －(CH 2 ) t5 －、
－(CH 2 ) s5 －O－(CH 2 ) u5 －(Si(R 53 ) 2 O) m5 －Si(R 53 ) 2 －(CH 2 ) t5 -or- (CH) 2 ) s5 －O－(CH 2 ) t5 －Si(R 53 ) 2 －(CH 2 ) u5 －Si(R 53 ) 2 －(C v H 2v )－
[ formula, R 53 M5, s5, t5 and u5 have the same meaning as above, and v5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.]。
In the above, - (C) v H 2v ) The group may be linear or branched, and may be-CH 2 CH 2 －、－CH 2 CH 2 CH 2 －、－CH(CH 3 )－、－CH(CH 3 )CH 2 －。
Above X A Can be independently selected from fluorine atoms, C 1－3 Alkyl and C 1－3 Fluoroalkyl (preferably C) 1－3 Perfluoroalkyl) is substituted with 1 or more substituents. In one embodiment, X A Is unsubstituted.
In addition, the X A Left side and R of the formulae (I) F1 Or R is F2 Combine, right side with R Si And (5) combining.
In one embodiment, X A Can be independently-O-C 1－6 Groups other than alkylene.
In another embodiment, as X A Examples of the group include the following:
[ formula, R 41 Independently of each other, a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1－6 Alkoxy, preferably methyl;
D is a group selected from the group consisting of:
－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 represents phenyl), and
(wherein R is 42 Each independently represents a hydrogen atom, C 1－6 Alkyl or C of (2) 1－6 Preferably represents methyl or methoxy, more preferably represents methyl. ),
e is- (CH) 2 ) n - (n is an integer of 2 to 6),
d and R of molecular main chain F1 Or R is F2 Combining E and R Si And (5) combining.]
As the above X A For example, specific examples of (a) include:
a single bond,
－CH 2 OCH 2 －、
－CH 2 O(CH 2 ) 2 －、
－CH 2 O(CH 2 ) 3 －、
－CH 2 O(CH 2 ) 4 －、
－CH 2 O(CH 2 ) 5 －、
－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 OCF 2 CHFOCF 2 CF 2 CF 2 －C(O)NH－CH 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 －Si(CH 3 ) 2 －(CH 2 ) 2 －、
－CH 2 －、
－(CH 2 ) 2 －、
－(CH 2 ) 3 －、
－(CH 2 ) 4 －、
－(CH 2 ) 5 －、
－(CH 2 ) 6 －、
－CO－、
－CONH－、
－CONH－CH 2 －、
－CONH－(CH 2 ) 2 －、
－CONH－(CH 2 ) 3 －、
－CONH－(CH 2 ) 4 －、
－CONH－(CH 2 ) 5 －、
－CONH－(CH 2 ) 6 －、
－CON(CH 3 )－CH 2 －、
－CON(CH 3 )－(CH 2 ) 2 －、
－CON(CH 3 )－(CH 2 ) 3 －、
－CON(CH 3 )－(CH 2 ) 4 －、
－CON(CH 3 )－(CH 2 ) 5 －、
－CON(CH 3 )－(CH 2 ) 6 －、
－CON(Ph)－CH 2 - (wherein Ph represents phenyl),
－CON(Ph)－(CH 2 ) 2 - (wherein Ph represents phenyl),
－CON(Ph)－(CH 2 ) 3 - (wherein Ph represents phenyl),
－CON(Ph)－(CH 2 ) 4 - (wherein Ph represents phenyl),
－CON(Ph)－(CH 2 ) 5 - (wherein Ph represents phenyl),
－CON(Ph)－(CH 2 ) 6 - (wherein Ph represents phenyl),
－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 －\
－OCH 2 －、
－O(CH 2 ) 3 －、
－OCFHCF 2 －、
Etc.
In yet another embodiment, X A Each independently is of the formula: - (R) 16 ) x1 －(CFR 17 ) y1 －(CH 2 ) z1 -the group shown. Wherein x1, y1 and z1 are each independently integers of 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of the presence of the repeating units bracketed is arbitrary in the formula.
In the above formula, R 16 Each occurrence of which is independently an oxygen atom, phenylene, carbazolylene, -NR 18 - (wherein R is 18 Represents a hydrogen atom or an organic group) or a 2-valent organic group. Preferably R 18 Is an oxygen atom or a 2-valent polar group.
The "2-valent polar group" is not particularly limited, and includes-C (O) -, -C (=NR) 19 ) -and-C (O) NR 19 - (in these formulae, R) 19 Represents a hydrogen atom or a lower alkyl group). The "lower alkyl" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, or n-propyl, and may be substituted with 1 or more fluorine atoms.
In the above formula, R 17 Each occurrence is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
In yet another embodiment, X is A The following groups may be mentioned as examples:
[ in the above-mentioned, a method for producing a semiconductor device,
R 41 independently of each other, a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1－6 Alkoxy is preferably methyl;
at each X A In the radicals, any several of T are R to the main chain of the molecule F1 Or R is F2 The following groups are combined:
－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 represents phenyl) or
[ formula, R 42 Each independently represents a hydrogen atom, C 1－6 Alkyl or C of (2) 1－6 Preferably represents methyl or methoxy, more preferably represents methyl.]，
Other T are associated with R of the molecular main chain Si Where present in combination, the remaining T's are each independently methyl, phenyl, C 1－6 Alkoxy or a radical scavenger or an ultraviolet absorber.
The radical trapping group is not particularly limited as long as it is a group capable of trapping radicals generated by light irradiation, and examples thereof include residues of benzophenone, benzotriazole, benzoate, salicylate, crotonate, malonate, organic acrylate, hindered amine, hindered phenol, and triazine.
The ultraviolet absorbing group is not particularly limited as long as it is a group capable of absorbing ultraviolet rays, and examples thereof include benzotriazole groups, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylic acid esters or alkoxycinnamic acid esters, oxamides, oxamide groups, benzoxazinones, and benzoxazole groups.
In a preferred embodiment, preferable radical-capturing groups or ultraviolet absorbing groups include:
in this embodiment, X A And each independently is an organic group having a valence of 3 to 10.
In yet another embodiment, X is A The following groups may be mentioned as examples:
[ formula, R 25 、R 26 And R is 27 Each independently is an organic group having a valence of 2 to 6,
R 25 and at least 1R F1 Binding, R 26 And R is 27 Respectively with at least 1R Si And (5) combining.]
In one embodiment, R is as defined above 25 Is a single bond, C 1－20 Alkylene, C 3－20 Cycloalkylene, C 5－20 Arylene, -R 57 －X 58 －R 59 －、－X 58 －R 59 -or-R 57 －X 58 -. Above, R is 57 And R is 59 Are each independently a single bond, C 1－20 Alkylene, C 3－20 Cycloalkylene or C 5－20 Arylene groups. Above X 58 is-O-, -S-, -CO-, -O-CO-or-COO－。
In one embodiment, R is as defined above 26 And R is 27 Are each independently a hydrocarbon group, or a group having at least 1 atom selected from N, O and S in the hydrocarbon terminal or main chain, preferably C 1－6 Alkyl, -R 36 －R 37 －R 36 －、－R 36 －CHR 38 2 -and the like. Wherein R is 36 Each independently represents a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. R37 is N, O or S, preferably N or O. R is R 38 is-R 45 －R 46 －R 45 －、－R 46 －R 45 -or-R 45 －R 46 -. Wherein R is 45 Each independently represents an alkyl group having 1 to 6 carbon atoms. R is R 46 N, O or S, preferably O.
In this embodiment, X A And each independently is an organic group having a valence of 3 to 10.
In yet another embodiment, X is A Examples of (a) include the following groups:
[ wherein X is a Is a single bond or a 2-valent organic group.]
Above X a Is a single bond or a divalent linking group directly bonded to the isocyanurate ring. As X a Preferably a single bond, an alkylene group or a divalent group containing at least 1 bond selected from the group consisting of an ether bond, an ester bond, an amide bond and a thioether bond, more preferably a single bond, an alkylene group having 1 to 10 carbon atoms or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least 1 bond selected from the group consisting of an ether bond, an ester bond, an amide bond and a thioether bond.
As X a More preferred is a group represented by the following formula:
－(CX 121 X 122 ) x1 －(X a1 ) y1 －(CX 123 X 124 ) z1 －
(in the process)，X 121 ～X 124 H, F, OH, OR-OSi (OR) 121 ) 3 (wherein 3R' s 121 Each independently represents an alkyl group having 1 to 4 carbon atoms. ),
above X a1 is-C (=O) NH-, -NHC (=O) -, -O-, -C (=O) O-, -OC (=O) O-, or-NHC (=O) NH- (left side of each bond and CX 121 X 122 And (5) combining. ),
x1 is an integer of 0 to 10, y1 is 0 or 1, and z1 is an integer of 1 to 10. ).
As the above X a1 preferably-O-or-C (=O) O-.
As the above X a Particularly preferred are groups of the formula:
－(CF 2 ) m11 －(CH 2 ) m12 －O－(CH 2 ) m13 －
(wherein m11 is an integer of 1 to 3, m12 is an integer of 1 to 3, and m13 is an integer of 1 to 3),
－(CF 2 ) m14 －(CH 2 ) m15 －O－CH 2 CH(OH)－(CH 2 ) m16 －
(wherein m14 is an integer of 1 to 3, m15 is an integer of 1 to 3, and m16 is an integer of 1 to 3),
－(CF 2 ) m17 －(CH 2 ) m18 －
(wherein m17 is an integer of 1 to 3, m18 is an integer of 1 to 3),
－(CF 2 ) m19 －(CH 2 ) m20 －O－CH 2 CH(OSi(OCH 3 ) 3 )－(CH 2 ) m21 －
(wherein m19 is an integer of 1 to 3, m20 is an integer of 1 to 3, and m21 is an integer of 1 to 3), or
－(CH 2 ) m22 －
(wherein m22 is an integer of 1 to 3).
As the above X a Specifically, there are no particular restrictions, and there may be mentionedCH 2 －、－C 2 H 4 －、－C 3 H 6 －、－C 4 H 8 －、－C 4 H 8 －O－CH 2 －、－CO－O－CH 2 －CH(OH)－CH 2 －、－(CF 2 ) n5 - (n 5 is an integer of 0 to 4)), and- (CF 2 ) n5 －(CH 2 ) m5 - (n 5 and m5 are each independently an integer of 0 to 4), -CF 2 CF 2 CH 2 OCH 2 CH(OH)CH 2 －、－CF 2 CF 2 CH 2 OCH 2 CH(OSi(OCH 3 ) 3 )CH 2 -and the like.
In this embodiment, X A Each independently is a 2 or 3 valent organic group.
The fluorinated polyether group-containing silane compound represented by the above formula (1) or (2) is not particularly limited and may have a concentration of 5X 10 2 ～1×10 5 Is a polymer having an average molecular weight of (3). Within this range, an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000 is preferable from the viewpoint of wear durability. Wherein the "average molecular weight" is the number average molecular weight, and the "average molecular weight" is determined by 19 F-NMR measured values.
In one embodiment, the composition of the present invention contains a compound represented by formula (1).
In one embodiment, the composition of the present invention contains a compound represented by formula (1) and does not contain a compound represented by formula (2).
In another embodiment, the composition of the present invention contains a compound represented by formula (1) and a compound represented by formula (2).
When the composition of the present invention contains the compound represented by the formula (1) and the compound represented by the formula (2), the compound represented by the formula (2) may be preferably 35 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, still more preferably 15 mol% or less, particularly preferably 10 mol% or less, for example 5 mol% or less, 3 mol% or less, 1 mol% or less, or 0.1 mol% or less, with respect to the total of the compound represented by the formula (1) and the compound represented by the formula (2). By setting the amount of the compound represented by the formula (2) in the above range, a layer having a relatively low polar component on the surface can be obtained. The compound represented by the formula (2) may be, for example, 0.01 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.5 mol% or more, 1 mol% or more, 2 mol% or more, or 5 mol% or more, based on the total of the compound represented by the formula (1) and the compound represented by the formula (2). The compound represented by the formula (2) is preferably 0.01 to 35 mol%, more preferably 0.01 to 30 mol%, still more preferably 0.01 to 20 mol%, still more preferably 0.01 to 10 mol%, for example, 0.1 to 30 mol%, 0.2 to 20 mol%, and 0.5 to 10 mol%, based on the total of the compound represented by the formula (1) and the compound represented by the formula (2).
The compound represented by the above formula (1) or (2) can be obtained by, for example, a known method, for example, a method described in International patent publication No. 97/07155, japanese patent application laid-open No. 2008-534696, japanese patent application laid-open No. 2014-218639, japanese patent application laid-open No. 2017-82194, or the like.
(composition)
In the composition of the present invention, the content of the fluorine-containing liquid-repellent compound (B) may be preferably 0.1 mass% or more, more preferably 0.5 mass% or more, still more preferably 1.0 mass% or more, for example, 5.0 mass% or more, 10.0 mass% or more, or 15.0 mass% or more, with respect to the total of the component (a) crosslinkable compound and the component (B) fluorine-containing liquid-repellent compound. The content of the fluorine-containing liquid-repellent compound (B) may be preferably 90.0 mass% or less, more preferably 50.0 mass% or less, still more preferably 30.0 mass% or less, particularly preferably 20.0 mass% or less, for example 15.0 mass% or less, 10.0 mass% or less, 5.0 mass% or 3.0 mass% or less, based on the total of the component (a) crosslinkable compound and the component (B) fluorine-containing liquid-repellent compound.
In one embodiment, the content of the fluorine-containing liquid-repellent compound (B) in the composition of the present invention may be preferably 0.1 to 90.0% by mass, more preferably 0.5 to 50.0% by mass, still more preferably 1.0 to 30.0% by mass, for example, 0.1 to 30.0% by mass, 0.1 to 20.0% by mass, 0.1 to 15.0% by mass, 0.5 to 30.0% by mass, 0.5 to 20.0% by mass, 0.5 to 15.0% by mass, 1.0 to 20.0% by mass, or 0.1 to 15.0% by mass, relative to the total of the component (a) crosslinkable compound and the component (B) fluorine-containing liquid-repellent compound.
The F/Si ratio of the surface of the layer formed of the composition of the present invention may be preferably 3.0 or more, more preferably 5.0 or more, still more preferably 8.0 or more, for example, 10.0 or more. The upper limit of the F/Si ratio of the surface of the layer formed of the composition of the present invention is not particularly limited, but the larger the upper limit is, the more preferable is, 30.0 or less, 20.0 or less, or 15.0 or less.
In one embodiment, the F/Si ratio of the surface of the layer formed from the composition of the present invention may be preferably 5.0 to 30.0, more preferably 5.0 to 20.0, still more preferably 8.0 to 20.0, for example 8.0 to 15.0.
The slip angle of water of the layer formed from the composition of the present invention may be preferably 60 ° or less, more preferably 50 ° or less, still more preferably 30 ° or less, still more preferably 25 ° or less, and particularly preferably 20 ° or less. The lower limit of the slip angle of water of the layer formed by the composition of the present invention is not particularly limited, but may be, for example, 1 ° or more, 5 ° or more, or 10 ° or more, as the lower limit is smaller.
The layer formed from the composition of the present invention may have a sliding angle of hexadecane of preferably 35 ° or less, more preferably 30 ° or less, still more preferably 25 ° or less, and still more preferably 20 ° or less. The lower limit of the slip angle of water of the layer formed by the composition of the present invention is not particularly limited, but may be, for example, 1 ° or more, 5 ° or more, or 10 ° or more, as the lower limit is smaller.
Method for measuring slip angle
The surface treatment layer side of the surface treatment sample placed horizontally was dropped with a liquid from a micro-syringe, the liquid was inclined to 90 ° at a speed of 2 ° per second, and the condition of the liquid droplet was observed, and the liquid droplet was moved by an angle of 5mm as a slip angle. With respect to the amount of droplets, water was 20. Mu.L and hexadecane was 5. Mu.L.
The composition of the present invention may further contain 1 or more other components selected from the group consisting of organic solvents, water and catalysts.
The organic solvent may be a fluorine-containing organic solvent or a fluorine-free organic solvent.
Examples of the fluorine-containing organic solvent include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkyl ethanol, perfluorobenzene, perfluorotoluene, perfluoroalkyl amine (trade name), perfluoroalkyl ether, perfluorobutyl tetrahydrofuran, polyfluoroaliphatic hydrocarbon (ASAHIKLIN AC) 6000 (trade name)), hydrochlorofluorocarbon (ASAHIKLIN AK-225 (trade name), hydrofluoroether (NOVEC (trade name), HFE-7100 (trade name), HFE-7300 (trade name), 1,2, 3, 4-heptafluorocyclopentane, fluoroalkyl alcohol, perfluoroalkyl bromide, perfluoroalkyl iodide, perfluoropolyether (Krytox (trade name), demum (trade name), fomblin (trade name), 1, 3-bistrifluoromethyl benzene, 2- (perfluoroalkyl) ethyl methacrylate, 2- (perfluoroalkyl) ethyl acrylate, perfluoroalkyl) vinyl fluoride, fluorocarbon 134a, and oligomer.
Examples of the fluorine-free organic solvent include acetone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether pentane, hexane, heptane, octane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, benzene, toluene, xylene, nitrobenzene, diethyl ether, dimethoxyethane, diglyme, triglyme, ethyl acetate, butyl acetate, dimethylformamide, dimethyl sulfoxide, 2-butanone, acetonitrile, benzonitrile, butanol, 1-propanol, 2-propanol, ethanol, methanol, and diacetone alcohol.
Among them, methyl isobutyl ketone, propylene glycol monomethyl ether, hexadecane, butyl acetate, acetone, 2-butanone, cyclohexanone, ethyl acetate, diacetone alcohol, ethanol or 2-propanol is preferable as the organic solvent.
The organic solvents may be used alone or in combination of at least 2 kinds.
The organic solvent is preferably used in a range of 10 to 99% by mass, more preferably 30 to 95% by mass, still more preferably 50 to 95% by mass in the composition.
Examples of the catalyst include acids (e.g., hydrochloric acid, acetic acid, and trifluoroacetic acid), bases (e.g., ammonia, triethylamine, and diethylamine), and transition metals (e.g., ti, ni, and Sn).
The above catalyst promotes hydrolysis and dehydration condensation of the composition of the present invention, and promotes a surface treatment reaction.
The composition of the present invention is preferably a surface treatment agent.
Hereinafter, the article of the present invention will be described.
In one embodiment, the article of the present invention comprises a substrate and a layer (surface treatment layer) formed from the composition of the present invention on the surface of the substrate.
In another embodiment, the article of the present invention comprises a substrate and a composition comprising (a): crosslinkable compound and component (B): the layer (surface treatment layer) formed of the above-described composition of the present invention containing a fluorine-containing liquid-repellent compound,
the following formula is satisfied:
P b －P c ＞0
[ formula:
P b the polar component ratio in the surface free energy of the layer formed of the fluorine-containing liquid-repellent compound is set to be a value,
P c is the value of the polar component ratio in the surface free energy of the layer formed from the above composition.]。
P b －P c The value of (2) may be preferably 3.0 or more, more preferably 3.6 or more, still more preferably 5.0 or more, and still more preferably 8.0 or more. By making P b －P c Within this range, the liquid repellency and the liquid repellency of the layer are improved.
In another embodiment, the article of the present invention comprises a substrate and a composition comprising (a): crosslinkable compound and component (B): the layer (surface-treated layer) formed from the composition of the present invention contains a fluorine-containing liquid-repellent compound, and the polar component ratio of the free energy of the surface of the layer is 20.0% or less.
The polar component ratio in the surface free energy of the layer may be preferably 20.0% or less, more preferably 10.0% or less, still more preferably 8.0% or less, and still more preferably 5.0% or less. By setting the polar component ratio in the surface free energy of the layer in this range, the liquid repellency and the liquid repellency of the layer are improved.
In a preferred embodiment, the F/Si ratio of the surface of the layer formed from the composition of the present invention in each of the above embodiments may be preferably 3.0 or more, more preferably 5.0 or more, still more preferably 8.0 or more, for example 10.0 or more. The upper limit of the F/Si ratio of the surface of the layer formed of the composition of the present invention is not particularly limited, but the larger the upper limit is, the more preferable is, 30.0 or less, 20.0 or less, or 15.0 or less.
In one embodiment, the F/Si ratio of the surface of the layer formed from the composition of the present invention may be preferably 5.0 to 30.0, more preferably 5.0 to 20.0, still more preferably 8.0 to 20.0, for example 8.0 to 15.0.
In a preferred embodiment, the slip angle of water of the layer formed from the composition of the present invention in each of the above embodiments may be preferably 60 ° or less, more preferably 50 ° or less, still more preferably 30 ° or less, still more preferably 25 ° or less, and particularly preferably 20 ° or less. The lower limit of the slip angle of water of the layer formed by the composition of the present invention is not particularly limited, but may be, for example, 1 ° or more, 5 ° or more, or 10 ° or more, as the lower limit is smaller.
In a preferred embodiment, the layer formed from the composition of the present invention in each of the above embodiments may have a slip angle of hexadecane of preferably 35 ° or less, more preferably 30 ° or less, still more preferably 25 ° or less, and still more preferably 20 ° or less. The lower limit of the slip angle of water of the layer formed by the composition of the present invention is not particularly limited, but may be, for example, 1 ° or more, 5 ° or more, or 10 ° or more, as the lower limit is smaller.
The substrate that can be used in the present invention may be made of, for example, glass, resin (natural or synthetic resin, for example, a conventional plastic material), metal, ceramic, semiconductor (silicon, germanium, etc.), fiber (fabric, nonwoven fabric, etc.), fur, leather, wood, tao Ciqi, stone, etc., building elements, etc., sanitary products, or any suitable material.
In a preferred embodiment, the substrate is glass, resin or metal, preferably glass.
The glass is preferably a sapphire glass, a soda lime glass, an alkali aluminosilicate glass, a borosilicate glass, an alkali-free glass, a crystal glass, or a quartz glass, and particularly preferably a chemically strengthened soda lime glass, a chemically strengthened alkali aluminosilicate glass, or a chemically bonded borosilicate glass.
For example, in the case where the object to be manufactured is an optical member, the material constituting the surface of the base material may be a material for an optical member, such as glass or transparent plastic. In the case where the article to be manufactured is an optical member, some layers (or films) may be provided on the surface (outermost layer) of the base material, and for example, a hard coat layer, an antireflection layer, or the like may be formed. In the antireflection layer, any of a single antireflection layer and a multilayer antireflection layer may be used. Examples of the inorganic substance that can be used for the antireflection layer include SiO 2 、SiO、ZrO 2 、TiO 2 、TiO、Ti 2 O 3 、Ti 2 O 5 、Al 2 O 3 、Ta 2 O 5 、Ta 3 O 5 ,Nb 2 O 5 、HfO 2 、Si 3 N 4 、CeO 2 、MgO、Y 2 O 3 、SnO 2 、MgF 2 、WO 3 Etc. These inorganic substances may be used alone or in combination (for example, as a mixture) of 2 or more of these. In the case of forming a multilayer antireflection layer, siO is preferably used as the outermost layer 2 And/or SiO. When the object to be manufactured is an optical glass member for a touch panel, a thin film using a transparent electrode, for example, indium Tin Oxide (ITO), indium zinc oxide, or the like, may be provided on a part of the surface of a substrate (glass). In addition, the base material may have an insulating layer, an adhesive layer, a protective layer, and a decorative frame layer according to specific requirements (I-CON), an atomized film layer, a hard coat film layer, a polarizing film, a retardation film, a liquid crystal display module, and the like.
The shape of the substrate is not particularly limited, and may be, for example, a plate, a film, or other forms. The surface area of the substrate on which the surface treatment layer is to be formed may be at least a part of the surface of the substrate, and may be appropriately determined according to the purpose of the article to be manufactured, specific requirements, and the like.
The article of the present invention can be produced by forming a layer of the composition of the present invention on the surface of the substrate, and if necessary, post-treating the layer to form a layer from the composition of the present invention.
The layer formation of the composition of the present invention can be performed by applying the above composition so as to cover the surface of the substrate. The covering method is not particularly limited. For example, a wet coverage method and a dry coverage method can be used.
As examples of the wet coating method, dip coating, bar coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and the like can be cited. The wet coating method is preferably bar coating, spin coating, flow coating, and roll coating.
Examples of the dry coating method include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and the like. Specific examples of the vapor deposition method (typically, vacuum vapor deposition method) include resistance heating, high-frequency heating using an electron beam, microwave, or the like, ion beam, and the like. Specific examples of the CVD method include plasma CVD, optical CVD, thermal CVD, and the like.
Further, the coating by the atmospheric pressure plasma method can be performed.
When the dry coating method is used, the composition of the present invention can be used as it is or diluted with the above-mentioned organic solvent and used in the dry coating method.
Regarding the layer formation of the composition of the present invention, it is preferable to conduct the layer formation in such a manner that the composition of the present invention is present together with a catalyst for hydrolysis and dehydration condensation. In short, in the case of using the wet coating method, the composition of the present invention is diluted with a solvent, and then a catalyst is added to the diluted solution of the composition of the present invention immediately before application to the surface of a substrate. When the dry coating method is used, the composition of the present invention to which the catalyst is added may be directly subjected to vapor deposition (usually vacuum vapor deposition), or may be subjected to vapor deposition (usually vacuum vapor deposition) using a particulate material in which the composition of the present invention to which the catalyst is added is impregnated into a porous metal body such as iron or copper.
The catalyst can use any suitable acid or base. As the acid catalyst, hydrochloric acid, acetic acid, formic acid, trifluoroacetic acid, and the like can be used, for example. As the base catalyst, ammonia, organic amines, or the like can be used, for example.
The surface treatment layer included in the article of the present invention has a liquid-repellent property. In addition to the high slip property, the surface treatment layer may have antibacterial properties, water repellency, oil repellency, stain resistance (for example, to prevent adhesion of dirt such as fingerprints), water repellency (to prevent water from penetrating into electronic parts, etc.), surface slip property (or lubricity, wiping property of dirt such as fingerprints, excellent touch feeling to fingers, etc.), and the like, depending on the composition of the composition used, and may be suitably used as a functional film.
The article of the present invention is useful for long-term use under severe environmental conditions such as outdoors, where it is necessary to maintain the sliding properties.
In a preferred embodiment, the article of the present invention is useful for glass or mirror glass for vehicles, ships or aircrafts, glass for automobile, door mirror for automobile, front cover mirror for automobile, or the like, or glass for in-vehicle cameras, automobile sensors, or the like. Further, the present invention is useful for substrates for outdoor applications such as glass for monitors, curve reflectors, solar panel surfaces, wind turbine blades, and outer walls of buildings.
The present invention therefore also relates to an optical material having the above surface-treated layer in the outermost layer.
As the optical material, various optical materials are preferably used in addition to those related to a display or the like which will be described later: such as a cathode ray tube (CRT; for example, a personal computer display), a liquid crystal display, a plasma display, an organic EL display, an inorganic thin film EL dot matrix display, a rear projection display, a display such as a fluorescent display tube (VFD), a field emission display (FED; field Emission Display), a protective plate for such a display, or a material having an antireflection film treatment applied to the surface thereof.
The article of the present invention is not particularly limited, and may be an optical member. Examples of the optical member include the following: lenses such as glasses; front protection plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDP and LCD; touch screen sheets for devices such as cellular phones and portable information terminals; optical disc surfaces of optical discs such as Blu-ray (registered trademark)) discs, DVD discs, and CD-R, MO; an optical fiber; a display surface of a timepiece, and the like.
In addition, the article of the present invention may be a medical device or a medical material.
The thickness of the layer is not particularly limited, and may be, for example, 1nm or more, 10nm or more, or 100nm or more. The thickness of the layer is not particularly limited, and may be 1000nm or less, 500nm or less, or 100nm or less.
The composition and article of the present invention are described in detail above. The composition, article, and the like of the present invention are not limited to the above-described examples.
Examples
Hereinafter, the composition of the present invention will be described based on examples, but the present invention is not limited to the following examples.
As the component (a) and the component (B), the following compounds were prepared.
(A－1)
(A－2)
(B－1)～(B－3)
(B－1)：PFPE＝CF 3 CF 2 CF 2 －(OCF 2 CF 2 CF 2 ) n －OCF 2 CF 2 CH 2 －Mn2000
(B－2)：PFPE＝CF 3 CF 2 CF 2 －(OCF 2 CF 2 CF 2 ) n －OCF 2 CF 2 CH 2 －Mn4000
(B－3)：PFPE＝CF 3 (OCF 2 CF 2 ) n (OCF 2 ) m OCF 2 CH 2 －Mn4000 n/m＝0.92
(B－4)～(B－6)
(B－4)：PFPE＝CF 3 CF 2 CF 2 －(OCF 2 CF 2 CF 2 ) n －OCF 2 CF 2 －Mn4000
(B－5)：PFPE＝CF 3 (OCF 2 CF 2 ) n (OCF 2 ) m －OCF 2 －Mn4000 n/m＝0.68
(B－6)：PFPE＝CF 3 CF 2 CF 2 (OCF(CF 3 )CF 2 ) n OCF(CF 3 ) Mn4000 examples 1 to 13
Preparation of surface treatment agents 1 to 5
The component (A) and the component (B) were dissolved in a mixture of ethanol (2.8 g), novec7200 (0.01 g) and 0.01M hydrochloric acid (0.5 g) at a ratio shown in Table 2 so that the total thereof became 17.3wt%, and the mixture was stirred at 30℃for 1 hour. Diluting the stirred solution by 4 times with ethanol to prepare 1-5 surface treating agents.
Preparation of surface treatment agents 6 to 11
The above component (A) and component (B) were dissolved in a total of 4.3wt% in hydrofluoroether (Novec HFE 7200) (4.1 g), isopropyl alcohol (0.7 g), 0.01M hydrochloric acid (0.005 g) and water (0.037 g) at the ratio shown in Table 2, and stirred at 50℃for about 1 hour to obtain surface-treating agents 6 to 11.
TABLE 2
Surface treatment
Using the surface treatment agents 1 to 11 prepared as described above, substrates (glass, aluminum, polycarbonate (PC)) were processed by a bar coater so that the film thickness became 2.0. Mu.m, and treated at 150℃for 30 minutes, to obtain surface-treated samples of examples 1 to 13.
Evaluation
For the resulting surface treated samples, the static contact angles of water, hexadecane and formamide, and the slip angles of water and hexadecane were determined. In addition, using the static contact angle of water and formamide, the polar component ratio was calculated according to the formula of Kaelble-Uy. The results are shown in Table 3 below.
Method for measuring static contact angle
The static contact angle can be determined as follows: 2. Mu.L of liquid was dropped on a horizontally placed surface-treated substrate by a micro-syringe using a full-automatic contact angle meter DropMaster501 (manufactured by Kyowa interface science Co., ltd.), and a still image was taken after 1 second of the drop was taken by a video microscope. For each sample, the average value was measured 5 times and used as the static contact angle of the sample.
Method for measuring slip angle
The surface-treated sample placed horizontally was dropped with a liquid by a micro-syringe, and the drop was observed while being inclined to 90 ° at a rate of 2 ° per second. The drop was moved by an angle of 5mm as a slip angle. The amount of the droplets was measured with water of 20. Mu.L and hexadecane of 5. Mu.L. For each sample, the average value was measured 3 times and used as the slip angle of the sample.
TABLE 3
Comparative examples 1 to 7
Preparation of surface treatment agent
The components (B) shown in Table 4 were dissolved in Novec7200 so as to be 0.1wt%, to obtain surface treatment agents 12 to 18.
TABLE 4
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Surface treatment
The substrates (glass) were spin-coated (2000 rpm,10 seconds) using the surface treatments 12 to 18 prepared as described above. The surface was rubbed with a wipe containing ethanol (kimuipes) at 150 ℃ for 30 minutes.
Evaluation
For the resulting surface treated samples, the static contact angles of water, hexadecane and formamide, and the slip angles of water and hexadecane were determined. In addition, using the static contact angle of water and formamide, the polar component ratio was calculated according to the formula of Kaelble-Uy. As comparative example 8, a glass substrate that was not treated with a surface treatment agent was evaluated. The results are shown in table 5 below.
TABLE 5
Examples 14 to 15 and comparative examples 9 to 11
As shown in table 6 below, a surface treatment layer was formed using the surface treatment agent 2 in the same manner as in example 3 above, except that the film thickness was changed and a silicon wafer was used as a base material.
Evaluation
For the resulting surface treated samples, the static contact angle of water and hexadecane, and the slip angle of water and hexadecane were determined. In addition, the polar component ratio was calculated from the equation of Kaelble-Uy using the static contact angle of water and hexadecane. The results are shown in Table 6 below. In addition, elemental analysis of the surface was performed using PHI 5000 Versamrobe II (ULVAC Co.). The detection angle was set at 45℃and the F/Si value was calculated from the measured value.
TABLE 6
Examples 16 to 20
As shown in table 7 below, a surface treatment layer was formed on a glass substrate using the surface treatment agent 6 in the same manner as in example 8 above, except that the ratio of the component a and the component B was changed.
Examples 21 to 26
As shown in table 7 below, a surface treatment layer was formed on a glass substrate using the surface treatment agent 6 in the same manner as in examples 8 and 16 to 20 above, except that the film thickness was changed.
Evaluation
For the resulting surface treated samples, the static contact angles of water, hexadecane and formamide, and the slip angles of water and hexadecane were determined. In addition, using the static contact angle of water and formamide, the polar component ratio was calculated according to the formula of Kaelble-Uy. The results are shown in Table 7 below.
TABLE 7
Industrial applicability
The composition of the present invention can be suitably used for various purposes.
Claims (30)
1. A composition comprising:
component (A): crosslinkable compound, and
component (B): a fluorine-containing liquid-repellent compound,
the composition satisfies the following formula:
P b －P c ＞0
wherein:
P b to the value of the polar component ratio in the surface free energy of the layer formed of the fluorine-containing liquid-repellent compound,
P c is the value of the polar component ratio in the surface free energy of the layer formed from the composition.
2. The composition of claim 1, wherein:
the following formula is satisfied:
P b －P c ≥3.0。
3. the composition of claim 1, wherein:
P c is 20.0 or less.
4. The composition of claim 1, wherein:
the crosslinkable compound has a metal alkoxide group.
5. The composition of claim 1, wherein:
the crosslinkable compound is a compound represented by the following formula (A1) or (A2):
A[Z a1 －M 1 (OR a1 ) n1 (R a2 ) n2－n1 ] m1 [Z a2 －R a3 ] m2 (A1)
in the formula (A1):
a is an organic group having a valence of 1 to 10,
Z a1 each independently a single bond or a 2-valent organic group,
M 1 al, ca, fe, ge, hf, in, si, ta, ti, sn, zr or Zn;
R a1 each independently is a hydrogen atom or C 1－6 An alkyl group, a hydroxyl group,
R a2 each independently is a hydrogen atom or a hydrocarbon group,
n1 is 1 or more and (M) 1 The valence of (2) is less than-1),
n2 is each independently (M) 1 Valence number-1) of (c) is set to be equal to or lower than the valence number-1),
Z a2 each independently a single bond or a 2-valent organic group,
R a3 each independently a reactive organic group,
m1 is an integer of 1 to 10,
m2 is an integer of 0 to 10,
the sum of m1 and m2 is the valence of A,
in formula (2A):
M 2 al, ca, fe, ge, hf, in, si, ta, ti, sn, zr or Zn; r is R a4 Are each independently a hydrogen atom, C 1－6 Alkyl or R a6 －CO－；
R a6 A hydrocarbon group having a valence of 1;
R a5 each independently is C 1－3 Alkyl or C 1－3 An alkoxy group;
n3 is the M 2 Valence of (2);
n4 is 0 or more and M 2 Below the valence number of (c).
6. The composition of claim 5, wherein:
n1 is 2 or more.
7. The composition of claim 5, wherein:
the R is a1 Based on C 1－4 An alkyl group.
8. The composition of claim 5, wherein:
a is an alkylene group or a group of the formula:
wherein:
X a each independently a single bond or a 2-valent organic group.
9. The composition of claim 5, wherein:
the reactive organic group is an isocyanate group, an epoxy group or a vinyl group.
10. The composition of claim 1, wherein:
the fluorine-containing liquid-repellent compound has a fluoroalkyl group or a fluoropolyether group.
11. The composition of claim 10, wherein:
the fluoropolyether group is a group represented by the following formula:
-(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 R Fa 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -
wherein R is Fa Each occurrence of which is independently a hydrogen atom, a fluorine atom or a chlorine atom,
a. b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f being 1 or more, the order of presence of the repeating units denoted by a, b, c, d, e or f and bracketed in the formula is arbitrary, wherein, in all R Fa In the case of a hydrogen atom or a chlorine atom, at least 1 of a, b, c, e and f is 1 or more.
12. The composition of claim 1, wherein:
the fluorine-containing liquid-repellent compound is a fluorinated polyether group-containing silane compound represented by the following formula (1) or (2):
R F1 α -X A -R Si β (1)
R Si γ -X A -R F2 -X A -R Si γ (2)
in formula (1) or formula (2):
R F1 each occurrence is independently Rf 1 -or Rf 1 －R F －O q －；
R F2 is-Rf 2 -or-Rf 2 p －R F －O q －；
Rf 1 Each occurrence is independently C which may be substituted with 1 or more fluorine atoms 1－16 An alkyl group;
Rf 2 for C which may be substituted by 1 or more fluorine atoms 1－6 An alkylene group;
R F a fluoropolyether group each independently at each occurrence being 2-valent;
p is 0 or 1;
q is independently 0 or 1 at each occurrence;
R Si each occurrence is independently a 1-valent group comprising a Si atom to which a hydroxyl group, a hydrolyzable group, or a 1-valent organic group is bonded, or a 1-valent group comprising a reactive organic group;
at least 1R Si A 1-valent group comprising a Si atom to which a hydroxyl group or a hydrolyzable group is bonded, or a 1-valent group comprising a reactive organic group;
X A each independently is a single bond or an organic group having a valence of 2 to 10;
alpha is an integer of 1 to 9;
beta is an integer of 1 to 9;
gamma is an integer of 1 to 9.
13. The composition of claim 12, wherein:
R F each occurrence is independently a group of the formula:
－(OC 6 F 12 ) a －(OC 5 F 10 ) b －(OC 4 F 8 ) c －(OC 3 R Fa 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f －
wherein R is Fa Each occurrence of which is independently a hydrogen atom, a fluorine atom or a chlorine atom,
a. b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f being 1 or more, the order of presence of the repeating units denoted by a, b, c, d, e or f and bracketed in the formula is arbitrary, wherein, in all R Fa In the case of a hydrogen atom or a chlorine atom, at least 1 of a, b, c, e and f is 1 or more.
14. The composition of claim 12, wherein:
R F each occurrence is independently a group represented by the following formula (f 1), formula (f 2), formula (f 3), formula (f 4), formula (f 5) or formula (f 6):
－(OC 3 F 6 ) d －(OC 2 F 4 ) e －(f1)
in the formula (f 1), d is an integer of 1 to 200, e is 0 or 1,
－(OC 4 F 8 ) c －(OC 3 F 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f －(f2)
in the formula (f 2), c and d are each independently an integer of 0 to 30;
e and f are each independently integers from 1 to 200;
c. d, e and f are integers from 10 to 200;
the order of the presence of the repeat units denoted by the subscripts c, d, e, or f and bracketed is arbitrary in the formula,
－(R 6 －R 7 ) g －(f3)
in the formula (f 3), R 6 Is OCF 2 Or OC (alpha) 2 F 4 ；
R 7 Is 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,
－(R 6 －R 7 ) g －R r －(R 7′ －R 6′ ) g′ －(f4)
in the formula (f 4), R 6 Is OCF 2 Or OC (alpha) 2 F 4 ，
R 7 Is 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 independently selected from these groups,
R 6′ is OCF 2 Or OC (alpha) 2 F 4 ，
R 7′ Is 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 independently selected from these groups,
g is an integer of 2 to 100,
g' is an integer of 2 to 100,
R r is that
Wherein, the formula (I) represents a binding site;
－(OC 6 F 12 ) a －(OC 5 F 10 ) b －(OC 4 F 8 ) c －(OC 3 F 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f － (f5)
in the formula (f 5), e is an integer of 1 to 200, a, b, c, d and f are each independently an integer of 0 to 200, and the order in which the repeating units are represented by a, b, c, d, e or f and bracketed is arbitrary in the formula,
－(OC 6 F 12 ) a －(OC 5 F 10 ) b －(OC 4 F 8 ) c －(OC 3 F 6 ) d －(OC 2 F 4 ) e －(OCF 2 ) f － (f6)
in the formula (f 6), f is an integer of 1 to 200, a, b, c, d and e are each independently an integer of 0 to 200, and the order in which the repeating units are represented by a, b, c, d, e or f and bracketed is arbitrary in the formula.
15. The composition of claim 12, wherein:
the reactive organic group is an isocyanate group, an epoxy group or a vinyl group.
16. The composition of claim 12, wherein:
R Si is a group represented by the following formula (S1), formula (S2), formula (S3), formula (S4) or formula (S5):
-SiR 11 n1 R 12 3-n1 (S2)
-SiR a1 k1 R b1 11 R c1 m1 (S3)
-CR d1 k2 R e1 12 R f1 m2 (S4)
-NR g1 R h1 (S5)
In the formula (S1), the formula (S2), the formula (S3), the formula (S4) or the formula (S5):
R 11 each occurrence is independently a hydroxyl group or a hydrolyzable group;
R 12 organic groups each independently at each occurrence being 1 valent;
n1 is defined in each (SiR 11 n1 R 12 3-n1 ) Each of the units is independently an integer of 0 to 3;
X 11 an organic group independently at each occurrence being a single bond or a 2-valent organic group;
R 13 an organic group which is independently a hydrogen atom or a valence 1 at each occurrence;
t is an integer of 2 or more independently at each occurrence;
R 14 each occurrence is independently a hydrogen atom, a halogen atom or-X 11 -SiR 11 n1 R 12 3-n1 ；
R 15 Each occurrence is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms;
R a1 are each independently-Z at each occurrence 1 -SiR 21 p1 R 22 q1 R 23 r1 ；
Z 1 An oxygen atom or a 2-valent organic group independently at each occurrence;
R 21 are each independently-Z at each occurrence 1′ -SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ；
R 22 Each occurrence is independently a hydroxyl group or a hydrolyzable group;
R 23 organic groups each independently at each occurrence being 1 valent;
p1 is independently an integer from 0 to 3 at each occurrence;
q1 is independently an integer from 0 to 3 at each occurrence;
r1 is independently an integer from 0 to 3 at each occurrence;
the sum of p1, q1 and r1 is in (SiR 21 p1 R 22 q1 R 23 r1 ) 3 in the unit;
Z 1′ an oxygen atom or a 2-valent organic group independently at each occurrence;
R 21′ are each independently-Z at each occurrence 1" －SiR 22" q1" R 23" r1" ；
R 22′ Each occurrence is independently a hydroxyl group or a hydrolyzable group;
R 23′ organic groups each independently at each occurrence being 1 valent;
p1' is independently an integer from 0 to 3 at each occurrence;
q1' is independently an integer from 0 to 3 at each occurrence;
r1' is independently an integer from 0 to 3 at each occurrence;
the sum of p1', q1' and r1' is in (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ) 3 in the unit;
Z 1" an oxygen atom or a 2-valent organic group independently at each occurrence;
R 22" each occurrence is independently a hydroxyl group or a hydrolyzable group;
R 23" organic groups each independently at each occurrence being 1 valent;
q1 "is independently an integer from 0 to 3 at each occurrence;
r1 "is independently an integer from 0 to 3 at each occurrence;
the sum of q1 'and r1' is in (SiR 22" q1" R 23" r1" ) 3 in the unit;
R b1 each occurrence is independently a hydroxyl group or a hydrolyzable group;
R c1 an organic compound having a valence of 1 at each occurrenceA group;
k1 is independently an integer of 0 to 3 at each occurrence;
l1 is independently an integer from 0 to 3 at each occurrence;
m1 is independently an integer of 0 to 3 at each occurrence;
the sum of k1, l1 and m1 is in (SiR a1 k1 R b1 l1 R c1 m1 ) 3 in the unit;
R d1 are each independently-Z at each occurrence 2 －CR 31 p2 R 32 q2 R 33 r2 ；
Z 2 An organic group independently at each occurrence being a single bond, an oxygen atom, or a valence 2; r is R 31 Are each independently-Z at each occurrence 2′ －CR 32′ q2′ R 33′ r2′ ；
R 32 Are each independently-Z at each occurrence 3 －SiR 34 n2 R 35 3－n2 ；
R 33 An organic group which is independently a hydrogen atom, a hydroxyl group, or a valence 1 at each occurrence; p2 is independently an integer from 0 to 3 at each occurrence;
q2 is independently an integer from 0 to 3 at each occurrence;
r2 is independently an integer from 0 to 3 at each occurrence;
the sum of p2, q2 and r2 is in (CR 31 p2 R 32 q2 R 33 r2 ) 3 in the unit;
Z 2′ an organic group independently at each occurrence being a single bond, an oxygen atom, or a valence 2;
R 32′ are each independently-Z at each occurrence 3 －SiR 34 n2 R 35 3－n2 ；
R 33′ An organic group which is independently a hydrogen atom, a hydroxyl group, or a valence 1 at each occurrence;
q2' is independently an integer from 0 to 3 at each occurrence;
r2' is independently an integer from 0 to 3 at each occurrence;
the sum of q2 'and r2' is equal to (CR 32′ q2′ R 33′ r2′ ) 3 in the unit;
Z 3 an organic group independently at each occurrence being a single bond, an oxygen atom, or a valence 2;
R 34 each occurrence is independently a hydroxyl group or a hydrolyzable group;
R 35 Organic groups each independently at each occurrence being 1 valent;
n2 is independently an integer from 0 to 3 at each occurrence;
R e1 are each independently-Z at each occurrence 3 －SiR 34 n2 R 35 3－n2 ；
R f1 An organic group which is independently a hydrogen atom, a hydroxyl group, or a valence 1 at each occurrence;
k2 is independently an integer of 0 to 3 at each occurrence;
l2 is independently an integer from 0 to 3 at each occurrence;
m2 is independently an integer from 0 to 3 at each occurrence;
the sum of k2, l2 and m2 is in (CR d1 k2 R e1 l2 R f1 m2 ) 3 in the unit;
R g1 and R is h1 Are each independently-Z at each occurrence 4 －SiR 11 n1 R 12 3－n1 、－Z 4 －SiR a1 k1 R b1 l1 R c1 m1 、－Z 4 －CR d1 k2 R e1 l2 R f1 m2 ；
Z 4 An organic group independently at each occurrence being a single bond, an oxygen atom, or a valence 2;
wherein at least one Si atom having a hydroxyl group or a hydrolyzable group bonded thereto is present in the formulae (S1), (S2), (S3), (S4) and (S5).
17. The composition of claim 12, wherein:
X A is a single bond or a 2-valent organic group represented by the following formula:
－(R 51 ) p5 －(X 51 ) q5 －
wherein:
R 51 is a single bond, - (CH) 2 ) s5 Either ortho-, meta-or para-phenylene,
s5 is an integer of 1 to 20,
X 51 is- (X) 52 ) l5 －，
X 52 At each occurrence is independently selected from the group consisting of-O-, -S-, O-phenylene m-or p-phenylene, -C (O) O-, -Si (R) 53 ) 2 －、－(Si(R 53 ) 2 O) m5 －Si(R 53 ) 2 －、－CONR 54 －、－O－CONR 54 －、－NR 54 -and- (CH) 2 ) n5 A group which is a radical of the formula,
R 53 at each occurrence is independently phenyl, C 1－6 Alkyl or C 1－6 An alkoxy group, an amino group,
R 54 each occurrence is independently a hydrogen atom, phenyl or C 1－6 An alkyl group, a hydroxyl group,
m5 is each independently an integer of 1 to 100,
n5 is each independently an integer of 1 to 20,
l5 is an integer of 1 to 10,
p5 is either 0 or 1 and,
q5 is either 0 or 1 and,
wherein at least one of p5 and q5 is 1, and the order in which the repeating units, denoted by p5 or q5 and bracketed, are present is arbitrary.
18. The composition of claim 12, wherein:
X A is a group of the formula:
wherein X is a Is a single bond or a 2-valent organic group.
19. The composition of claim 12, wherein:
the fluorine-containing liquid-repellent compound is a fluorinated polyether silane compound represented by formula (1).
20. The composition of claim 1, wherein:
the content of the fluorine-containing liquid-repellent compound is 0.1 to 90.0% by mass relative to the total of the crosslinkable compound and the fluorine-containing liquid-repellent compound.
21. The composition of claim 1, wherein:
the F/Si ratio of the surface of the layer formed from the composition is 5.0 to 20.0.
22. The composition of claim 1, wherein:
the water of the layer formed by the composition has a slip angle of 25 DEG or less.
23. The composition of claim 1, wherein:
and further comprises other components selected from the group consisting of organic solvents, water and catalysts.
24. The composition of claim 1, wherein:
which is a surface treatment agent.
25. An article, comprising:
a substrate, and a layer formed on the substrate from the composition of claim 24.
26. An article, comprising:
a base material, and a composition comprising (A): crosslinkable compound and component (B): a layer formed from a composition comprising a fluorine-containing liquid-repellent compound,
the composition satisfies the following formula:
P b －P c ＞0
wherein:
P b to the value of the polar component ratio in the surface free energy of the layer formed of the fluorine-containing liquid-repellent compound,
P c is the value of the polar component ratio in the surface free energy of the layer formed from the composition.
27. An article, comprising:
a base material, and a composition comprising (A): crosslinkable compound and component (B): a layer formed from a composition of a fluorine-containing liquid-repellent compound, wherein the layer has a polar component ratio of 20.0% or less in the surface free energy.
28. An article as claimed in claim 26 or 27, wherein:
the F/Si ratio of the surface of the layer is 5.0 or more.
29. An article as claimed in claim 26 or 27, wherein:
the water of the layer has a slip angle of 25 ° or less.
30. An article as claimed in claim 26 or 27, wherein:
the thickness of the layer is 0.01 μm or more.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150034593A1 (en) * | 2013-07-31 | 2015-02-05 | Tokyo Ohka Kogyo Co., Ltd. | Method of producing structure containing phase-separated structure, method of forming pattern and method of forming fine pattern |
| CN104797612A (en) * | 2012-11-13 | 2015-07-22 | 大金工业株式会社 | Surface treatment composition |
| CN105849222A (en) * | 2013-12-26 | 2016-08-10 | 大金工业株式会社 | Surface treating agent including perfluoro(poly)ether-group-containing silane compound |
| JP2017019948A (en) * | 2015-07-13 | 2017-01-26 | ダイキン工業株式会社 | Surface treatment agent |
| CN109016719A (en) * | 2017-06-08 | 2018-12-18 | 大金工业株式会社 | Surface treating agent |
| WO2021049240A1 (en) * | 2019-09-10 | 2021-03-18 | ダイキン工業株式会社 | Surface treatment agent |
| CN114040897A (en) * | 2019-05-14 | 2022-02-11 | 康宁公司 | 3D structure for easy-clean coating |
-
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- 2023-02-24 JP JP2023027574A patent/JP2023127558A/en active Pending
- 2023-02-28 CN CN202310175852.3A patent/CN116694203A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104797612A (en) * | 2012-11-13 | 2015-07-22 | 大金工业株式会社 | Surface treatment composition |
| US20150034593A1 (en) * | 2013-07-31 | 2015-02-05 | Tokyo Ohka Kogyo Co., Ltd. | Method of producing structure containing phase-separated structure, method of forming pattern and method of forming fine pattern |
| CN105849222A (en) * | 2013-12-26 | 2016-08-10 | 大金工业株式会社 | Surface treating agent including perfluoro(poly)ether-group-containing silane compound |
| JP2017019948A (en) * | 2015-07-13 | 2017-01-26 | ダイキン工業株式会社 | Surface treatment agent |
| CN109016719A (en) * | 2017-06-08 | 2018-12-18 | 大金工业株式会社 | Surface treating agent |
| CN114040897A (en) * | 2019-05-14 | 2022-02-11 | 康宁公司 | 3D structure for easy-clean coating |
| WO2021049240A1 (en) * | 2019-09-10 | 2021-03-18 | ダイキン工業株式会社 | Surface treatment agent |
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