WO2019088117A1 - 硬化性組成物 - Google Patents
硬化性組成物 Download PDFInfo
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- WO2019088117A1 WO2019088117A1 PCT/JP2018/040365 JP2018040365W WO2019088117A1 WO 2019088117 A1 WO2019088117 A1 WO 2019088117A1 JP 2018040365 W JP2018040365 W JP 2018040365W WO 2019088117 A1 WO2019088117 A1 WO 2019088117A1
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
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- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- 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
Definitions
- the present invention relates to a curable composition.
- compositions containing certain fluoropolyether compounds have excellent water repellency, oil repellency and the like.
- Patent Document 1 describes a rubber on which a cured film of a room temperature curing type perfluoropolyether composition is formed on the surface, and the releasability, solvent resistance, chemical resistance, weather resistance, water repellency It is stated that a rubber to which oil repellency and the like are imparted is provided.
- the composition of Patent Document 1 contains a condensation promoter, and in the examples, dibutyltin dimethoxide or dibutyltin laurate is used as the condensation promoter.
- An object of the present invention is to provide a composition suitable for the formation of a cured product with good transparency.
- a fluorine-containing silane compound having two or more Si atoms bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolysable group An organosilicon compound having at least two -O-R g3 bonded to a Si atom, wherein R g3 is each independently a hydrogen atom or a monovalent organic group at each occurrence, and M (-O -R h ) metal-based catalyst represented by ⁇
- An object of the present invention is to provide a composition suitable for the formation of a cured product with good transparency.
- the curable composition of the present invention is A fluorine-containing silane compound having two or more Si atoms bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolysable group (hereinafter sometimes referred to as “fluorine-containing silane compound”)
- Organosilicon compounds having at least two —O—R g3 bonded to Si atoms (wherein, R g3 is each independently a hydrogen atom or a monovalent organic group at each occurrence) (hereinafter referred to as “crosslinking Agent) and a metal-based catalyst represented by M (-O-R h ) ⁇ , Have.
- M represents a metal atom
- R h is each independently a hydrocarbon group having 1 to 3 carbon atoms at each occurrence
- ⁇ is a coordination number of M.
- the fluorine-containing silane compound is not particularly limited as long as it has a fluorine-containing moiety that imparts water repellency and chemical resistance and a silane moiety that imparts bonding ability to other substances.
- the fluorine-containing silane compound is a compound in which at least one of the hydrogen atoms bonded to a carbon atom is substituted with a fluorine atom.
- the fluorine-containing silane compound preferably further has a perfluoro (poly) ether group. That is, the fluorine-containing silane compound is preferably a perfluoropolyether group-containing silane compound (hereinafter, also referred to as “PFPE-containing silane compound (A)”).
- PFPE-containing silane compound (A) perfluoropolyether group-containing silane compound
- the perfluoropolyether group means a group in which all hydrogen atoms of the polyether group are substituted by fluorine atoms.
- Hydrolyzable group as used herein means a group capable of undergoing a hydrolysis reaction, ie, a group capable of leaving a main skeleton of a compound by a hydrolysis reaction.
- R examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl; and substituted alkyl groups such as chloromethyl.
- an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
- the hydroxyl group is not particularly limited, but may be formed by hydrolysis of a hydrolyzable group.
- a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom can be mentioned, Among these, a chlorine atom is preferable.
- the Si atom bonded to at least one group selected from the group consisting of the hydroxyl group and the hydrolyzable group is present at both ends of the molecular main chain of the fluorine-containing silane compound (eg, PFPE-containing silane compound (A)) Is preferred.
- the molecular main chain of the fluorine-containing silane compound for example, PFPE-containing silane compound (A)
- PFPE-containing silane compound (A) is relatively most in the molecule of the fluorine-containing silane compound (for example, PFPE-containing silane compound (A)) Represents a long binding chain.
- the PFPE-containing silane compound (A) is preferably at least one compound represented by formulas (A), (B), (C), or (D).
- the PFPE-containing silane compound (A) represented by the above formulas (A), (B), (C) and (D) will be described below.
- divalent to divalent organic group refers to a carbon containing di- to divalent group.
- the di- to deca-valent organic group is not particularly limited, and examples thereof include di- to 10-valent groups obtained by further removing 1 to 9 hydrogen atoms from a hydrocarbon group.
- the divalent organic group is not particularly limited, and examples thereof include divalent groups in which one hydrogen atom is further eliminated from a hydrocarbon group.
- hydrocarbon group means a group containing carbon and hydrogen wherein one hydrogen atom has been eliminated from the molecule.
- a hydrocarbon group is not particularly limited, but is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, for example, an aliphatic hydrocarbon group And aromatic hydrocarbon groups.
- the “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated.
- the hydrocarbon group may also contain one or more ring structures.
- Such a hydrocarbon group may have one or more of N, O, S, Si, an amide, a sulfonyl, a siloxane, a carbonyl, a carbonyloxy and the like in the terminal or molecular chain thereof.
- the substituent of the “hydrocarbon group” is not particularly limited, and for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5- to 10-membered heterocyclyl group, 5- to 10-membered unsaturated heterocyclyl Groups, one or more groups selected from C 6-10 aryl groups and 5-10 membered heteroaryl groups.
- an alkyl group and a phenyl group may be unsubstituted or substituted, unless otherwise specified.
- the substituent of such group is not particularly limited, and one or more groups selected from, for example, a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group and a C 2-6 alkynyl group It can be mentioned.
- PFPE is independently at each occurrence: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 10 6) d - (OC 2 F 4) e - (OCF 2) f - Is a group represented by
- a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1.
- a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less.
- the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more.
- the sum of a, b, c, d, e and f is 200 or less, more preferably 100 or less, for example 10 or more and 200 or less, more specifically 10 or more and 100 or less.
- the order in which each repeating unit enclosed in parentheses with a, b, c, d, e or f is present is arbitrary in the formula.
- X 10 each independently at each occurrence is a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.
- repeating units may be linear or branched, but are preferably linear.
- - (OC 6 F 12) - is, - (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 (CF 3) CF 2 CF 2) -, - (OCF 2 CF 2 CF (CF 3) CF 2) - And-(OCF 2 CF 2 CF 2 CF (CF 3 ))-may be used, but-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-is preferable.
- - (OC 5 F 10) - is, - (OCF 2 CF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2 CF 2) -, - (OCF 2 CF (CF 3) It may be CF 2 CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-or the like, preferably-( OCF 2 CF 2 CF 2 CF 2 CF 2) - a.
- - (OC 4 F 8) - is, - (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)) -, - (OCF 2 CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF 3) CF ( It may be any of CF 3 )),-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-, but preferably-(OCF 2 CF 2).
- - (OC 3 F 6) - (i.e., in the above formulas, X 10 is a fluorine atom) is, - (OCF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2) - and - ( It may be any of OCF 2 CF (CF 3 ))-, but is preferably-(OCF 2 CF 2 CF 2 )-.
- - (OC 2 F 4) - is, - (OCF 2 CF 2) - and - (OCF (CF 3)) - but it may be any of, preferably - (OCF 2 CF 2) - in is there.
- the PFPE is — (OC 3 F 6 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) .
- PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) or OCF (CF 3 ) CF 2 ) d — (wherein, d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less).
- PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) .
- the PFPE is — (OC 4 F 8 ) c — (OC 3 F 6 ) d — (OC 2 F 4 ) e — (OCF 2 ) f —, wherein c and d are each independently And e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and c, d, e and The sum of f is at least 5 or more, preferably 10 or more, and the order in which each repeating unit enclosed in parentheses with the subscript c, d, e or f is given is arbitrary in the formula).
- PFPE is, - (OCF 2 CF 2 CF 2 CF 2) c - (OCF 2 CF 2 CF 2) d - (OCF 2 CF 2) e - (OCF 2) f - a.
- PFPE is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed in parentheses with the subscript e or f is attached may be arbitrary in the formula).
- e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed in parentheses with the subscript e or f is attached may be arbitrary in the formula).
- PFPE is a group represented by-(R 6 -R 7 ) j- .
- R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 .
- R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or selected independently from these groups A combination of two or three groups.
- R 7 is a group 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 And more preferably a group selected from OC 3 F 6 and OC 4 F 8 .
- the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited.
- the j is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably 50 or less.
- OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be linear or branched, preferably linear .
- PFPE is preferably, - (OC 2 F 4 -OC 3 F 6) j - or - (OC 2 F 4 -OC 4 F 8) j - is.
- the ratio of e to f (hereinafter referred to as “e / f ratio”) is 0.1 or more and 10 or less, preferably 0.2 or more and 5 or less, and more preferably 0.2 or more and 2 or less More preferably, it is 0.2 or more and 1.5 or less.
- e / f ratio the water repellency, oil repellency and chemical resistance of the cured product obtained from this compound (for example, durability against aqueous solution of salt, acid or basic solution, acetone, oleic acid or hexane) ) Can be further improved.
- the smaller the e / f ratio the better the water repellency, oil repellency and chemical resistance of the cured product.
- the stability of the compound can be further enhanced. The higher the e / f ratio, the better the stability of the compound.
- the e / f ratio may be less than 1.0, may be 0.10 or more, may be 0.20 or more, and may be 0.40 or more.
- the e / f ratio may be 0.90 or less, 0.85 or less, or 0.80 or less.
- the e / f ratio is, for example, 0.10 or more and less than 1.0, specifically 0.20 or more and 0.90 or less, more specifically 0.40 or more and 0.85 or less, more specifically It is 0.40 or more and 0.80 or less.
- the e / f ratio may be 1.0 or more, 1.1 or more, 1.2 or more, 10.0 or less, or 5.0 or less , Or 2.0 or less, or 1.5 or less.
- the e / f ratio is, for example, 1.0 or more and 10.0 or less, specifically, 1.0 or more and 5.0 or less, more specifically, 1.0 or more and 2.0 or less, more specifically Is 1.0 or more and 1.5 or less.
- a curable composition having an e / f ratio in the above range may have a relatively high 1% decomposition temperature of the cured product. That is, such a curable composition can contribute to the formation of a usable cured product over a wide temperature range.
- 1% decomposition temperature means a temperature at which 1% by mass of the cured product decomposes with respect to the entire cured product.
- the 1% decomposition temperature means a value measured by thermogravimetry / differential heat (TG / DTA). Specifically, under an oxygen atmosphere, the heating rate is 10 ° C./min, 25 ° C. to 600 ° C. Measure in the range of As said TG / DTA, DTG-60 by SHIMADZU can be mentioned, for example.
- the number average molecular weight of the -PFPE- moiety may be in the range of 2,000 to 200,000, and may be in the range of 3,000 to 100,000.
- the above-mentioned number average molecular weight is a value measured by 19 F-NMR.
- the number average molecular weight of the -PFPE- moiety is not particularly limited, but for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2 And 10,000 to 10,000.
- the number average molecular weight of -PFPE- moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, still more preferably 2,000 to It may be 10,000, for example 3,000 to 6,000.
- the number average molecular weight of the -PFPE- moiety may be 4,000 to 30,000, preferably 5,000 to 10,000, more preferably 6,000 to 10,000.
- the number average molecular weight of the -PFPE- moiety may be in the range of 2,000 to 10,000, preferably in the range of 2,000 to 3,000.
- the viscosity of the curable composition may be low and the handleability may be good.
- the curable composition having the number average molecular weight of the -PFPE- moiety as described above is also advantageous from the viewpoint of suppression of viscosity, for example, when it is used together with a solvent and in a solution state.
- the number average molecular weight of the -PFPE- moiety may be in the range of 10,000 to 100,000, preferably in the range of 10,000 to 50,000.
- R 13 independently at each occurrence represents a hydroxyl group or a hydrolysable group.
- the hydrolyzable group is as defined above.
- R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
- each occurrence of R 11 independently represents a hydrogen atom or a halogen atom.
- the halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, and more preferably a fluorine atom.
- each occurrence of R 12 independently represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group.
- R 11 ′ ′ , R 12 ′ ′ , R 13 ′ ′ and R 14 ′ ′ are respectively the same as R 11 , R 12 , R 13 and R 14 .
- the Si atom bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolysable group is an integer in which n1 is an integer of 1 to 3 and (-SiR 13 n1 R The Si atom contained in 14 3-n1 ) or (-SiR 13 " n1 R 14" 3-n1 ) is shown.
- n1 is an integer of 0 to 3 independently for each (-SiR 13 n1 R 14 3-n 1 ) unit or for each (-SiR 13 ′ ′ n1 R 14 ′ 3-n 1 ) unit, Preferably, it is 1 to 3, and more preferably 3.
- at least two n1 are integers of 1 to 3, that is, all n1 are never 0 simultaneously. That is, in the formula, there are at least two bonded Si atoms of R 13 or R 13 ′ ′.
- —SiR 13 n1 R 14 3-n1 structure (n1 is 1 or more) That is, there exist at least two structures selected from the group consisting of -SiR 13 " n1 R 14" 3-n1 structure (ie, -SiR 13 " part) in which -SiR 13 part) and n1 are 1 or more.
- Si atoms bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group are present at both ends of the molecular main chain. That is, in the formula (A), at least one —SiR 13 n1 R 14 3-n1 structure (that is, —SiR 13 portion) in which n1 is 1 or more, and at least one n1 is 1 or more— SiR 13 ′ ′ n 1 R 14 ′ ′ 3-n 1 structure (ie, —SiR 13 ′ ′ moiety) is present.
- each X 1 independently represents a single bond or a di- to 10-valent organic group.
- said X 1 mainly has a water-repellent property, a surface sliding property and the like, ie, a binding property between a perfluoropolyether part (ie, -PFPE-part) and a substrate. It is understood as a linker linking the provided silane moiety (ie the group bracketed with ⁇ 1). Accordingly, X 1 may be a single bond or any organic group as long as the compound represented by the formula (A) can be stably present.
- a group described as X 1 is bonded to a group represented by PFPE on the left side and a group enclosed in parentheses with ⁇ 1 attached on the right side.
- X 1 can be X e .
- X e represents a single bond or 2-10 divalent organic group, preferably a single bond or -C 6 H 4 -, (i.e. - - phenylene.
- Each R 4 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom or a methyl group.
- the —C 6 H 4 —, —CO—, —NR 4 — or —SO 2 — is preferably contained in the molecular main chain of the PFPE-containing silane compound (A).
- X e is more preferably a single bond or -C 6 H 4 -, - CONR 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 4 -, - SO 2 NR 4 -C 6 H 4 -, - SO 2 -, and -SO 2 -C 6 H 4 - represents a 2-10 monovalent organic group having at least one selected from the group consisting of .
- Additional -C 6 H 4 -, - CONR 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 4 -, - SO 2 NR 4 - C 6 H 4 -, - SO 2 -, or -SO 2 -C 6 H 4 - is preferably contained in the molecular backbone of the PFPE-containing silane compound (a).
- ⁇ 1 is an integer of 1 to 9 and can be changed according to the valence of X 1 .
- [alpha] 1 is the value obtained by subtracting 1 from the valence of X 1.
- ⁇ 1 is 1.
- the above X 1 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, and still more preferably a divalent organic group.
- X 1 is a divalent to tetravalent organic group, and ⁇ 1 is 1 to 3.
- X 1 is a divalent organic group and ⁇ 1 is 1.
- the formula (A) is represented by the following formula (A ′).
- R 31 represents a single bond,-(CH 2 ) s ' -or o-, m- or p-phenylene group, preferably-(CH 2 ) s'- s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
- X a represents-(X b ) l ' - X b is independently at each occurrence -O-, -S-, o-, m- or p-phenylene, -C (O) O-, -Si (R 33 ) 2 -,-( Si (R 33) 2 O) m '-Si (R 33) 2 -, - CONR 34 -, - O-CONR 34 -, - NR 34 - and - (CH 2)
- n' - is selected from the group consisting of Represents a group R 33 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, more preferably a methyl group
- R 34 independently at each occurrence represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group),
- R 31 and X a are one or more selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group It may be substituted by the substituent of
- l ' is 1.
- X 1 is- (R 31 ) p ' -(X a ) q' -R 32- .
- R 32 represents a single bond,-(CH 2 ) t ' -or o-, m- or p-phenylene group, preferably-(CH 2 ) t'- .
- t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.
- R 32 (typically a hydrogen atom in R 32 ) is substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group It may be done.
- said X 1 is Single bond, C 1-20 alkylene group, -R 31 -X c -R 32- or -X d -R 32- [Wherein, R 31 and R 32 are as defined above. ] It can be.
- the alkylene group, - (C ⁇ H 2 ⁇ ) - a group having the structure, may be substituted or unsubstituted, may be linear or branched.
- X 1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s' -X c- , -(CH 2 ) s ' -X c- (CH 2 ) t'- -X d- or -X d- (CH 2 ) t ' - [Wherein, s ′ and t ′ are as defined above. ] It is.
- X 1 is -X f -, -X f -C 1-20 alkylene group, -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' - It is.
- s 'and t' are as defined above.
- X f is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, such as a methylene group.
- the hydrogen atom in X f may be substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group, preferably substituted There is.
- X f may be linear or branched, and is preferably linear.
- X c is -O-, -S-, -C (O) O-, -CONR 34 -, -O-CONR 34 -, -Si (R 33 ) 2- , - (Si (R 33) 2 O) m '-Si (R 33) 2 -, -O- (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -O- (CH 2) u '-Si (R 33) 2 -O-Si (R 33) 2 -CH 2 CH 2 -Si (R 33) 2 -O-Si (R 33) 2 -, -O- (CH 2) u '-Si (OCH 3) 2 OSi (OCH 3) 2 -, -CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -CONR 34
- X d is -S-, -C (O) O-, -CONR 34 -, -CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -CONR 34 - (CH 2) u '-N (R 34) -, or -CONR 34 - (o-, m- or p- phenylene) -Si (R 33) 2 - [Wherein each symbol is as defined above. ] Represents
- X 1 is -X f -, -X f -C 1-20 alkylene group, -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' - [Wherein, X f , s ′ and t ′ are as defined above.
- X c is, -O-, or -CONR 34 -
- X d is, -CONR 34 -
- R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence.
- X 1 is -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' -
- X f , s ′ and t ′ are as defined above.
- X c is, -CONR 34 -
- X d is, -CONR 34 -, R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence.
- X 1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s' -X c- (CH 2 ) t ' -or -X d- (CH 2 ) t'- [Wherein each symbol is as defined above. ] It can be.
- said X 1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s ' -O- (CH 2 ) t'- , -(CH 2 ) s' -(Si (R 33 ) 2 O) m ' -Si (R 33 ) 2- (CH 2 ) t'- , - (CH 2) s '-O- (CH 2) u' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, or - (CH 2) s' -O- (CH 2) t '-Si (R 33) 2 - (CH 2) u' -Si (R 33) 2 - (C v H 2v) - [Wherein, R 33 , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more
- -(C v H 2v ) - may be linear or branched, and for example, -CH 2- , -CH 2 CH 2- , -CH 2 CH 2 CH 2 -, - CH (CH 3 ) -, - CH (CH 3) CH 2 - may be.
- the X 1 group is substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group) It may be done.
- the X 1 group may be other than an —O—C 1-6 alkylene group.
- the X 1 group includes, for example, the following groups: [Wherein each R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; D is -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 means phenyl), and (Wherein, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a a methyl
- X 1 include, for example: Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -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 -,
- X 1 is -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 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- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2
- X 1 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)
- X 1 represents X e ′ .
- X e ′ is a single bond, an alkylene group having 1 to 6 carbon atoms, -R 51 -C 6 H 4 -R 52- , -R 51 -CONR 4 -R 52- , -R 51 -CONR 4 -C 6 H 4 -R 52 -, - R 51 -CO-R 52 -, - R 51 -CO-C 6 H 4 -R 52 -, - R 51 -SO 2 NR 4 -R 52 -, - R 51 - SO 2 NR 4 -C 6 H 4 -R 52- , -R 51 -SO 2 -R 52- , or -R 51 -SO 2 -C 6 H 4 -R 52- .
- R 51 and R 52 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 3 carbon atoms.
- R 4 is as defined above.
- the alkylene group is substituted or unsubstituted, preferably unsubstituted.
- a halogen atom Preferably a fluorine atom can be mentioned, for example.
- the alkylene group is linear or branched, and is preferably linear.
- X e ′ is Single bond, -X f -, An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group, -C 6 H 4 -R 52 ' -, -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -CO-R 52 ' -, -CO-C 6 H 4 -R 52 ' -, -SO 2 NR 4 '-R 52' -, -SO 2 NR 4 '-C 6 H 4 -R 52' -, -SO
- R 4 ′ is a hydrogen atom or a methyl group. ) It can be.
- X e ′ is preferably -X f -, An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group, -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -R 51 '-CONR 4' -, -R 51 '-CONR 4' -C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 - ,
- X e ′ is more preferably -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -R 51 '-CONR 4' -, -R 51 '-CONR 4' -C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 - , -X f -CONR 4 '- or -X f -CONR 4,' -C 6 H 4 -, It can be.
- X e ′ include, for example, Single bond, Perfluoroalkylene groups having 1 to 6 carbon atoms (eg, -CF 2 -,-(CF 2 ) 2-, etc.), An alkylene group having 1 to 6 carbon atoms, -CF 2 -C 1-6 alkylene group, -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CF 2 -CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 ) -CH 2- , -CON (CH 3 )-(CH 2 ) 2- , -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 )-
- preferable X e ′ is An alkylene group having 1 to 6 carbon atoms, Perfluoroalkylene groups having 1 to 6 carbon atoms (eg, -CF 2 -,-(CF 2 ) 2-, etc.), -CF 2 -C 1-6 alkylene group, -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 ) -CH 2- , -CON (CH 3 )-(CH 2 ) 2- , -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 ) CH 2- ,
- more preferable X e ′ is -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 ) -CH 2- , -CON (CH 3 )-(CH 2 ) 2- , -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 ) CH 2- , -CF 2 -CON (CH 3 )-(CH 2 ) 2- , -CF 2 -CON (CH 3 )-(CH 2 ) 3- , -CH 2 -CONH-, -CH 2 -CONH-CH 2- ,
- X e ′ is a single bond.
- a group having a binding ability between PFPE and a substrate that is, a group enclosed in parentheses with ⁇ 1 in (A) is directly bonded.
- X 1 is a group represented by the formula:-(R 16 ) x- (CFR 17 ) y- (CH 2 ) z- .
- x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order of existence of each parenthesized parenthesis is in the formula Is optional.
- R 16 are each independently at each occurrence, an oxygen atom, a phenylene, carbazolylene, -NR 18 - (wherein, R 18 represents a hydrogen atom or an organic group) or a divalent organic group is there.
- R 16 is an oxygen atom or a divalent polar group.
- the “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group or an n-propyl group, which are substituted by one or more fluorine atoms It is also good.
- R 17 in 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 trifluoro It is a methyl group, a pentafluoroethyl group, more preferably a trifluoromethyl group.
- X 1 is preferably of the formula: — (O) x — (CF 2 ) y — (CH 2 ) z —, wherein x, y and z are as defined above, in parentheses The order of existence of each repeating unit enclosed is arbitrary group in the formula).
- Examples of the group represented by the above formula:-(O) x- (CF 2 ) y- (CH 2 ) z- include, for example,-(O) x ' -(CH 2 ) z " -O-[(CH 2 ) 2) z '''-O-] z "", and - (O) x' - ( CF 2) y "- (CH 2) z” -O - [(CH 2) z '''-O- Z ′ ′ ′ ′ ′ (wherein, x ′ is 0 or 1, y ′ ′, z ′ ′ and z ′ ′ ′ are each independently an integer of 1 to 10, and z ′ ′ ′ is 0 or 1 The left end of these groups is bonded to the PFPE side.
- X 1 is —O—CFR 20 — (CF 2 ) e ′ —.
- the above R 20 each independently represents a fluorine atom or a lower fluoroalkyl group.
- the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, further preferably It is a trifluoromethyl group.
- the above e's are each independently 0 or 1.
- R 20 is a fluorine atom and e ′ is 1.
- examples of X 1 groups include: [In the formula, Each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; In each X 1 group, any part of T is attached to PFPE of the molecular backbone: -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CF 2 O (CH 2 ) 3- , -CH 2- , -(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 means phenyl), or [Wherein, R 42 each independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkyl group or
- T's are — (CH 2 ) n ′ ′ (n ′ ′ is an integer from 2 to 6) attached to the group opposite to the PFPE of the molecular main chain, and, if present, the remaining T may be each independently a methyl group, a phenyl group, a C 1-6 alkoxy group or a radical scavenging group or an ultraviolet absorbing group.
- the group described as X 1 is bonded to the group represented by PFPE on the left side and the group enclosed in parentheses with ⁇ 1 on the right side.
- the radical scavenging group is not particularly limited as long as it can scavenge a radical generated upon irradiation with light, for example, benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates And residues of hindered amines, hindered phenols, or triazines.
- the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, and examples thereof include benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, The residue includes oxanilides, benzoxazinones and benzoxazoles.
- preferred radical scavenging groups or ultraviolet absorbing groups are Can be mentioned.
- X 1 (and X 3 , X 5 and X 7 described below) may be a trivalent to dodecavalent organic group.
- X 2 each independently represents a single bond or a divalent organic group at each occurrence.
- X 2 is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably — (CH 2 ) u — (wherein u is an integer of 0 to 2).
- t is each independently an integer of 1 to 10. In a preferred embodiment, t is an integer of 1 to 6. In another preferred embodiment, t is an integer of 2 to 10, preferably an integer of 2 to 6.
- the compound represented by the preferred formula (A) has the following formula (A ′): [In the formula: The PFPEs each independently at each occurrence have 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 - (Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; The order in which each repeating unit in parentheses is attached with a, b, c, d, e or f is arbitrary in the formula.) A group represented by R 13 independently at each occurrence independently represents a hydroxyl group or a hydrolysable group; R 14 independently represents at each occurrence a hydrogen atom or an alkyl group having 1 to 22 carbon
- the compound represented by the above-mentioned formula (A) can be obtained, for example, by introducing iodine into the terminal using a perfluoropolyether derivative corresponding to the -PFPE- moiety as a raw material, and then introducing -CH 2 CR 12 (X 2 -SiR 13 n 1 It can be obtained by reacting a vinyl monomer corresponding to R 14 3-n 1 )-.
- PFPE, R 13 , R 13 ′ ′ , R 14 , R 14 ′ ′ and n 1 are as defined for the above formula (A).
- the Si atom bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolysable group is an integer of 1 to 3 as n1 and (-SiR 13 n1 R 14 3 represents an Si atom contained in 3-n1 ) or (-SiR13 " n1 R14 " 3-n1 ).
- n1 is an integer of 0 to 3 independently for each (-SiR 13 n1 R 14 3-n 1 ) unit or for each (-SiR 13 ′ ′ n1 R 14 ′ 3-n 1 ) unit, preferably Is 1 to 3, more preferably 3.
- at least two n1 are integers of 1 to 3, that is, all n1 are never 0 simultaneously. That is, in the formula, at least two are R 13 or R 13 ′ ′ .
- —SiR 13 n 1 R 14 3-n 1 structure ie, —SiR 13 moiety
- n 1 is 1 or more
- at least two structures selected from the group consisting of —SiR 13 ′ ′ n1 R 14 ′ ′ 3-n 1 structures ie, —SiR 13 ′ ′ moieties in which n 1 is 1 or more.
- At least one Si bonded to a hydroxyl group or a hydrolyzable group is present at each end of the molecular backbone of the PFPE-containing silane compound (A). That is, at least one —SiR 13 moiety is present and at least one —SiR 13 ′ ′ moiety is present.
- each X 3 independently represents a single bond or a di- to 10-valent organic group.
- said X 3 mainly has a water-repellent property, a surface slip property and the like, and a bonding ability between a substrate and a perfluoropolyether part (ie, -PFPE-part). It is understood as a linker connecting the provided silane moiety (specifically, -SiR 13 n1 R 14 3-n 1 or -SiR 13 " n 1 R 14" 3- n 1 ).
- X 3 may be a single bond or any organic group as long as the compound represented by the formula (B) can be stably present.
- the left side is bonded to a group represented by PFPE, and the right side is bonded to a group enclosed in parentheses with ⁇ 1 attached.
- X 3 represents X e .
- X e is as defined above.
- ⁇ 1 is an integer of 1 to 9 and can vary depending on the valence of X 3 .
- ⁇ 1 is a value obtained by subtracting 1 from the value of the valence of X 3 .
- ⁇ 1 is 1.
- the above X 3 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 3 is a divalent to tetravalent organic group, and ⁇ 1 is 1 to 3.
- X 3 is a divalent organic group and ⁇ 1 is 1.
- the formula (B) is represented by the following formula (B ′).
- Examples of the X 3, is not particularly limited, examples thereof include the same as described for X 1.
- preferred specific X 3 is Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -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
- X 3 is -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 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- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2
- X 3 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 3-
- X 3 represents X e ′ .
- X e ′ is as defined above.
- X e ′ is a single bond.
- a group having a binding ability between PFPE and a substrate that is, a group which is attached with ⁇ 1 and bracketed in (B) is directly bonded.
- At least two Si bonded to a hydroxyl group or a hydrolyzable group are present. That is, in Formula (B), there are at least two SiR 13 moieties.
- the compound represented by the preferred formula (B) has the following formula (B ′): [In the formula: The PFPEs each independently at each occurrence have 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 - (Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; The order in which each repeating unit in parentheses is attached with a, b, c, d, e or f is arbitrary in the formula.) A group represented by R 13 independently at each occurrence independently represents a hydroxyl group or a hydrolysable group; R 14 independently represents at each occurrence a hydrogen atom or an alkyl group having 1 to 22 carbon
- the compound represented by the above formula (B) can be produced by a known method, for example, the method described in JP 2013-117012 A or its improved method.
- PFPE is as defined above.
- each X 5 independently represents a single bond or a di- to 10-valent organic group.
- said X 5 mainly has the ability to bond the substrate with the perfluoropolyether moiety (ie, -PFPE- moiety) which provides water repellency and surface slippage etc. (specifically, -SiR a k1 R b l1 R c m1 group or -SiR a "k1 R b" l1 R c "m1 group) silane unit to provide the solution with a linker connecting. Therefore,
- the X 5 may be a single bond or any organic group as long as the compound represented by the formula (C) can be stably present. structure is described as X 5 is a group left represented by PFPE, based on the right in parentheses are given the .gamma.1, respectively coupled.
- X 5 represents X e .
- X e is as defined above.
- ⁇ 1 is an integer of 1 to 9, and ⁇ 1 may change according to the valence of X 5 .
- ⁇ 1 is a value obtained by subtracting 1 from the value of the valence of X 5 .
- ⁇ 1 is 1.
- the above X 5 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 5 is a divalent to tetravalent organic group, and ⁇ 1 is 1 to 3.
- X 5 is a divalent organic group and ⁇ 1 is 1.
- the formula (C) is represented by the following formula (C ′).
- Examples of X 5 include, but are not particularly limited to, the same ones as described for X 1 .
- preferred specific X 5 is Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -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
- X 5 is preferably -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -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 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- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -
- X 5 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 3-
- X 5 represents X e ′ .
- X e ′ is as defined above.
- X e ′ is a single bond.
- a group having a binding ability between PFPE and a substrate that is, a group enclosed in parentheses in the formula (C) with ⁇ 1 attached thereto is directly bonded.
- R a independently represents -Z 3 -SiR 71 p 1 R 72 q 1 R 73 r 1 at each occurrence.
- each Z 3 independently represents an oxygen atom or a divalent organic group.
- the above Z 3 is preferably a divalent organic group, and does not include those forming a siloxane bond with the Si atom at the end of the molecular main chain in the formula (C) (Si atom to which R a is bonded) .
- the above Z 3 is preferably a C 1-6 alkylene group,-(CH 2 ) g -O- (CH 2 ) h- (wherein, g is an integer of 1 to 6 and h is 1 to 6) Or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and more preferably a C 1-3 alkylene group.
- These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
- the above Z 3 is more preferably a linear or branched alkylene group, and still more preferably a linear alkylene group.
- the number of carbon atoms constituting the above Z 3 alkylene group is preferably in the range of 1 to 6, and more preferably in the range of 1 to 3.
- the alkylene group is as described above.
- R 71 independently represents Ra ' at each occurrence.
- R a ′ is as defined in R a .
- the maximum number of Sis linked in a linear fashion via a Z 3 group is five. That is, in the above R a , when at least one R 71 is present, two or more Si atoms linearly linked through the Z 3 group are present in R a , but through such Z 3 group Thus, the number of Si atoms linked in a linear manner is at most five. Note that the "through Z 3 group in R a number of Si atoms linearly linked" is equal to -Z 3 -Si- repetition number of which is connected to a linear during R a become.
- * means a site to be bonded to Si in the main chain, ... indicates that a predetermined group other than Z 3 Si is bonded, that is, all three bonds of Si atoms are ... In this case, it means the end of the repetition of Z 3 Si.
- the number on the right of Si means the appearance number of Si linearly linked via Z 3 group counted from *. That is, the chain in which the Z 3 Si repeat is completed in Si 2 is “the number of Si atoms linearly linked via the Z 3 group in R a ” is 2, similarly, Si 3 , And Si 4 and Si 5 in which the Z 3 Si repeat ends are “number of Si atoms linearly linked via Z 3 group in R a ” of 3, 4 and 5, respectively Is one.
- a plurality of Z 3 Si chains are present in R a , but they do not have to have the same length, and may have any length.
- the number of Si atoms linearly linked via the Z 3 group in R a is 1 (left equation) or 2 (all the chains) in all chains. Right).
- the number of Si atoms linearly linked via the Z 3 group in R a is one or two, preferably one.
- each R 72 independently at each occurrence represents a hydroxyl group or a hydrolysable group.
- the "hydrolyzable group” is as defined above.
- R 72 is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
- R 73 each independently represents a hydrogen atom or a lower alkyl group at each occurrence.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- '(if R a' is absent, R a) terminal of R a in R a in the above q1 is preferably 2 or more, for example 2 or 3, more preferably 3.
- At least one of the terminal parts of R a is —Si (—Z 3 -SiR 72 q1 R 73 r1 ) 2 R 72 q1 ′ R 73 r1 ′ (wherein any one of q1 ′ and r1 ′ Is 1 and the other is 0) or -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 (herein And the sum of q1 and r1 is 3.
- (- Z 3 -SiR 72 q1 R 73 r1) units is preferably (-Z 3 -SiR 72 3).
- all the terminal parts of R a may be -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably -Si (-Z 3 -SiR 72 3 ) 3 .
- the ends of the groups represented by (SiR a k1 R b l1 R c m1) is, -Si (-Z 3 -SiR 72 q1 R 73 r1) 2 R b l1 R c m1 ( However, l1 and one of m1 is 1 and the other is 0), -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 2 R 72 q1 ' R 73 r1' (however, either q1 'or r1' Or one is 1 and the other is 0), or -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 (Where the sum of q1 and r1 is 3). More preferably, the ends of the groups represented by (SiR a k1 R b l1 R c
- R a ′ ′ independently represents —Z 3 —SiR 71 p1 R 72 ′ ′ q1 R 73 r 1 at each occurrence.
- Z 3 , R 71 , R 73 , p1, q1 and r1 are as defined above.
- R 72 ′ ′ has the same meaning as R 72 .
- At least one of the terminal parts of R a ′ ′ is —Si (—Z 3 -SiR 72 ” q 1 R 73 r 1 ) 2 R 72” q 1 ′ R 73 r 1 ′ (wherein q 1 ′ and r 1 ′ Either one is 1 and the other is 0) or -Si (-Z 3 -SiR 72 " q1 R 73 r1 ) 3 , preferably -Si (-Z 3 -SiR 72" q1 R 73 r1 ) 3 (total 3 is here, q1 and r1) in formula, which may be a,.
- (- Z 3 -SiR 72 " units of q1 R 73 r1) is preferably (-Z 3 -SiR 72" 3)
- all the terminal parts of R a are -Si (-Z 3 -SiR 72 " q 1 R 73 r 1 ) 3 , preferably -Si (-Z 3 -SiR 72" 3 ) 3 obtain.
- the end of the group represented by (SiR a " k1 R b" l1 R c " m1 ) is -Si (-Z 3 -SiR 72" q1 R 73 r1 ) 2 R b " l1 R c" m1 (wherein, one of l1 and m1 is 1 and the other is 0), -Si (-Z 3 -SiR 72 " q1 R 73 r1 ) 2 R 72" q1 ' R 73 r1' (where , one of q1 'and r1' is 1 and the other is 0), or -Si (-Z 3 -SiR 72 "q1 R 73 r1) 3, preferably -Si (-Z 3 -SiR 72 ′ ′ q1 R 73 r1 ) 3 (where the sum of q 1 and r 1 is 3).
- the end of the group represented by (SiR a ′ ′ k1 R b ′ ′ l1 R c ′ ′ m1 ) is —Si ( ⁇ Z 3 —SiR 72 ′ ′ 3 ) 3 .
- SiR 72 specifically, a group represented by -SiR 71 p1 R 72 q1 R 73 r 1, provided that q1 is an integer of 1 to 3
- SiR 72 ′ ′ specifically, -SiR 71 p1 R 72 "q1 group represented by R 73 r1, however, integers q1 is 1-3
- the SiR b specifically, the group represented by -SiR a k1 R b l1 R c m1, where l1 A group consisting of SiR b ′ ′ (specifically, a group represented by —SiR a ′ ′ k1 R b ′ ′ i1 R c ′ ′ m1 , provided that l1 is an integer of 1 to 3)
- R b and R b " will be described
- At least one Si bonded to a hydroxyl group or a hydrolyzable group is present at each end of the molecular backbone of the PFPE-containing silane compound (A). That is, there is at least one structure of SiR 72 and / or SiR b and at least one structure of SiR 72 ′ ′ and / or SiR b ′ ′.
- each R b independently represents a hydroxyl group or a hydrolysable group.
- R 1 represents an alkyl group having 1 to 4 carbon atoms), and more preferably -OR.
- R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
- an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
- the hydroxyl group is not particularly limited, but may be formed by hydrolysis of a hydrolyzable group. More preferably, R b is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
- R b ′ ′ is as defined in R b .
- R c independently at each occurrence represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- R c ′ ′ has the same meaning as R c .
- k1 is each independently an integer of 0 to 3 at each occurrence; 11 is each independently an integer of 0 to 3 at each occurrence; m1 is each independently at each occurrence Is an integer of 0 to 3.
- SiR a k1 R b l1 R c m1 or every each (SiR a "k1 R b" l1 R c "m1), the sum of k1, l1 and m1 is 3.
- k1 is preferably 1 to 3, and more preferably 3.
- the compounds represented by the above formula (C) can be synthesized, for example, as described in WO 2014/069592.
- PFPE is as defined in the above formula (A).
- each X 7 independently represents a single bond or a di- to 10-valent organic group.
- said X 7 mainly has the ability to bind to the substrate with the perfluoropolyether moiety (that is, -PFPE- moiety), which provides water repellency and surface slippage etc. It is understood as a linker linking the provided moiety (ie the group bracketed with ⁇ 1). Therefore, the X 7 may be a single bond or any organic group as long as the compound represented by the formula (D) can be stably present.
- the left side is bonded to a group represented by PFPE, and the right side is bonded to a group enclosed in parentheses with ⁇ 1.
- X 7 represents X e .
- X e is as defined above.
- ⁇ 1 is an integer of 1 to 9, and ⁇ 1 can change according to the valence of X 7 .
- ⁇ 1 is the value obtained by subtracting 1 from the valence of X 7.
- ⁇ 1 is 1.
- the above-mentioned X 7 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 7 is a divalent to tetravalent organic group, and ⁇ 1 is 1 to 3.
- X 7 is a divalent organic group and ⁇ 1 is 1.
- the formula (D) is represented by the following formula (D ′).
- Examples of X 7 include, but are not particularly limited to, the same ones as those described for X 1 .
- preferred specific X 7 is Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -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
- more preferred specific X 7 is -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -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 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- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
- X 7 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 3-
- X 7 represents X e ′ .
- X e ′ is as defined above.
- X e ′ is a single bond.
- a group having a binding ability between PFPE and a substrate that is, a group which is attached with .delta.1 in parentheses in the formula (D)
- a bonding strength between PFPE and a group enclosed in parentheses with ⁇ 1 becomes stronger.
- a carbon atom directly bonded to PFPE ie, a carbon atom bonded to R d , R e and R f in the parenthesized group attached with ⁇ 1, or R d ′ ′ , R e ′ ′ and R f ′ ′
- the carbon atom bonded to is less in charge bias, and as a result, it is difficult for a nucleophilic reaction or the like to occur at the above carbon atom, and the compound is stably bonded to the substrate. It is advantageous because the friction durability of the layer formed by the compound can be further improved.
- R d independently represents -Z 4 -CR 81 p 2 R 82 q 2 R 83 r 2 at each occurrence.
- Z 4 independently represents an oxygen atom or a divalent organic group at each occurrence.
- the above Z 4 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein, g is an integer of 0 to 6, for example, an integer of 1 to 6) H is an integer of 0 to 6, for example, an integer of 1 to 6) or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and Preferably, it is a C 1-3 alkylene group. These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
- R 81 independently represents R d ′ at each occurrence.
- R d ′ is as defined the R d .
- Cs linked in a linear fashion via a Z 4 group are at most 5 pieces. That is, in the above Rd , when at least one R 81 is present, two or more C atoms linked in a straight line via the Z 4 group are present in R d , and such a C 4 group is intervened.
- the maximum number of C atoms linked in a straight chain is five. Note that the "through Z 4 group in R d number of C atoms linearly linked" is equal to the number of repetitions of -Z 4 -C- being linearly linked in a R d Become.
- the number of C atoms linearly linked via the Z 4 group in R d is 1 (left) or 2 (the left expression) in all chains. Right).
- the number of C atoms to be linked via Z 4 groups R d linearized is one or two, preferably one.
- R 82 independently represents -Y-SiR 85 n 2 R 86 3- n 2 at each occurrence.
- Y's each independently represent a divalent organic group at each occurrence.
- Y C 1-6 alkylene group, - (CH 2) g ' -O- (CH 2) h' - (wherein, g 'is from 0 to 6 integer, for example from 1 to 6 H is an integer of 0 to 6, for example, an integer of 1 to 6, or -phenylene- (CH 2 ) i ' -(wherein i' is an integer of 0 to 6) ).
- These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
- Y can be a C 1-6 alkylene group or -phenylene- (CH 2 ) i ' -.
- the light resistance in particular the UV resistance, may be higher.
- R 85 each independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
- hydrolyzable group examples include those similar to the formula (C).
- R 85 is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl group or a methyl group, in particular a methyl group.
- R 86 each independently represents a hydrogen atom or a lower alkyl group at each occurrence.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- n2 is, (- Y-SiR 85 n2 R 86 3-n2) each unit or (-Y-SiR 85 "n2 R 86" 3-n2) independently for each unit, an integer of 0 to 3, preferably Is an integer of 1 to 3, more preferably 2 or 3, particularly preferably 3.
- R 85 ′ ′ and R 86 ′ ′ will be described later.
- the aforementioned R 83 each independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group, preferably a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- '(if R d' is absent, R d) end of R d in R d in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.
- At least one of the terminal parts of R d is -C (-Y-SiR 85 n 2 R 86 3- n 2 ) 2 (specifically, -C (-Y-SiR 85 n 2 R 86 3-) n2) 2 R 83) or -C (-Y-SiR 85 n2 R 86 3-n2) 3, may be preferably -C (-Y-SiR 85 n2 R 86 3-n2) 3.
- n2 is an integer of 1 to 3.
- (- Y-SiR 85 n2 R 86 3-n2) units is preferably (-Y-SiR 85 3).
- the distal end of the R d are all -C (-Y-SiR 85 n2 R 86 3-n2) 3, may be preferably -C (-Y-SiR 85 3) 3.
- the end of the group represented by (CR d k 2 R e 1 2 R f m 2 ) is C (-Y-SiR 85 n 2 R 86 3- n 2 ) 2 R f ), C (-Y-SiR 85 n 2 R 86 3- n 2 ) 2 R 83 or C (-Y-SiR 85 n 2 R 86 3- n 2 ) 3 , preferably C (-Y-SiR 85 n 2 R 86 3- n 2 ) 3
- n2 is an integer of 1 to 3.
- (- Y-SiR 85 n2 R 86 3-n2) units is preferably (-Y-SiR 85 3).
- all the terminal parts of the above groups may be -C (-Y-SiR 85 n 2 R 86 3- n 2 ) 3 , preferably -C (-Y-SiR 85 3 ) 3 .
- R d ′ ′ independently represents -Z 4 -CR 81 p2 R 82 ′ ′ q 2 R 83 r 2 at each occurrence.
- Z 4 , R 81 , R 83 , p 2, q 2 and r 2 are as defined above.
- R 82 ′ ′ each independently represents -Y-SiR 85 ′ ′ n 2 R 86 ′ ′ 3- n 2 at each occurrence, wherein Y and n 2 are as defined above.
- R 85 ′ ′ and R 86 ′ ′ is as defined for R 85 and R 86 , respectively.
- R d in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3 is there.
- At least one of the terminal parts of Rd ′ ′ is —C (—Y—SiR 85 ′ ′ n2 R 86 ′ ′ 3- n 2 ) 2 (specifically, —CR 81 p 2 (—Y—SiR 85) “ N 2 R 86” 3- n 2 ) 2 R 83 ) or —C (—Y—SiR 85 ” n 2 R 86” 3- n 2 ) 3 , preferably —C (—Y—SiR 85 ” n 2 R 86” 3- n2 ) 3 may be, wherein n2 is an integer of 1 to 3, wherein the unit of (-Y-SiR 85 " n2 R 86" 3-n2 ) is preferably (-Y-SiR 85) " 3 ).
- the distal end of the R d are all -C (-Y-SiR 85 "n2 R 86" 3-n2) 3, may be preferably -
- the end of the group represented by (CR d ′ ′ k2 R e ′ ′ l2 R f ′ ′ m2 ) is C (—Y—SiR 85 ′ ′ n2 R 86 ′ ′ 3-n2 ) 2 R f ′ ′ , C (-Y-SiR 85 '' n2 R 86 '' 3- n 2 ) 2 R 83 or C (-Y-SiR 85 '' n 2 R 86 '' 3- n 2 ) 3 , preferably C (-Y-SiR 85 '' n 2 R 86 " 3- n 2 ) 3 .
- n2 is an integer of 1 to 3.
- (- Y-SiR 85 "n2 R 86" 3-n2) units is preferably (-Y-SiR 85 "3)
- the distal end of the base, all - It may be C (-Y-SiR 85 " n2 R 86" 3-n2 ) 3 , preferably -C (-Y-SiR 85 " 3 ) 3 .
- R e independently represents -Y-SiR 85 n 2 R 86 3- n 2 at each occurrence.
- Y, R 85 , R 86 and n 2 are as defined in R 82 above.
- R e ′ ′ independently at each occurrence is —Y—SiR 85 ′ ′ n 2 R 86 ′ ′ 3- n 2 where R 85 ′ ′ , R 86 ′ ′ , Y and n 2 are It is as defined above.
- R f each independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group at each occurrence.
- each R f independently at each occurrence represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- R f ′ ′ has the same meaning as R f .
- k2 is independently an integer of 0 to 3 at each occurrence; 12 is an integer of 0 to 3 independently at each occurrence; m2 is independently at each occurrence Is an integer of 0 to 3. However, the sum of k2, l2 and m2 is 3.
- At least one k2 is 2 or 3, preferably 3.
- k2 is 2 or 3, preferably 3.
- l2 is 2 or 3, preferably 3.
- n2 is an integer of 1 to 3, and at least one q2 is 2 or 3, or at least one 12 is 2 or 3.
- the compound represented by the said Formula (D) can be manufactured by combining a well-known method.
- the PFPE-containing silane compound (A) is represented by the formula (B) or (C).
- the above-mentioned PFPE-containing silane compound (A) is not particularly limited, but may have a number average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 . Within this range, it is preferable to have a number average molecular weight of 2,000 to 30,000, more preferably 2,500 to 12,000, still more preferably 3,000 to 6,000. In the present invention, the number average molecular weight is a value measured by 19 F-NMR.
- the PFPE-containing silane compound (A) may be a compound represented by Formula (A), (C) or (D).
- the adhesion to the substrate can be improved by using such a silane compound.
- the PFPE-containing silane compound (A) has two or more, preferably three or more Si atoms having a hydroxyl group or a hydrolyzable group at at least one end.
- the crosslinking agent is a fluorine-containing silane compound (for example, a PFPE-containing silane compound (A), specifically, a silane moiety having a hydroxyl group or a hydrolyzable group bonded to the Si atom of the PFPE-containing silane compound (A))
- the compound is not particularly limited as long as it is a compound having a moiety capable of undergoing a crosslinking reaction (condensation reaction).
- the physical properties for example, tensile strength and elastic modulus of the cured product obtained from the curable composition of the present invention It can be.
- the cross-linking agent is an organosilicon compound having at least two -O-R g3 bonded to a Si atom.
- R g3 is independently at each occurrence a hydrogen atom or a monovalent organic group.
- the monovalent organic group means a group containing a carbon atom.
- the monovalent organic group is not particularly limited, and examples thereof include groups in which one hydrogen atom is further eliminated from a hydrocarbon group.
- the hydrocarbon group is as defined above.
- the crosslinking agent has a structure different from that of the fluorine-containing silane compound (specifically, the PFPE-containing silane compound (A)).
- Organosilicon compounds having at least two silanol groups in one molecule In the organic silicon compound, the silanol group is preferably present at both ends of the molecular main chain.
- the molecular main chain represents the relatively longest bond chain in the molecule of the organosilicon compound.
- R g1 is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms.
- R g1 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl or nonyl Alkyl groups such as decyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, cyclohexenyl group and the like Alkenyl groups; aryl groups such as phenyl, tolyl, xylyl and
- R g2 is independently at each occurrence independently a substituted or unsubstituted C 1-20 carbon atom, preferably a divalent C 2-10 carbon atom. It is a hydrocarbon group.
- R g2 include alkylene groups such as methylene, ethylene, propylene, methylethylene, butylene and hexamethylene; cycloalkylenes such as cyclohexylene, phenylene, tolylene and xylylene And arylene groups such as naphthylene group and biphenylene group; groups in which a part or all of hydrogen atoms of these groups are substituted with a halogen atom or the like; and combinations of these substituted or unsubstituted alkylene groups and arylene groups are exemplified.
- R g2 a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, a cyclohexylene group and a phenylene group are preferable, and an ethylene group, a propylene group, a butylene group and a phenylene group are particularly preferable.
- a compound having a silanol group in the molecule R g1 3 SiO 1/2 , R g1 2 SiO, R g1 SiO 3/2 , and a combination of one or more kinds of SiO 2 units and a silanol group
- the resinous compound comprised by these is mentioned.
- the structural units in the resinous compound may be directly bonded to each other, or may be bonded to each other via a divalent or higher hydrocarbon group.
- ⁇ 1 is independently an integer of 1 or more at each occurrence.
- ⁇ 1 is preferably 2 or more, more preferably 5 or more, preferably 50 or less, more preferably 20 or less.
- the organosilicon compound having at least two silanol groups in one molecule preferably has no PFPE structure in its molecular structure.
- R g3 is as defined above.
- the above R g3 is a moiety having a hydroxyl group or a hydrolysable group bonded to the Si atom of the PFPE-containing silane compound (A) represented by the above formulas (A), (B), (C) or (D) It is a part that can react with.
- the R g3 is preferably a monovalent organic group.
- R g4 is independently at each occurrence a monovalent organic group.
- R g4 is preferably a substituted or unsubstituted monovalent hydrocarbon group, and more preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms.
- R g4 is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups such as decyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; such as benzyl group, phenylethyl group and phenylpropyl group Aralkyl groups; Alkenyl groups such as vinyl group, allyl group, propenyl group and butenyl group; and groups in which part or all of the hydrogen atoms of these groups are substituted with halogen atom
- R g4 may be a group represented by the following general formula.
- Rf 1 -R g5- In the above formula, Rf 1 is a monovalent fluorinated polyether group.
- Rf 1 above CF 3 O—, CF 3 CF 2 O—, CF 3 CF 2 CF 2 O—, (CF 3 ) 2 CFO—, or CF 3 CF 2 CF 2 CF 2 at the CF 2 end of the above PFPE 2 O- and the like are exemplified.
- R g5 is a divalent organic group.
- the divalent organic group is as defined above.
- R g5 may contain, for example, one or more of an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom, and may contain an amide bond or a sulfonamide bond, which may be substituted or unsubstituted Or a divalent hydrocarbon group of
- the divalent hydrocarbon group preferably has 2 to 20 carbon atoms.
- substituted or unsubstituted divalent hydrocarbon group which does not intervene an oxygen atom, a nitrogen atom, a silicon atom or a sulfur atom and does not contain an amide bond or a sulfonamide bond
- ethylene groups Alkylene groups such as propylene, methylethylene, butylene and hexamethylene; cycloalkylenes such as cyclohexylene; arylenes such as phenylene, tolylene, xylylene, naphthylene and biphenylene; And combinations thereof with arylene groups; and groups in which part or all of the hydrogen atoms of these alkylene groups and arylene groups are substituted with halogen atoms.
- the oxygen atom is -O-
- the nitrogen atom is -NR g51-
- R g51 is a hydrogen atom or an alkyl or aryl group having 1 to 10 carbon atoms
- -N Silicon atoms may be included as -SiR g52 R g53- (R g52 , R g53 each independently at each occurrence is an alkyl group or aryl group having from 1 to 10 carbon atoms) and a sulfur atom may be included as -S- .
- the following are mentioned as a specific example of such a bivalent hydrocarbon group.
- Me represents a methyl group and Ph represents a phenyl group, and in each of the following formulas, an Rf 1 group is bonded to the left side.
- ⁇ 2 is independently 2 or 3 at each occurrence, and ⁇ 3 is 2 or 3 independently at each occurrence.
- R g3 and R g4 are as defined above.
- R g6 - is independently at each occurrence, R g8 -R g7 - represents a.
- R g7 independently represents a single bond, an oxygen atom or a divalent organic group at each occurrence.
- the divalent organic group is as described above.
- R g7 is preferably an alkylene group having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms and containing a nitrogen atom or an oxygen atom in the main chain.
- R g7 is more preferably An alkylene group having 1 to 3 carbon atoms, CH 2 CH 2 -NH-CH 2 CH 2 CH 2 or CH 2 -O-CH 2 CH 2 CH 2 .
- the above R g8 is a reactive functional group.
- the above R g8 is preferably each independently an amino group, an epoxy group, a methacryl group, a vinyl group, or a mercapto group, and more preferably an amino group.
- ⁇ 4 is an integer of 2 or more, preferably 2 or 3, and more preferably 3.
- ⁇ 5 is an integer of 0 or more, preferably 0 or 1.
- ⁇ 6 is 1 or 2, preferably 1. However, the sum of ⁇ 4, ⁇ 5 and ⁇ 6 is 4.
- ⁇ 4 is 2 or 3
- ⁇ 5 is 0 or 1
- ⁇ 6 is 1 or 2
- ⁇ 5 is 0 and ⁇ 6. Is one.
- the crosslinking agent is a compound represented by Formula (E3) or Formula (E5), and more preferably a compound represented by Formula (E3).
- the crosslinking agent does not have a group represented by PFPE in the molecular chain.
- the molecular weight of the crosslinker is 1000 or less, preferably 600 or less, more preferably 250 or less.
- the lower limit value of the molecular weight of the crosslinking agent may be 50 or more, or 100 or more.
- the crosslinker is tetraethoxysilane, tetratrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, dimethyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, tripropylsilane. It is at least one selected from the group consisting of decafluoro-n-octyltriethoxysilane and tridecafluoro-n-octyltrimethoxysilane.
- the crosslinking agent may be used alone or in combination of two or more.
- the crosslinking agent may be contained, for example, 0.1 parts by mass or more, specifically 0.3 parts by mass or more, per 100 parts by mass of the PFPE-containing silane compound (a) in the curable composition of the present invention It can be obtained, and can be contained in an amount of 30 parts by mass or less, specifically, 10 parts by mass or less.
- the above crosslinking agent can be contained, for example, in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the PFPE-containing silane compound (A) in the curable composition of the present invention. It can contain up to 10 parts by mass.
- the above crosslinking agent is more preferably contained in the range of 0.01 to 30 parts by mass with respect to 100 parts by mass of the curable composition of the present invention in the curable composition of the present invention. More preferably, it is included in the range of 0 parts by mass.
- the metal-based catalyst is represented by M (-O-R h ) ⁇ .
- M represents a metal atom
- R h is each independently a hydrocarbon group having 1 to 3 carbon atoms at each occurrence
- ⁇ is a coordination number of M.
- the condensation reaction between the fluorine-containing silane compound (for example, PFPE-containing silane compound (A)) and the crosslinking agent is promoted.
- the metal-based catalyst as described above can be easily dissolved or dispersed in the curable composition, and can contribute to the promotion of a uniform reaction.
- the curable composition of the present invention containing the metal-based catalyst as described above can contribute to the formation of a cured product of a highly transparent curable composition containing few foreign substances.
- the above M is preferably at least one selected from the group consisting of titanium, zirconium and tin.
- M is a titanium atom or a zirconium atom.
- a metal atom as described above as M it can be particularly suitable for use in electric material applications (eg, semiconductor applications, information terminals) and automotive applications.
- electric material applications eg, semiconductor applications, information terminals
- automotive applications By including such metal atoms, the environmental load of the curable composition of the present invention can be reduced.
- R h is a hydrocarbon group of 1 to 3 carbon atoms, preferably an alkyl group of 1 to 3 carbon atoms.
- the alkyl group having 1 to 3 carbon atoms is a methyl group, an ethyl group, an n-propyl group or an i-propyl group.
- ⁇ is the coordination number of the metal atom M. It is preferable that ⁇ be an integer of 1 to 8. For example, when M is a titanium atom or a zirconium atom, ⁇ is 4.
- Preferred metal-based catalysts include at least one selected from the group consisting of tetrapropyl titanate and tetrapropyl zirconate.
- the tetrapropyl titanate include tetraisopropyl titanate (tetraisopropoxytitanium) and tetranormal propyl titanate
- examples of the tetrapropyl zirconate include tetraisopropyl zirconia, tetranormal propyl zirconate and the like.
- Such metal-based catalysts are particularly easy to dissolve or disperse in the curable composition, and can contribute to the promotion of a uniform reaction.
- a curable composition containing such a metal-based catalyst can contribute to the formation of a cured product of a highly transparent curable composition with less foreign matter.
- the metal-based catalyst is preferably contained in an amount of 0.05 parts by mass or more based on 100 parts by mass of the fluorine-containing silane compound (for example, PFPE-containing silane compound (A)) in the curable composition of the present invention More preferably, .07 parts by mass or more is included.
- the metal-based catalyst is preferably contained in an amount of 5.0 parts by mass or less based on 100 parts by mass of the fluorine-containing silane compound (for example, PFPE-containing silane compound (A)) in the curable composition of the present invention More preferably, it is contained in an amount of not more than 0 parts by mass.
- the condensation reaction of the fluorine-containing silane compound and the crosslinking agent is particularly promoted by containing the metal-based catalyst at the above-mentioned concentration.
- the metal-based catalyst is contained in an amount of 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the fluorine-containing silane compound (for example, PFPE-containing silane compound (A)) in the curable composition of the present invention
- the fluorine-containing silane compound for example, PFPE-containing silane compound (A)
- 0.07 to 1.0 parts by mass is more preferable.
- the above metal-based catalysts may be used alone or in combination of two or more.
- the curable composition of the present invention may contain a solvent.
- a solvent for example, a fluorine atom-containing solvent
- the concentration of the solvent may be, for example, 80 parts by mass or less, 50 parts by mass or less, or 40 parts by mass or less based on 100 parts by mass of the curable composition It may be at most parts by mass, or at most 20 parts by mass.
- the composition when using the curable composition of the present invention, may be further diluted with a solvent depending on its use and purpose.
- a solvent used for dilution the agent for fluorine type illustrated above can be used.
- it may be used by dissolving it in a desired concentration in 1,3-bis (trifluoromethyl) benzene, Fluorinert (manufactured by 3M), perfluorobutyl methyl ether, perfluorobutyl ethyl ether or the like as a solvent.
- the curable composition of the present invention may further contain a compound represented by the following Formula (A1), (B1), (C1) or (D1).
- R f independently at each occurrence represents an alkyl group of 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms.
- alkyl group having 1 to 16 carbon atoms in the alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms is a branched or branched straight chain Is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms It is.
- Rf is preferably an alkyl group having 1 to 16 carbon atoms which is substituted by one or more fluorine atoms, more preferably a CF 2 H—C 1-15 fluoroalkylene group or a C 1 ⁇ group. It is a 16 perfluoroalkyl group, more preferably a C 1-16 perfluoroalkyl group.
- the perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, preferably linear or branched, having 1 to 6 carbon atoms, in particular carbon atoms It is a perfluoroalkyl group of 1 to 3 and more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically, -CF 3 , -CF 2 CF 3 , or -CF 2 CF 2 CF 3.
- ⁇ 1 is an integer of 1 to 9
- ⁇ 1 ′ is an integer of 1 to 9.
- ⁇ 1 ′ may vary depending on the valence of X 1 .
- the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 1 .
- X 1 is a 10-valent organic group
- [alpha] 1 and [alpha] 1 'sum is 10, for example, [alpha] 1 is 9 and [alpha] 1' is 1, [alpha] 1 is 5 and [alpha] 1 'is 5 or [alpha] 1 is 1 and [alpha] 1, 'Can be nine.
- X 1 is a divalent organic group
- ⁇ 1 and ⁇ 1 ′ are 1.
- X 1 is a single bond
- ⁇ 1 and ⁇ ′ 1 are 1.
- the above X 1 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, and still more preferably a divalent organic group.
- X 1 is a divalent to tetravalent organic group
- ⁇ 1 is 1 to 3
- ⁇ 1 ′ is 1.
- X 1 is a divalent organic group
- ⁇ 1 is 1
- ⁇ 1 ′ is 1.
- n1 ' is independently an integer of 0 to 3, preferably 1 to 3, and more preferably, for each (-SiR 13 n1' R 14 3-n1 ' ) unit. It is three.
- at least one n1 ' is an integer of 1 to 3, that is, all n1' are never 0 simultaneously.
- at least one R 13 exists.
- ⁇ 1 is an integer of 1 to 9
- ⁇ 1 ′ is an integer of 1 to 9.
- These ⁇ 1 and ⁇ 1 ′ can change according to the valence of X 3 .
- the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 3 .
- X 3 is a 10-valent organic group
- the sum of ⁇ 1 and ⁇ 1 ′ is 10, for example, ⁇ 1 is 9 and ⁇ 1 ′ is 1, ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1 'Can be nine.
- X 3 is a divalent organic group
- ⁇ 1 and ⁇ 1 ′ are 1.
- X 3 is a single bond
- ⁇ 1 and ⁇ ′ 1 are 1.
- the above X 3 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 3 is a divalent to tetravalent organic group
- ⁇ 1 is 1 to 3
- ⁇ 1 ′ is 1.
- X 3 is a divalent organic group
- ⁇ 1 is 1 and ⁇ 1 ′ is 1.
- n1 ' is as defined in (A1).
- ⁇ 1 is an integer of 1 to 9
- ⁇ 1 ′ is an integer of 1 to 9.
- These ⁇ 1 and ⁇ 1 ′ may change according to the valence of X 5 .
- the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 5 .
- X 5 is a 10-valent organic group
- the sum of ⁇ 1 and ⁇ 1 ′ is 10, for example, ⁇ 1 is 9 and ⁇ 1 ′ is 1, ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1 'Can be nine.
- X 5 is a divalent organic group
- ⁇ 1 and ⁇ 1 ′ are 1.
- X 5 is a single bond
- ⁇ 1 and ⁇ ′ 1 are 1.
- the above X 5 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 5 is a divalent to tetravalent organic group
- ⁇ 1 is 1 to 3 and ⁇ 1 ′ is 1.
- X 5 is a divalent organic group
- ⁇ 1 is 1 and ⁇ 1 ′ is 1.
- ⁇ 1 is an integer of 1 to 9
- ⁇ 1 ′ is an integer of 1 to 9.
- These ⁇ 1 and ⁇ 1 ′ can change according to the valence of X 7 .
- the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 7 .
- X 7 is a 10-valent organic group
- the sum of ⁇ 1 and ⁇ 1 ′ is 10, for example, ⁇ 1 is 9 and ⁇ 1 ′ is 1, ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1 'Can be nine.
- X 7 is a divalent organic group
- ⁇ 1 and ⁇ 1 ′ are 1.
- X 7 is a single bond
- ⁇ 1 and ⁇ ′ 1 are 1.
- the above-mentioned X 7 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 7 is a divalent to tetravalent organic group, ⁇ 1 is 1 to 3 and ⁇ 1 ′ is 1.
- X 7 is a divalent organic group, ⁇ 1 is 1 and ⁇ 1 ′ is 1.
- the compound represented by Formula (A1), (B1), (C1) or (D1) is a compound represented by Formula (A1), (C1) or (D1) preferable.
- the adhesion to the substrate can be improved by using such a silane compound.
- a compound represented by the formulas (A), (B), (C) and (D) (hereinafter also referred to as "component (1)"), Formulas (A1), (B1), (B1), (B1), (B1), (B1), (B1), (C1), and (D1)
- the compound represented by C1) and (D1) is 0.1 mol% or more and 35 mol% or less.
- the lower limit of the content of the compounds represented by formulas (A1), (B1), (C1) and (D1) relative to the total of components (1) and (2) is preferably 0.1 mol%, more preferably It may preferably be 0.2 mol%, more preferably 0.5 mol%, even more preferably 1 mol%, particularly preferably 2 mol%, especially 5 mol%.
- the upper limit of the content of the compounds represented by formulas (A1), (B1), (C1), and (D1) to the total of components (1) and (2) is preferably 35 mol%, more preferably It may be 30 mole%, more preferably 20 mole%, even more preferably 15 mole% or 10 mole%.
- the compound represented by the formulas (A1), (B1), (C1) and (D1) relative to the total of the components (1) and (2) is preferably 0.1 mol% or more and 30 mol% or less, more preferably It is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%, still more preferably 0.5 to 10 mol%, particularly preferably 1 to 10 mol%. It is the mole% or less, for example, 2 mole% or more and 10 mole% or less, or 5 mole% or more and 10 mole% or less.
- the curable composition of the present invention can contribute to the formation of a cured product having good friction durability.
- the combination of the component (1) and the component (2) is preferably a combination of a compound represented by the formula (A) and a compound represented by the formula (A1), a table of the formula (B) Of the compound represented by the formula (B1), the combination of the compound represented by the formula (C) and the compound represented by the formula (C1), the compound represented by the formula (D) It is a combination of compounds represented by D1).
- the compounds represented by the formula (A) and the formula (A1) are preferably t is an integer of 2 or more, more preferably an integer of 2 to 10, and still more preferably an integer of 2 to 6.
- t is an integer of 2 or more, more preferably an integer of 2 to 10, and still more preferably an integer of 2 to 6.
- the compounds represented by the formula (C) and the formula (C1) preferably have k1 of 2 or 3, more preferably 3.
- the compounds represented by formula (C) is terminated, -Si- (Z 3 -SiR 72 3 ) 2, -Si- (Z 3 -SiR 72 "3) 2, -Si- (Z It has a structure represented by 3 -SiR 72 3 ) 3 or -Si- (Z 3 -SiR 72 ′ ′ 3 ) 3 , and more preferably —Si— (Z 3 —SiR 72 3 ) 3 or —Si— (Z 3 -SiR 72 "3) has a structure represented by 3; compound of formula (C1) is terminated, -Si- (Z 3 -SiR 72 3 ) 2, or, -Si - (Z 3 -SiR 72 3) it has a structure represented by 3, more preferably by a -Si- (Z 3 -SiR 72 3) having a structure represented by the 3-terminal such structures.
- the group represented by -Si- (Z 3 -SiR 72 3 ) 2 or -Si- (Z 3 -SiR 72 ′ ′ 3 ) 2 is specifically In -Si-R a 2 R b l1 R c m1, a group R a is represented by -Z 3 -SiR 72 3, the sum is 1 l1 and m1, In —Si—R a ′ ′ 2 R b ′ ′ 1 1 R c ′ ′ m 1 , R a ′ ′ is a group represented by —Z 3 —SiR 72 ′ ′ 3 and the total of l 1 and m 1 is 1; In -Si-R 71 2 R 72 q1 R 73 r1, a group R 71 is represented by -Z 3 -SiR 72 3, the
- the compounds represented by Formula (D) and Formula (D1) preferably have 12 of 2 or 3, more preferably 3.
- the compounds represented by the formula (D) is terminated, -C- (Y-SiR 85 3 ) 2, -C- to (Y-SiR 85 "3) 2 ( specifically, -C - (Y-SiR 85 3) 2 R 83, -C- (Y-SiR 85 "3) 2 R 83), - C- (Y-SiR 85) 3 or -C- (Y-SiR 85," )
- It has three structures, more preferably -C- (Y-SiR 85 ) 3 or -C- (Y-SiR 85 ′ ′ ) 3 structure;
- the compound represented by the formula (D1) has a terminal, -C- (Y-SiR 85 3 ) 2 (specifically, -C- (Y-SiR 85 3 ) 2 R 83 ), or -C- (Y-SiR 85 ) 3 structure, more preferably Has a —C— (Y—SiR 85 ) 3 structure.
- the curable composition of the present invention may further contain other components.
- the other components are not particularly limited, and for example, (non-reactive) fluoropolyether compounds which can be understood as fluorine-containing oils, preferably perfluoro (poly) ether compounds (hereinafter referred to as “fluorine-containing compounds”) Oil), stabilizer (dehydrating agent, molecular sieve, magnesium sulfate or methyl orthoformate), viscosity modifier, filler, fluorescent agent, storage stabilizer, filler, coloring agent, heat resistance improver, cold resistance It may contain an improver, a rust inhibitor, an adhesion improver, a liquid reinforcing agent and the like.
- R f 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms
- R f 6 represents ,
- a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom
- R f 5 and R f 6 is more preferably each independently a C 1-3 perfluoroalkyl group.
- a ′, b ′, c ′ and d ′ each represent the number of repeating units of four types of perfluoro (poly) ethers constituting the main skeleton of the polymer, and are each independently an integer of 0 or more and 300 or less;
- the sum of a ′, b ′, c ′ and d ′ is at least 1, preferably 1 to 300, more preferably 20 to 300.
- the order in which each repeating unit enclosed in parentheses with a subscript a ', b', c 'or d' is given is arbitrary in the formula.
- - (OC 4 F 8) - is, - (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)) -, - (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 )) —, which may be any of - (OCF 2 CF 2 CF 2 CF 2) - a.
- - (OC 3 F 6) - is, - (OCF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2) - and - (OCF 2 CF (CF 3 )) - be any of Well, preferably-(OCF 2 CF 2 CF 2 )-.
- -(OC 2 F 4 )- may be either-(OCF 2 CF 2 )-or-(OCF (CF 3 ))-, but is preferably-(OCF 2 CF 2 )-.
- Rf 5 and Rf 6 are as described above; in formula (IIIa), b ′ ′ is an integer of 1 or more and 100 or less; in formula (IIIb), a ′ ′ and b ′ ′ are Each is independently an integer of 1 or more and 30 or less, and c ′ ′ and d ′ ′ are each independently an integer of 1 or more and 300 or less.
- the order in which each repeating unit enclosed in parentheses with the subscripts a ′ ′, b ′ ′, c ′ ′ and d ′ ′ is given is arbitrary in the formula.
- the fluorine-containing oil may have a number average molecular weight of 1,000 to 30,000.
- the number average molecular weight of the compound represented by the formula (IIIa) is preferably 2,000 to 8,000.
- the number average molecular weight of the compound represented by formula (IIIb) is 3,000 to 8,000.
- the number average molecular weight of the compound represented by formula (IIIb) is 8,000 to 30,000.
- the fluorine-containing oil is, for example, 0 to 500 parts by mass, preferably 0 to 500 parts by mass with respect to 100 parts by mass of the fluorine-containing silane compound (more specifically, PFPE-containing silane compound (A)). It may be contained in 100 parts by mass, more preferably 1 to 50 parts by mass, and even more preferably 1 to 5 parts by mass.
- the fluorine-containing oil may be a compound represented by the general formula Rf′-F (wherein Rf ′ is a C 5-16 perfluoroalkyl group).
- Rf ′ is a C 5-16 perfluoroalkyl group
- a chloro trifluoro ethylene oligomer may be sufficient.
- the compound represented by Rf′-F and the chlorotrifluoroethylene oligomer are preferable in that high affinity is obtained with the above perfluoro (poly) ether group-containing silane compound in which Rf is a C 1-16 perfluoroalkyl group. .
- the curable composition of the present invention can form a softer cured product.
- the average molecular weight of the fluorine-containing oil is made larger than the average molecular weight of the fluorine-containing silane compound (eg, a compound represented by the formula (A), (B), (C) or (D)) May be By setting it as such an average molecular weight, more superior friction durability and surface slip property can be obtained in the hardened
- the fluorine-containing silane compound eg, a compound represented by the formula (A), (B), (C) or (D)
- the average molecular weight of the fluorine-containing oil is made smaller than the average molecular weight of the fluorine-containing silane compound (for example, the compound represented by the formula (A), (B), (C) or (D)) May be By setting it as such an average molecular weight, the curable composition of this invention is high friction durability and high surface slip, suppressing the fall of transparency of the hardened
- Examples of the above-mentioned storage stabilizer include methyltrimethoxysilane, methyltripropenoxysilane, vinyltributanoxylsilane, methyltriacetoxysilane and the like.
- filler examples include fibrous fillers such as asbestos, glass fibers and organic fibers.
- Examples of the colorant include pigments and dyes.
- heat resistance improver examples include bengara and cerium oxide.
- ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldiethoxy Silane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane Silane etc. can be mentioned.
- liquid reinforcing agents mention may be made of reticulated polysiloxane consisting triorganosiloxy units and SiO 2 units.
- An adhesion promoter such as carboxylic acid anhydride or pyromellitic acid tetraallyl ester can be further added to the curable composition of the present invention.
- curable composition depending on the application, it may be configured as a so-called one-component type, or may be configured as a two-component type, and both may be mixed at the time of use.
- the cured product of the curable composition of the present invention can be used, for example, for potting materials, sealing materials and the like.
- the cured product of the curable composition of the present invention is, for example, filled in the air gap of the electronic member (for example, the bonded portion between the housing and the printed board, or the gap between the resin molded metal terminal portion and the mold resin). Then, it can be used by drying.
- a cured product for example, a potting material, a sealing material
- Is in order to remove oil on the wall of the air gap prior to the treatment with the curable composition of the present invention, Is preferably washed with acetone, hydrofluoroether or the like and then dried.
- the abrasion resistance of the cured product can be further improved by pre-treatment with UV ozone, oxygen plasma or the like.
- the adhesiveness of the potting material formed from the curable composition is improved by applying primer treatment to the walls of the voids, etc., if necessary. Wear resistance can be further improved.
- the primer treatment may be carried out according to a conventional method under the same conditions as the primer treatment in the case of using a silane coupling agent.
- the temperature at the time of treatment is not particularly limited, and usually, treatment may be carried out at room temperature.
- the treatment time is also not particularly limited, but may be, for example, 5 minutes to 1 hour.
- the curable composition can cure at room temperature.
- Such curable compositions are particularly useful as compositions for forming potting materials.
- the composition when using the curable composition of the present invention, may be further diluted with a solvent depending on its use and purpose.
- a solvent used for dilution the agent for fluorine type illustrated above can be used.
- it may be used by dissolving it in a desired concentration in 1,3-bis (trifluoromethyl) benzene, Fluorinert (manufactured by 3M), perfluorobutyl methyl ether, perfluorobutyl ethyl ether or the like as a solvent.
- the curable composition of the present invention can form a cured product having good adhesion to metal or plastic substrates, it is particularly useful as an adhesive for use in the vicinity of electric and electronic parts and in automotive parts. possible. Since the curable composition of the present invention has a good elastic modulus especially at low temperatures, it can be used particularly in cold regions (for example, -50.degree. C. or less) such as automobile members (for example, sealing materials, specifically, gaskets). It can be usefully used in usable automobile parts.
- the cured product of the curable composition of the present invention is good in chemical resistance, acid resistance and base resistance.
- Such a cured product of the curable composition of the present invention can also be used in a chemical plant, a semiconductor manufacturing apparatus, and the like.
- the cured product of the curable composition of the present invention may have good transparency.
- Such a cured product can be particularly used in members required to be transparent, for example, optical materials such as lenses, display materials, and illumination materials.
- the present invention will be more specifically described through the following examples, but the present invention is not limited to these examples.
- the existing order of the repeating unit which comprises perfluoropolyether is arbitrary.
- Example 1-1 100 parts by weight of Compound 1 as a fluorine-containing silane compound, 5 parts by weight of tetraethoxysilane as a crosslinking agent, 0.1 parts by weight of teloraisopropoxytitanium as a curing catalyst, and weighed in a glass container for mixing The mixture was stirred using to prepare a curable composition.
- Example 1-2 A curable composition was obtained in the same manner as in Example 1-1 except that the addition amount of the catalyst was changed to the amount described in Table 1.
- Example 1-1 Example 1-1 was repeated except that Compound 2 was used as the fluorine-containing silane compound, Zr (OC 3 H 7 ) 4 was used as the catalyst, and the amount of the catalyst was as shown in Table 1, respectively The composition was obtained.
- Example 1-3 A curable composition was obtained in the same manner as in Example 1-3 except that Zr (OC 4 H 9 ) 4 was used as the catalyst and the amount of the catalyst added was the amount described in Table 1.
- Example 1-4 Curing was conducted in the same manner as in Example 1-3 except that Ti (OC 3 H 7 ) 2 (C 6 H 9 O 3 ) 2 was used as the catalyst and the amount of the catalyst added was the amount described in Table 1. The composition was obtained.
- the haze value of the obtained cured product was measured in accordance with ASTM D1003 using a haze card II manufactured by Toyo Seiki Seisaku-sho, Ltd. The results are shown in Table 1.
- the unit "%" of the addition amount of the crosslinking agent and the catalyst means the ratio (mass%) to the mass of the fluorine-containing silane compound.
- Example 2-1 A curable composition having a solid content concentration of 10% by mass was prepared, containing the following PFPE-containing silane compound, a crosslinking agent, a catalyst, and a solvent.
- solid content concentration means the mass ratio of a PFPE containing silane compound, a crosslinking agent, and a catalyst with respect to 100 mass parts of curable compositions below.
- Crosslinking agent tetraethoxysilane (TEOS) (10 parts by mass with respect to 100 parts by mass of the PFPE-containing silane compound)
- Catalyst Tetraisopropyl titanate (0.09 parts by mass with respect to 100 parts by mass of the PFPE-containing silane compound)
- Solvent Novec HFE 7200
- Example 2-2 to 2-4 A curable composition was prepared in the same manner as in Example 2-1 except that the solid content concentration was changed to the values described in Table 2.
- the thickness of the obtained cured product was measured using a laser microscope (model number: VK9710, manufactured by Keyence Corporation). The results are shown in Table 2.
- film thickness indicates the minimum value and the maximum value of the measured thickness.
- uniform indicates a state in which a continuous film is formed without a non-coated area such as a pinhole. Specifically, the image obtained from the laser microscope was visually confirmed, and it was determined that the portion where the glass surface was facing out had pinholes.
- Comparative example 2-1 A composition having a solid content concentration of 80% by mass was prepared, containing a compound having the following PFPE, and a solvent.
- the curable composition of the present invention was able to form a continuous and uniform film.
- the present invention can be suitably used to form a fluorine-containing sealing material for filling a void (for example, a void of a display end face) between electronic members such as a display or a printed circuit board in an electronic device or the like.
- a void for example, a void of a display end face
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Abstract
Description
水酸基および加水分解可能な基からなる群より選ばれる少なくとも1の基と結合したSi原子を2以上有する、含フッ素シラン化合物、
Si原子と結合した-O-Rg3を少なくとも2有する有機ケイ素化合物
(式中、Rg3は、各出現においてそれぞれ独立して、水素原子または1価の有機基である)、および
M(-O-Rh)ηで表される金属系触媒、
を有する、硬化性組成物
(式中:
Mは、金属原子を表し;
Rhは、各出現においてそれぞれ独立して、炭素原子数1~3の炭化水素基であり;
ηは、Mの配位数である)
が提供される。
水酸基および加水分解可能な基からなる群より選ばれる少なくとも1の基と結合したSi原子を2以上有する、含フッ素シラン化合物(以下において、「含フッ素シラン化合物
」と称することがある)、
Si原子と結合した-O-Rg3を少なくとも2有する有機ケイ素化合物
(式中、Rg3は、各出現においてそれぞれ独立して、水素原子または1価の有機基である)(以下において、「架橋剤」と称することがある)、および
M(-O-Rh)ηで表される金属系触媒、
を有する。式中、Mは、金属原子を表し、Rhは、各出現においてそれぞれ独立して、炭素原子数1~3の炭化水素基であり、ηは、Mの配位数である。
上記含フッ素シラン化合物は、撥水性、耐ケミカル性を与えるフッ素含有部と他の物質への結合能を与えるシラン部とを有するものであれば特に限定されない。上記含フッ素シラン化合物は、炭素原子に結合した水素原子の少なくとも1がフッ素原子に置換された化合物をいう。
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3X10 6)d-(OC2F4)e-(OCF2)f-
で表される基である。式中、a、b、c、d、eおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1である。好ましくは、a、b、c、d、eおよびfは、それぞれ独立して、0以上100以下の整数である。好ましくは、a、b、c、d、eおよびfの和は5以上であり、より好ましくは10以上である。好ましくは、a、b、c、d、eおよびfの和は200以下であり、より好ましくは100以下であり、例えば10以上200以下であり、より具体的には10以上100以下である。また、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、好ましくは水素原子またはフッ素原子であり、より好ましくはフッ素原子である。
また、e/f比が上記の範囲にある硬化性組成物は、その硬化物の1%分解温度が比較的高い温度であり得る。即ち、このような硬化性組成物は、広い温度範囲で使用可能な硬化物の形成に寄与し得る。本明細書において、「1%分解温度」とは、硬化物全体に対して、該硬化物の1質量%が分解する温度を意味する。1%分解温度は、熱重量・示差熱(TG/DTA)によって測定された値を意味し、具体的には、酸素雰囲気下で、昇温レートを10℃/分とし、25℃~600℃の範囲で測定する。上記TG/DTAとしては、例えば、SHIMADZU社製DTG-60を挙げることができる。
-(R31)p’-(Xa)q’-
[式中:
R31は、単結合、-(CH2)s’-またはo-、m-もしくはp-フェニレン基を表し、好ましくは-(CH2)s’-であり、
s’は、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数、さらにより好ましくは1または2であり、
Xaは、-(Xb)l’-を表し、
Xbは、各出現においてそれぞれ独立して、-O-、-S-、o-、m-もしくはp-フェニレン基、-C(O)O-、-Si(R33)2-、-(Si(R33)2O)m’-Si(R33)2-、-CONR34-、-O-CONR34-、-NR34-および-(CH2)n’-からなる群から選択される基を表し、
R33は、各出現においてそれぞれ独立して、フェニル基、C1-6アルキル基またはC1-6アルコキシ基を表し、好ましくはフェニル基またはC1-6アルキル基であり、より好ましくはメチル基であり、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表し、
m’は、各出現において、それぞれ独立して、1~100の整数、好ましくは1~20の整数であり、
n’は、各出現において、それぞれ独立して、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数であり、
l’は、1~10の整数、好ましくは1~5の整数、より好ましくは1~3の整数であり、
p’は、0または1であり、
q’は、0または1であり、
ここに、p’およびq’の少なくとも一方は1であり、p’またはq’を付して括弧でくくられた各繰り返し単位の存在順序は任意である]
で表される2価の基が挙げられる。ここに、R31およびXa(典型的にはR31およびXaの水素原子)は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよい。
単結合、
C1-20アルキレン基、
-R31-Xc-R32-、または
-Xd-R32-
[式中、R31およびR32は、上記と同意義である。]
であり得る。なお、アルキレン基とは、-(CδH2δ)-構造を有する基であり、置換または非置換であってよく、直鎖状または分枝鎖状であってもよい。
単結合、
C1-20アルキレン基、
-(CH2)s’-Xc-、
-(CH2)s’-Xc-(CH2)t’-
-Xd-、または
-Xd-(CH2)t’-
[式中、s’およびt’は、上記と同意義である。]
である。
-Xf-、
-Xf-C1-20アルキレン基、
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
である。式中、s’およびt’は、上記と同意義である。
上記式中、Xfは、炭素原子数1~6、好ましくは炭素原子数1~4、より好ましくは炭素原子数1~2のアルキレン基、例えばメチレン基である。Xf中の水素原子は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよく、好ましくは置換されている。Xfは、直鎖状または分枝鎖状であってもよく、好ましくは直鎖状である。
-O-、
-S-、
-C(O)O-、
-CONR34-、
-O-CONR34-、
-Si(R33)2-、
-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-Si(R33)2-O-Si(R33)2-CH2CH2-Si(R33)2-O-Si(R33)2-、
-O-(CH2)u’-Si(OCH3)2OSi(OCH3)2-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、R33、R34およびm’は、上記と同意義であり、
u’は1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]を表す。Xcは、好ましくは-O-である。
-S-、
-C(O)O-、
-CONR34-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、各記号は、上記と同意義である。]
を表す。
-Xf-、
-Xf-C1-20アルキレン基、
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
[式中、Xf、s’およびt’は、上記と同意義である。]
であり、
Xcが、-O-、または-CONR34-、
Xdが、-CONR34-、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表す。]
で表される基である。
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
[式中、Xf、s’およびt’は、上記と同意義である。]
であり、
Xcが、-CONR34-、
Xdが、-CONR34-、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表す。]
で表される基である。
単結合、
C1-20アルキレン基、
-(CH2)s’-Xc-(CH2)t’-、または
-Xd-(CH2)t’-
[式中、各記号は、上記と同意義である。]
であり得る。
単結合、
C1-20アルキレン基、
-(CH2)s’-O-(CH2)t’-、
-(CH2)s’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、
-(CH2)s’-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、または
-(CH2)s’-O-(CH2)t’-Si(R33)2 -(CH2)u’-Si(R33)2-(CvH2v)-
[式中、R33、m’、s’、t’およびu’は、上記と同意義であり、vは1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]
である。
Dは、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、および
から選択される基であり、
Eは、-(CH2)ne-(neは2~6の整数)であり、
Dは、分子主鎖のPFPEに結合し、Eは、PFPEと反対の基に結合する。]
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、または
-OCFHCF2-、
であることが好ましい。
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
である。
単結合、
-Xf-、
炭素原子数1~6、好ましくは炭素原子数1~3のアルキレン基、
-Xf-C1-6アルキレン基、好ましくは-Xf-C1-3アルキレン基、より好ましくは
-Xf-C1-2アルキレン基、
-C6H4-R52’-、
-CONR4’-R52’-、
-CONR4’-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-CO-R52’-、
-CO-C6H4-R52’-、
-SO2NR4’-R52’-、
-SO2NR4’-C6H4-R52’-、
-SO2-R52’-、
-SO2-C6H4-R52’-、
-R51’-C6H4-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-R51’-CO-、
-R51’-CO-C6H4-、
-R51’-SO2NR4’-、
-R51’-SO2NR4’-C6H4-、
-R51’-SO2-、
-R51’-SO2-C6H4-、
-C6H4-、
-CONR4’-、
-CONR4’-C6H4-、
-Xf-CONR4’-、
-Xf-CONR4’-C6H4-、
-CO-、
-CO-C6H4-、
-SO2NR4’-、
-SO2NR4’-C6H4-、
-SO2-、または
-SO2-C6H4-
(式中、R51’およびR52’は、それぞれ独立して、炭素原子数1~6、好ましくは炭素原子数1~3の直鎖のアルキレン基である。上記したように、上記アルキレン基は、置換または非置換であり、上記アルキレン基の置換基としては、例えばハロゲン原子、好ましくはフッ素原子を挙げることができる。
R4’は、水素原子またはメチル基である。)
であり得る。
-Xf-、
炭素原子数1~6、好ましくは炭素原子数1~3のアルキレン基、
-Xf-C1-6アルキレン基、好ましくは-Xf-C1-3アルキレン基、より好ましくは
-Xf-C1-2アルキレン基、
-CONR4’-R52’-、
-CONR4’-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-CONR4’-、
-CONR4’-C6H4-、
-Xf-CONR4’-、
-Xf-CONR4’-C6H4-、
-R51’-CONR4’-、または
-R51’-CONR4’-C6H4-、
であり得る。式中、Xf、R4’、R51’およびR52’は、それぞれ上記と同意義である。
-CONR4’-R52’-、
-CONR4’-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-CONR4’-、
-CONR4’-C6H4-、
-Xf-CONR4’-、または
-Xf-CONR4’-C6H4-、
であり得る。
単結合、
炭素原子数1~6のパーフルオロアルキレン基(例えば、-CF2-、-(CF2)2-等)、
炭素原子数1~6のアルキレン基、
-CF2-C1-6アルキレン基、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CF2-CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CON(CH3)-、
-CON(CH3)-CH2-、
-CON(CH3)-(CH2)2-、
-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-CONH-C6H4-、
-CON(CH3)-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CON(CH3)-C6H4-、
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-C6H4-、
-CO-、
-CO-C6H4-、
-C6H4-、
-SO2NH-、
-SO2NH-CH2-、
-SO2NH-(CH2)2-、
-SO2NH-(CH2)3-、
-SO2NH-C6H4-、
-SO2N(CH3)-、
-SO2N(CH3)-CH2-、
-SO2N(CH3)-(CH2)2-、
-SO2N(CH3)-(CH2)3-、
-SO2N(CH3)-C6H4-、
-SO2-、
-SO2-CH2-、
-SO2-(CH2)2-、
-SO2-(CH2)3-、または
-SO2-C6H4-
などが挙げられる。
炭素原子数1~6のアルキレン基、
炭素原子数1~6のパーフルオロアルキレン基(例えば、-CF2-、-(CF2)2-等)、
-CF2-C1-6アルキレン基、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CON(CH3)-、
-CON(CH3)-CH2-、
-CON(CH3)-(CH2)2-、
-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-CONH-C6H4-、
-CON(CH3)-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CON(CH3)-C6H4-
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-C6H4-、
などが挙げられる。
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CON(CH3)-、
-CON(CH3)-CH2-、
-CON(CH3)-(CH2)2-、
-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-CONH-C6H4-、
-CON(CH3)-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CON(CH3)-C6H4-
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、または
-CF2-CON(CH3)-C6H4-、
などが挙げられる。
R41は、それぞれ独立して、水素原子、フェニル基、炭素原子数1~6のアルキル基、またはC1-6アルコキシ基、好ましくはメチル基であり;
各X1基において、Tのうち任意のいくつかは、分子主鎖のPFPEに結合する以下の基:
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、または
であり、別のTのいくつかは、分子主鎖のPFPEと反対の基に結合する-(CH2)n”-(n”は2~6の整数)であり、存在する場合、残りのTは、それぞれ独立して、メチル基、フェニル基、C1-6アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。なお、上記態様においても、X1として記載している基は、左側がPFPEで表される基に、右側がα1を付して括弧でくくられた基に、それぞれ結合する。
PFPEは、各出現においてそれぞれ独立して、式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f-
(式中、a、b、c、d、eおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。)
で表される基であり;
R13は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R14は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基を表し;
R11は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し;
R12は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
R11”、R12”、R13”、R14”は、それぞれ、R11、R12、R13、R14と同意義であり;
n1は、1~3の整数であり、好ましくは3であり;
X1は、各出現においてそれぞれ独立して、-O-CFR20-(CF2)e’-であり;
R20は、各出現においてそれぞれ独立して、フッ素原子または低級フルオロアルキル基であり;
e’は、各出現においてそれぞれ独立して、0または1であり;
X2は、-(CH2)u-であり;
uは、各出現においてそれぞれ独立して、0~2の整数であり;
tは、各出現においてそれぞれ独立して、2~10の整数である。]
で表される化合物である。
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
である。
PFPEは、各出現においてそれぞれ独立して、式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f-
(式中、a、b、c、d、eおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。)
で表される基であり;
R13は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R14は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基を表し;
R13”、R14”は、それぞれ、R13、R14と同意義であり;
n1は、1~3の整数であり、好ましくは3であり;
X3は、-CH2O(CH2)2-、-CH2O(CH2)3-または-CH2O(CH2)6-である。]
で表される化合物である。
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
である。
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
である。
上記架橋剤は、含フッ素シラン化合物(例えば、PFPE含有シラン化合物(A)、具体的には、PFPE含有シラン化合物(A)のSi原子に結合した水酸基または加水分解可能な基を有するシラン部分)と架橋反応(縮合反応)を行い得る部分を有する化合物であれば特に限定されない。含フッ素シラン化合物(例えば、PFPE含有シラン化合物(A))と架橋剤とを含むことにより、本発明の硬化性組成物から得られる硬化物の物性(例えば、引張強度、弾性率)は良好になり得る。
・Rg3が水素原子である有機化合物、即ち、1分子中にシラノール基を少なくとも2有する有機ケイ素化合物、
・後述する式(E3)~(E5)で表される有機ケイ素化合物、
等を挙げることができる。
上記有機ケイ素化合物において、上記シラノール基は、分子主鎖の両末端に存在することが好ましい。ここで、分子主鎖とは、該有機ケイ素化合物の分子中で相対的に最も長い結合鎖を表す。
である。
Rf1-Rg5-
上記式中、Rf1は1価のフッ素化ポリエーテル基である。上記Rf1としては、上記PFPEのCF2末端にCF3O-、CF3CF2O-、CF3CF2CF2O-、(CF3)2CFO-、またはCF3CF2CF2CF2O-等が結合された構造のものが例示される。
炭素原子数1~3のアルキレン基、
CH2CH2-NH-CH2CH2CH2、または
CH2-O-CH2CH2CH2である。
上記金属系触媒は、M(-O-Rh)ηで表される。式中、Mは、金属原子を表し、Rhは、各出現においてそれぞれ独立して、炭素原子数1~3の炭化水素基であり、ηは、Mの配位数である。上記のような金属系触媒を用いると、含フッ素シラン化合物(例えば、PFPE含有シラン化合物(A))と架橋剤との縮合反応が促進される。上記のような金属系触媒は、硬化性組成物に溶解または分散しやすく、均一な反応の促進に寄与し得る。上記のような金属系触媒を含む本発明の硬化性組成物は、異物が少なく、透明性の高い硬化性組成物の硬化物の形成に寄与し得る。
本発明の硬化性組成物は、溶剤を含んでいてもよい。この場合、硬化性組成物の用途、目的に応じて適当な溶剤(例えばフッ素原子含有溶剤)に所望の濃度に溶解して使用し得る。上記溶剤の濃度は、例えば、硬化性組成物100質量部に対して、80質量部以下であってもよく、50質量部以下であってもよく、40質量部以下であってもよく、30質量部以下であってもよく、20質量部以下であってもよい。
パーフルオロヘキサン、CF3CF2CHCl2、CF3CH2CF2CH3、CF3CHFCHFC2F5、1,1,1,2,2,3,3,4,4,5,5,6,6-トリデカフルオロオクタン、1,1,2,2,3,3,4-ヘプタフルオロシクロペンタン((ゼオローラH(商品名)等)、C4F9OCH3、C4F9OC2H5、CF3CH2OCF2CHF2、C6F13CH=CH2、キシレンヘキサフルオリド、パーフルオロベンゼン、メチルペンタデカフルオロヘプチルケトン、トリフルオロエタノール、ペンタフルオロプロパノール、ヘキサフルオロイソプロパノール、HCF2CF2CH2OH、メチルトリフルオロメタンスルホネート、トリフルオロ酢酸およびCF3O(CF2CF2O)m1(CF2O)n1CF2CF3[式中、m1およびn1は、それぞれ独立して0以上1000以下の整数であり、m1またはn1を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、但しm1およびn1の和は1以上である。]、1,1-ジクロロ-2,3,3,3-テトラフルオロ-1-プロペン、1,2-ジクロロ-1,3,3,3-テトラフルオロ-1-プロペン、1,2-ジクロロ-3,3,3-トリフルオロ-1-プロペン、1,1-ジクロロ-3,3,3-トリフルオロ-1-プロペン、1,1,2-トリクロロ―3,3,3-トリフルオロ-1-プロペン、1,1,1,4,4,4-ヘキサフルオロ-2-ブテン、エチルパーフルオロブチルエーテル、およびメチルパーフルオロブチルエーテルからなる群から選択されるフッ素原子含有溶剤等が挙げられる。これらの溶剤は、単独で、または、2種以上の混合物として用いることができる。
上記-Si-(Z3-SiR72 3)2または-Si-(Z3-SiR72” 3)2で表される基は、具体的には、
-Si-Ra 2Rb l1Rc m1において、Raが-Z3-SiR72 3で表される基であり、l1およびm1の合計が1である、
-Si-Ra” 2Rb” l1Rc” m1において、Ra”が-Z3-SiR72” 3で表される基であり、l1およびm1の合計が1である、
-Si-R71 2R72 q1R73 r1において、R71が-Z3-SiR72 3で表される基であり、q1およびr1の合計が1である、または
-Si-R71 2R72” q1R73 r1において、R71が-Z3-SiR72 3で表される基であり、q1およびr1の合計が1である、を挙げることができる。
本発明の硬化性組成物は、さらに、他の成分を含んでいてもよい。他の成分としては、特に限定されるものではないが、例えば、含フッ素オイルとして理解され得る(非反応性の)フルオロポリエーテル化合物、好ましくはパーフルオロ(ポリ)エーテル化合物(以下、「含フッ素オイル」と言う)、安定化材(脱水剤、モレキュラーシーブ、硫酸マグネシウムまたはオルソギ酸メチル)、粘度調節剤、フィラー、蛍光剤、保存安定剤、充填剤、着色剤、耐熱性向上剤、耐寒性向上剤、防錆剤、接着性向上剤、液状補強剤等を含んでいてもよい。
Rf5-(OC4F8)a’-(OC3F6)b’-(OC2F4)c’-(OCF2)d’-Rf6 ・・・(III)
a’、b’、c’およびd’は、ポリマーの主骨格を構成するパーフルオロ(ポリ)エーテルの4種の繰り返し単位数をそれぞれ表し、互いに独立して0以上300以下の整数であって、a’、b’、c’およびd’の和は少なくとも1、好ましくは1~300、より好ましくは20~300である。添字a’、b’、c’またはd’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。これら繰り返し単位のうち、-(OC4F8)-は、-(OCF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2)-、-(OCF2CF(CF3)CF2)-、-(OCF2CF2CF(CF3))-、-(OC(CF3)2CF2)-、-(OCF2C(CF3)2)-、-(OCF(CF3)CF(CF3))-、-(OCF(C2F5)CF2)-および-(OCF2CF(C2F5))-のいずれであってもよいが、好ましくは-(OCF2CF2CF2CF2)-である。-(OC3F6)-は、-(OCF2CF2CF2)-、-(OCF(CF3)CF2)-および-(OCF2CF(CF3))-のいずれであってもよく、好ましくは-(OCF2CF2CF2)-である。-(OC2F4)-は、-(OCF2CF2)-および-(OCF(CF3))-のいずれであってもよいが、好ましくは-(OCF2CF2)-である。
Rf5-(OCF2CF2CF2)b’’-Rf6 ・・・(IIIa)
Rf5-(OCF2CF2CF2CF2)a’’-(OCF2CF2CF2)b’’-(OCF2CF2)c’’-(OCF2)d’’-Rf6
・・・(IIIb)
これら式中、Rf5およびRf6は上記の通りであり;式(IIIa)において、b’’は1以上100以下の整数であり;式(IIIb)において、a’’およびb’’は、それぞれ独立して1以上30以下の整数であり、c’’およびd’’はそれぞれ独立して1以上300以下の整数である。添字a’’、b’’、c’’、d’’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。
本発明の硬化性組成物の硬化物は、例えば、ポッティング材、シール材等に使用し得る。本発明の硬化性組成物の硬化物は、例えば、電子部材の空隙(例えば、筐体とプリント基板の張り合わせ部、または樹脂モールドされた金属端子部とモールド樹脂の隙間等)に充填し、充填後、乾燥させることによって使用し得る。
含フッ素シラン化合物
化合物1:(C2H5O)3SiCH2CH2CH2NHCOCF2(OC2F4)e-(OCF2)f-CF2CONHCH2CH2CH2Si(OC2H5)3
(式中、e=48、f=37)
化合物2:(C2H5O)3SiCH2CH2CH2NHCOCF2(OCF2CF(CF3))mOCF2CF2O(CF(CF3)CF2O)n-CF2CONHCH2CH2CH2Si(OC2H5)3
(式中、m+n=54)
架橋剤
テトラエトキシシラン(TEOS)
含フッ素シラン化合物として化合物1を100重量部、架橋剤としてテトラエトキシシランを5重量部、硬化触媒としてテロライソプロパキシチタンを0.1重量部、混合用のガラス容器に秤量し、マグネチックスターラーを用いて撹拌を行い、硬化性組成物を調製した。
触媒の添加量を、表1に記載の量とした以外は、実施例1-1と同様に行い、硬化性組成物を得た。
触媒としてTi(OC4H9)4を用い、触媒の添加量をそれぞれ表1に記載の量とした以外は、実施例1-1と同様に行い、硬化性組成物を得た。
含フッ素シラン化合物として化合物2、触媒としてZr(OC3H7)4を用い、触媒の添加量をそれぞれ表1に記載の量とした以外は、実施例1-1と同様に行い、硬化性組成物を得た。
触媒としてZr(OC4H9)4を用い、触媒の添加量を表1に記載の量とした以外は、実施例1-3と同様に行い、硬化性組成物を得た。
触媒としてTi(OC3H7)2(C6H9O3)2を用い、触媒の添加量を表1に記載の量とした以外は、実施例1-3と同様に行い、硬化性組成物を得た。
実施例および比較例で得られた硬化性組成物を、25℃湿度65%の雰囲気下において24時間静置し、硬化物を得た。
以下のPFPE含有シラン化合物、架橋剤、触媒、および溶剤を含み、固形分濃度が10質量%の硬化性組成物を調製した。なお、以下において固形分濃度とは、硬化性組成物100質量部に対する、PFPE含有シラン化合物、架橋剤および触媒の質量比をいう。
PFPE含有シラン化合物:(C2H5O)3SiCH2CH2CH2NHCOCF2(OC2F4)e-(OCF2)f-CF2CONHCH2CH2CH2Si(OC2H5)3 (式中、e=40、f=58)
架橋剤:テトラエトキシシラン(TEOS)(PFPE含有シラン化合物100質量部に対して、10質量部)
触媒:テトライソプロピルチタネート(PFPE含有シラン化合物100質量部に対して0.09質量部)
溶剤:ノベックHFE7200
固形分濃度を表2に記載の数値に変更した以外は、実施例2-1と同様に行い、硬化性組成物を調製した。
以下のPFPEを有する化合物、および溶剤を含み、固形分濃度が80質量%の組成物を調製した。
PFPEを有する化合物:
CF3(OC3F6)eCF2(CH2CH(Si(OCH3)3))3H
(式中、e=24)
溶剤:ノベックHFE7200
比較例2で得られた組成物から、実施例で得られた組成物と同様の操作によって硬化物を形成した。比較例2の組成物から得られた硬化物は、ゲル状ではなく、形成された膜は均一でなかった。
Claims (10)
- 水酸基および加水分解可能な基からなる群より選ばれる少なくとも1の基と結合したSi原子を2以上有する、含フッ素シラン化合物、
Si原子と結合した-O-Rg3を少なくとも2有する有機ケイ素化合物
(式中、Rg3は、各出現においてそれぞれ独立して、水素原子または1価の有機基である)、および
M(-O-Rh)ηで表される金属系触媒、
を有する、硬化性組成物
(式中:
Mは、金属原子を表し;
Rhは、各出現においてそれぞれ独立して、炭素原子数1~3の炭化水素基であり;
ηは、Mの配位数である)。 - Mが、チタン、ジルコニウム、およびスズからなる群より選ばれる少なくとも1である、請求項1に記載の硬化性組成物。
- Mが、チタン、またはジルコニウムである、請求項1または2に記載の硬化性組成物。
- 金属系触媒が、テトラプロピルチタネート、およびテトラプロピルジルコネートからなる群より選ばれる少なくとも1である、請求項1~3のいずれか1項に記載の硬化性組成物。
- 金属系触媒が、含フッ素シラン化合物100質量部に対して、0.05~5.0質量部含まれる、請求項1~4のいずれか1項に記載の硬化性組成物。
- 含フッ素シラン化合物が、パーフルオロポリエーテル基含有シラン化合物である、請求項1~5のいずれか1項に記載の硬化性組成物。
- 含フッ素シラン化合物が、式(A)、(B)、(C)、または(D):
[式中:
PFPEは、各出現においてそれぞれ独立して、式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3X10 6)d-(OC2F4)e-(OCF2)f-
(式中、a、b、c、d、eおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子である。)
で表される基であり;
R13は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R14は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基を表し;
R11は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し;
R12は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
R11”、R12”、R13”、およびR14”は、それぞれ、R11、R12、R13、およびR14と同意義であり;
n1は、(-SiR13 n1R14 3-n1)単位毎または(-SiR13” n1R14” 3-n1)単位毎に独立して、0~3の整数であり;
ただし、式(A)、および(B)において、各出現においてそれぞれ独立して、R13およびR13”からなる群より選ばれる基が少なくとも2存在し;
X1は、各出現においてそれぞれ独立して、単結合または2~10価の有機基を表し;
X2は、各出現においてそれぞれ独立して、単結合または2価の有機基を表し;
tは、各出現においてそれぞれ独立して、1~10の整数であり;
α1は、各出現においてそれぞれ独立して、1~9の整数であり;
X3は、各出現においてそれぞれ独立して、単結合または2~10価の有機基を表し;
β1は、各出現においてそれぞれ独立して、1~9の整数であり;
X5は、各出現においてそれぞれ独立して、単結合または2~10価の有機基を表し;
γ1は、各出現においてそれぞれ独立して、1~9の整数であり;
Raは、各出現においてそれぞれ独立して、-Z3-SiR71 p1R72 q1R73 r1を表し;
Z3は、各出現においてそれぞれ独立して、酸素原子または2価の有機基を表し;
R71は、各出現においてそれぞれ独立して、Ra’を表し;
Ra’は、Raと同意義であり;
Ra中、Z3基を介して直鎖状に連結されるSiは最大で5個であり;
R72は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R73は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
p1は、各出現においてそれぞれ独立して、0~3の整数であり;
q1は、各出現においてそれぞれ独立して、0~3の整数であり;
r1は、各出現においてそれぞれ独立して、0~3の整数であり;
Ra”は、各出現においてそれぞれ独立して、-Z3-SiR71 p1R72” q1R73 r1を表し;
R72”は、R72と同意義であり;
ただし、(-Z3-SiR71 p1R72 q1R73 r1)毎、または(-Z3-SiR71 p1R72” q1R73 r1)毎において、p1、q1およびr1の和は3であり、式(C)において、少なくとも1つのq1が1~3の整数であり;
Rbは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
Rcは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
Rb”、およびRc”は、それぞれ、Rb、およびRcと同意義であり;
k1は、各出現においてそれぞれ独立して、0~3の整数であり;
l1は、各出現においてそれぞれ独立して、0~3の整数であり;
m1は、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiRa k1Rb l1Rc m1)毎、または(SiRa” k1Rb” l1Rc” m1)毎において、k1、l1およびm1の和は3であり;
(C)において、Rb、Rb”、R72、およびR72”からなる群より選ばれる基が少なくとも2存在し;
X7は、それぞれ独立して、単結合または2~10価の有機基を表し;
δ1は、それぞれ独立して、1~9の整数であり;
Rdは、各出現においてそれぞれ独立して、-Z4-CR81 p2R82 q2R83 r2を表し;
Z4は、各出現においてそれぞれ独立して、酸素原子または2価の有機基を表し;
R81は、各出現においてそれぞれ独立して、Rd’を表し;
Rd’は、Rdと同意義であり;
Rd中、Z4基を介して直鎖状に連結されるCは最大で5個であり;
R82は、各出現においてそれぞれ独立して、-Y-SiR85 n2R86 3-n2を表し;
Yは、各出現においてそれぞれ独立して、2価の有機基を表し;
R85は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R86は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
R83は、各出現においてそれぞれ独立して、水素原子、水酸基または低級アルキル基を表し;
p2は、各出現においてそれぞれ独立して、0~3の整数であり;
q2は、各出現においてそれぞれ独立して、0~3の整数であり;
r2は、各出現においてそれぞれ独立して、0~3の整数であり;
Rd”は、各出現においてそれぞれ独立して、-Z4-CR81 p2R82” q2R83 r2を表し;
R82”は、-Y-SiR85” n2R86” 3-n2を表し;
ただし、(-Z4-CR81 p2R82 q2R83 r2)毎または(-Z4-CR81 p2R82” q2R83 r2)毎において、p2、q2およびr2の和は3であり;
n2は、(-Y-SiR85 n2R86 3-n2)単位毎または(-Y-SiR85” n2R86” 3-n2)単位毎に独立して、0~3の整数を表し;
R85”、およびR86”は、それぞれ、R85、およびR86と同意義であり;
Reは、各出現においてそれぞれ独立して、-Y-SiR85 n2R86 3-n2を表し;
Re”は、各出現においてそれぞれ独立して、-Y-SiR85” n2R86” 3-n2を表し;
Rfは、各出現においてそれぞれ独立して、水素原子、水酸基または低級アルキル基を表し;
Rf”は、Rfと同意義であり;
k2は、各出現においてそれぞれ独立して、0~3の整数であり;
l2は、各出現においてそれぞれ独立して、0~3の整数であり;
m2は、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(CRd k2Re l2Rf m2)毎または(CRd” k2Re” l2Rf” m2)毎において、k2、l2およびm2の和は3であり、式(D)において、n2が1以上である-Y-SiR85 n2R86 3-n2で表される基およびn2が1以上である-Y-SiR85” n2R86” 3-n2で表される基からなる群より選ばれる基が2以上存在する。]
で表される少なくとも1種のパーフルオロポリエーテル基含有シラン化合物である、請求項1~6のいずれか1項に記載の硬化性組成物。 - X10が、フッ素原子である、請求項7に記載の硬化性組成物。
- 含フッ素シラン化合物において、水酸基および加水分解可能な基からなる群より選ばれる少なくとも1の基と結合したSi原子が、含フッ素シラン化合物の分子主鎖の両末端に存在する、請求項1~8のいずれか1項に記載の硬化性組成物。
- 有機ケイ素化合物が、下記式(E-1)~(E-5)で表される有機ケイ素化合物を含む、請求項1~9のいずれか1項に記載の硬化性組成物。
[式中:
Rg1は、各出現においてそれぞれ独立して、置換または非置換の炭素原子数1~8の1価炭化水素基であり;
Rg2は、各出現においてそれぞれ独立して、置換または非置換の炭素原子数1~20であり;
Rg3は、各出現においてそれぞれ独立して、水素原子または1価の有機基であり;
Rg4は、各出現においてそれぞれ独立して、1価の有機基であり;
Rg6は、Rg8-Rg7-を表し;
Rg7は、各出現においてそれぞれ独立して、単結合、酸素原子または2価の有機基を表し;
Rg8は、各出現においてそれぞれ独立して、アミノ基、エポキシ基、メタクリル基、ビニル基、またはメルカプト基であり;
ε1は、各出現においてそれぞれ独立して、1以上の整数であり;
ε2は、出現においてそれぞれ独立して、2または3であり;
ε3は、各出現においてそれぞれ独立して、2または3であり;
ε4は、2以上の整数であり;
ε5は、1または2であり;
ε6は、0以上の整数である。]
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