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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
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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  • C07—ORGANIC CHEMISTRY
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
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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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  • C08G77/00—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
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
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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
  • C08G77/54—Nitrogen-containing linkages
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • 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
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  • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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• • G—PHYSICS
  • G02—OPTICS
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  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Definitions

• the present disclosure relates to surface treatment agents.
• Patent Document 1 It is known that certain silane compounds can provide excellent water and oil repellency when used for surface treatment of substrates.
• the silane compound described in Patent Document 1 can provide a surface treatment layer with excellent fingerprint wiping properties, but there is a demand for a surface treatment layer with higher functionality.
• An object of the present disclosure is to provide a surface treatment agent capable of forming a surface treatment layer with excellent fingerprint wiping properties.
• R S1 is independently at each occurrence R 1 -R S -R 2 q -; R S2 is —O p —R S —R 2 q —; R S is independently at each occurrence a divalent linear organosiloxane group; R 1 is a hydrocarbon group; R 2 is -SiR 3 2 -; R 3 is independently at each occurrence a hydrocarbon group; p is 0 or 1; each q is independently 0 or 1; RH is independently at each occurrence a monovalent group comprising a Si atom to which is attached a hydroxyl group, a hydrolyzable group, or a monovalent organic group; Two or more Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the RH ; each X A is independently a single bond or a divalent to decavalent organic group; ⁇ is an integer from 1 to
• R S is —(SiR 3 2 —O) a —; R 3 is independently at each occurrence a hydrocarbon group; a is 2 to 1500; The siloxane group-containing silane compound according to [1] above.
• R 3 The siloxane group-containing according to [1] or [2] above, wherein each occurrence of R 3 is independently a C 1-6 alkyl group or aryl group optionally substituted by a halogen atom. silane compound.
• R 4 The siloxane group-containing silane compound according to any one of [1] to [3] above, wherein each occurrence of R 3 is independently a methyl group or a phenyl group.
• R H is represented by the following formula (S1), (S2), (S3), or (S4): [In the formula: R 11 is independently at each occurrence a hydroxyl group or a hydrolyzable group; R 12 is independently at each occurrence a monovalent organic group; n1 is an integer of 0 to 3 independently for each (SiR 11 n1 R 12 3-n1 ) unit; X 11 is independently at each occurrence a single bond or a divalent organic group; R 13 is independently at each occurrence a hydrogen atom or a monovalent organic group; t is independently at each occurrence an integer greater than or equal to 2; R 14 is independently at each occurrence a hydrogen atom, a halogen atom or —X 11 —SiR 11 n1 R 12 3-n1 ; each occurrence of R 15 is independently a single bond, an oxygen
• R g1 and R h1 are independently at each occurrence -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , or -Z 4 -CR d1 k2 R e1 l2 R f1 m2 ;
• Z 4 is independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
• the group represented by the formula (S1) is represented by the following formula (S1-b): [Wherein, R 11 , R 12 , R 13 , X 11 , n1 and t have the same meanings as described in formula (S1) above]
• the siloxane group-containing silane compound according to [6] above, which is a group represented by [8] The siloxane group-containing silane compound according to [6] above, wherein each occurrence of R H is independently a group represented by formula (S2), (S3), or (S4).
• X A is a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 - [In the formula: R 51 is a single bond, —(CH 2 ) s5 — or an o-, m- or p-phenylene group, s5 is an integer from 1 to 20, X 51 is -(X 52 ) l5 -, X 52 is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -CO-, -C(O)O-, -CONR 54 -, -O a group selected from the group consisting of -CONR 54 -, -NR 54 - and -(CH 2 ) n5 -; each occurrence of R 54 is independently a hydrogen atom or a monovalent organic group; n5 is independently at each occurrence an integer from 1 to 20; l5 is an integer from 1 to 10, p
• X A is each independently: [In the formula, each X a is independently a single bond or a divalent organic group. ]
• X 121 to X 124 are each independently H, OH, or —OSi(OR 121 ) 3 (wherein each R 121 is independently an alkyl group having 1 to 4 carbon atoms).
• R 122 is a C 1-6 hydrocarbon chain, x1 is an integer from 0 to 10, y1 is 0 or 1; z1 is an integer from 1 to 10; ]
• the siloxane group-containing silane compound according to [17] above, which is a group represented by [19] A composition containing the siloxane group-containing silane compound according to any one of [1] to [18] above.
• [20] Containing at least one of the siloxane-containing silane compound according to any one of [1] to [18] above and a compound consisting of a condensate obtained by condensation of at least a portion of the siloxane-containing silane compound, Composition.
• R 71 to R 79 are each independently a monovalent organic group having 1 to 10 carbon atoms
• m8 is an integer from 1 to 6
• m9 is an integer from 3 to 8
• n8 is an integer of 0-6.
• composition according to [19] or [20] above comprising a solvent selected from the compounds represented by [22]
• the solvent is hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, or decamethylcyclopentasiloxane. .
• composition according to any one of [19] to [23] above which is a surface treatment agent.
• composition according to [19] or [24] above which is for vacuum deposition.
• composition according to [19] or [24] above which is for wet coating.
• [28] A substrate, and, on the substrate, the siloxane group-containing silane compound according to any one of [1] to [18] above, and the silane compound according to any one of [19] to [26] above. and a layer formed from the composition of [29]
• the article according to [28] above which is an optical member.
• a surface treatment agent capable of forming a surface treatment layer with excellent fingerprint wiping properties is provided.
• monovalent organic group means a monovalent group containing carbon.
• the monovalent organic group is not particularly limited, it may be a hydrocarbon group or a derivative thereof.
• a derivative of a hydrocarbon group is a group having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain.
• organic group when it shows simply as an "organic group”, it means a monovalent organic group.
• the “divalent to decavalent organic group” means a divalent to decavalent group containing carbon.
• Such a divalent to decavalent organic group is not particularly limited, but includes a divalent to decavalent group in which 1 to 9 hydrogen atoms are further eliminated from an organic group.
• the divalent organic group is not particularly limited, but includes a divalent group in which one hydrogen atom is further eliminated from the organic group.
• hydrocarbon group means a group containing carbon and hydrogen from which one hydrogen atom has been removed from a hydrocarbon.
• Such hydrocarbon groups include, but are not limited to, C 1-20 hydrocarbon groups optionally substituted by one or more substituents, such as aliphatic hydrocarbon groups, aromatic A hydrocarbon group etc. are mentioned.
• the above “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated. Hydrocarbon groups may also contain one or more ring structures.
• the substituent of the "hydrocarbon group” is not particularly limited, but 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, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl groups, C 6-10 aryl groups and 5-10 membered heteroaryl groups.
• hydrolyzable group means a group capable of undergoing a hydrolysis reaction, ie, a group capable of being detached from the backbone of a compound by a hydrolysis reaction.
• R S1 is independently at each occurrence R 1 -R S -R 2 q -; R S2 is —O p —R S —R 2 q —; R S is independently at each occurrence a divalent linear organosiloxane group; R 1 is a hydrocarbon group; R 2 is -SiR 3 2 -; R 3 is independently at each occurrence a hydrocarbon group; p is 0 or 1; each q is independently 0 or 1; RH is independently at each occurrence a monovalent group comprising a Si atom to which is attached a hydroxyl group, a hydrolyzable group, or a monovalent organic group; RH has two or more Si atoms to which hydroxyl groups or hydrolyzable groups are bonded; each X A is independently a single bond or a divalent to decavalent organic group; ⁇ is an integer from 1 to 9; ⁇ is an integer from 1 to 9
• each occurrence of R S above is independently a divalent linear organosiloxane group.
• the divalent linear organosiloxane group means an organosiloxane group in which the siloxane main skeleton (—SiR 2 —O—SiR 2 —) is linear, and the R group bonded to the Si atom is linear. It may be chain or branched.
• R S has the formula: —(SiR 3 2 —O) a — [In the formula: R 3 is independently at each occurrence a hydrocarbon group; a is 2 to 1500; ] is a group represented by
• Each occurrence of R 3 above is independently a hydrocarbon group. Such hydrocarbon groups may be optionally substituted.
• R 3 is independently at each occurrence preferably an unsubstituted hydrocarbon group or a hydrocarbon group substituted by a halogen atom.
• halogen atoms are preferably fluorine atoms.
• R 3 is independently preferably a C 1-6 alkyl or aryl group optionally substituted by a halogen atom, more preferably a C 1-6 alkyl or aryl group.
• the C 1-6 alkyl group may be linear or branched, but is preferably linear.
• the C 1-6 alkyl group is preferably a C 1-3 alkyl group, more preferably a methyl group.
• the aryl group is preferably a phenyl group.
• R 3 is independently at each occurrence a C 1-6 alkyl group, preferably a C 1-3 alkyl group, more preferably a methyl group.
• R3 is a phenyl group.
• R 3 is independently at each occurrence a methyl group or a phenyl group, preferably a methyl group.
• a is 2 to 1,500.
• a may preferably be 5 or more, more preferably 10 or more, even more preferably 15 or more, for example 30 or more, or 50 or more.
• a may preferably be 1000 or less, more preferably 500 or less, even more preferably 200 or less, even more preferably 150 or less, such as 100 or less, or 80 or less.
• a can be preferably 5-1000, more preferably 10-500, even more preferably 15-200, still more preferably 15-150.
• R 1 above is a hydrocarbon group and has the same meaning as R 3 above.
• R 1 is preferably a C 1-6 alkyl or aryl group optionally substituted by a halogen atom, more preferably a C 1-6 alkyl or aryl group.
• R 1 is a C 1-6 alkyl group, preferably a C 1-3 alkyl group, more preferably a methyl group.
• R 1 is a phenyl group.
• R 1 is a methyl group or a phenyl group, preferably a methyl group.
• p is 0 or 1 independently at each occurrence. In one aspect, p is zero. In another aspect, p is 1.
• q is 0 or 1 independently at each occurrence. In one aspect, q is zero. In another aspect q is 1.
• p is 0 and q is 1.
• R H above is independently a hydroxyl group , a hydrolyzable group, or a monovalent group containing a Si atom to which a monovalent organic group is bonded. There are two or more Si atoms to which the functional groups are bonded.
• R H is represented by the following formula (S1), (S2), (S3), or (S4): [In the formula: R 11 is independently at each occurrence a hydroxyl group or a hydrolyzable group; R 12 is independently at each occurrence a monovalent organic group; n1 is an integer of 0 to 3 independently for each (SiR 11 n1 R 12 3-n1 ) unit; X 11 is independently at each occurrence a single bond or a divalent organic group; R 13 is independently at each occurrence a hydrogen atom or a monovalent organic group; t is independently at each occurrence an integer greater than or equal to 2; R 14 is independently at each occurrence a hydrogen atom, a halogen atom or —X 11 —SiR 11 n1 R 12 3-n1 ; each occurrence of R 15 is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms; R
• R g1 and R h1 are independently at each occurrence -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , or -Z 4 -CR d1 k2 R e1 l2 R f1 m2 ;
• Z 4 is independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
• Si atoms to which hydroxyl groups or hydrolyzable groups are bonded. ] is a group represented by
• each occurrence of R 11 is independently a hydroxyl group or a hydrolyzable group.
• R 11 is preferably independently at each occurrence a hydrolyzable group.
• R h include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
• an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
• R h is a methyl group, and in another aspect R h is an ethyl group.
• R 12 at each occurrence is independently a monovalent organic group.
• a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
• the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, even more preferably a methyl group.
• n1 is an integer of 0 to 3 independently for each (SiR 11 n1 R 12 3-n1 ) unit.
• formula (S1) there are at least two (SiR 11 n1 R 12 3-n1 ) units in which n1 is 1-3.
• formula (S1) there are at least two Si atoms to which hydroxyl groups or hydrolyzable groups are bonded.
• n1 is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR 11 n1 R 12 3-n1 ) unit.
• X 11 at each occurrence is independently a single bond or a divalent organic group.
• divalent organic groups are preferably —R 28 —O x —R 29 —, wherein R 28 and R 29 are each independently at each occurrence a single bond or a C 1-20 alkylene group. , x is 0 or 1.).
• Such C 1-20 alkylene groups may be straight chain or branched, but are preferably straight chain.
• Such C 1-20 alkylene groups are preferably C 1-10 alkylene groups, more preferably C 1-6 alkylene groups, still more preferably C 1-3 alkylene groups.
• X 11 is independently at each occurrence -C 1-6 alkylene-O-C 1-6 alkylene- or -O-C 1-6 alkylene-.
• each occurrence of X 11 is independently a single bond or a straight-chain C 1-6 alkylene group, preferably a single bond or a straight-chain C 1-3 alkylene group, more preferably a single It is a bond or straight chain C 1-2 alkylene group, more preferably a straight chain C 1-2 alkylene group.
• each occurrence of R 13 is independently a hydrogen atom or a monovalent organic group.
• Such monovalent organic groups are preferably C 1-20 alkyl groups.
• R 13 is independently at each occurrence a hydrogen atom or a linear C 1-6 alkyl group, preferably a hydrogen atom or a linear C 1-3 alkyl group, preferably a hydrogen atom or a methyl group.
• each occurrence of R 15 is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
• each occurrence of R 15 is independently an oxygen atom, a C 1-6 alkylene group, or a C 1-6 alkyleneoxy group.
• R 15 is a single bond.
• t is an integer of 2 or more independently at each occurrence.
• t is independently an integer of 2-10, preferably an integer of 2-6 at each occurrence.
• each occurrence of R 14 is independently a hydrogen atom, a halogen atom, or —X 11 —SiR 11 n1 R 12 3-n1 .
• a halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.
• R 14 is a hydrogen atom.
• formula (S1) is the following formula (S1-a).
• R 11 , R 12 , R 13 , X 11 , and n1 have the same meanings as described in formula (S1) above;
• t1 and t2 are each independently at each occurrence an integer of 1 or greater, preferably an integer of 1 to 10, more preferably an integer of 2 to 10, such as an integer of 1 to 5 or an integer of 2 to 5;
• the order of existence of each repeating unit bracketed with t1 and t2 is arbitrary in the formula.
• formula (S1) is the following formula (S1-b). [Wherein, R 11 , R 12 , R 13 , X 11 , n1 and t have the same meanings as described in formula (S1) above]
• each occurrence of R a1 is independently —Z 1 —SiR 21 p1 R 22 q1 R 23 r1 .
• Z 1 is independently an oxygen atom or a divalent organic group.
• the right side is bound to (SiR 21 p1 R 22 q1 R 23 r1 ).
• Z 1 is a divalent organic group.
• Z 1 does not include those that form a siloxane bond with the Si atom to which Z 1 is bonded.
• (Si—Z 1 —Si) does not contain a siloxane bond.
• the above Z 1 is preferably a C 1-6 alkylene group, —(CH 2 ) z1 —O—(CH 2 ) z2 — (wherein z1 is an integer of 0 to 6, for example an integer of 1 to 6 and z2 is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 -, wherein z3 is an integer of 0 to 6, For example, it is an integer from 1 to 6, and z4 is an integer from 0 to 6, such as an integer from 1 to 6).
• Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. is preferably unsubstituted.
• Z 1 is a C 1-6 alkylene group or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 -, preferably -phenylene-(CH 2 ) z4 -.
• Z 1 above is a C 1-3 alkylene group.
• Z 1 can be -CH 2 CH 2 CH 2 -.
• Z 1 can be -CH 2 CH 2 -.
• R 21 above is independently at each occurrence —Z 1′ —SiR 21′ p1′ R 22′ q1′ R 23′ r1′ .
• Z 1′ is independently an oxygen atom or a divalent organic group.
• the right side is bound to (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ).
• Z 1' is a divalent organic group.
• Z 1' does not include those that form a siloxane bond with the Si atom to which Z 1' is bonded.
• (Si—Z 1′ —Si) does not contain a siloxane bond.
• the above Z 1′ is preferably a C 1-6 alkylene group, —(CH 2 ) z1′ —O—(CH 2 ) z2′ — (wherein z1′ is an integer of 0 to 6, for example 1 to is an integer of 6 and z2' is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z3' -phenylene-(CH 2 ) z4' - (wherein z3' is an integer from 0 to 6, such as an integer from 1 to 6, and z4' is an integer from 0 to 6, such as an integer from 1 to 6).
• Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. is preferably unsubstituted.
• Z 1' is a C 1-6 alkylene group or -(CH 2 ) z3' -phenylene-(CH 2 ) z4' -, preferably -phenylene-(CH 2 ) z4' -.
• Z 1′ above is a C 1-3 alkylene group.
• Z 1' can be -CH 2 CH 2 CH 2 -.
• Z 1' can be -CH 2 CH 2 -.
• R 21′ above is independently at each occurrence —Z 1′′ —SiR 22′′ q1′′ R 23′′ r1′′ .
• Each occurrence of Z 1′′ above is independently an oxygen atom or a divalent organic group . ).
• Z 1′′ is a divalent organic group.
• Z 1′′ does not include those that form a siloxane bond with the Si atom to which Z 1′′ is bonded.
• Si—Z 1′′ —Si does not contain a siloxane bond.
• Z 1′′ is preferably a C 1-6 alkylene group, —(CH 2 ) z1′′ —O—(CH 2 ) z2′′ — (wherein z1′′ is an integer of 0 to 6, for example 1 to is an integer of 6, and z2′′ is an integer of 0 to 6, such as an integer of 1 to 6) or —(CH 2 ) z3′′ —phenylene-(CH 2 ) z4′′ —, wherein z3′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z4′′ is an integer from 0 to 6, such as an integer from 1 to 6).
• Such C 1-6 alkylene groups are linear or branched, but preferably straight-chain, these groups are, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2- It may be substituted with one or more substituents selected from 6 alkynyl groups, but is preferably unsubstituted.
• Z 1′′ is a C 1-6 alkylene group or -(CH 2 ) z3′′ -phenylene-(CH 2 ) z4′′ -, preferably -phenylene-(CH 2 ) z4′′ -.
• Z 1′′ is such a group, it can be more light-resistant, especially UV-resistant.
• Z 1′′ is a C 1-3 alkylene group. In one aspect, Z 1′′ can be —CH 2 CH 2 CH 2 —. In another aspect, Z 1′′ can be —CH 2 CH 2 —.
• R 22′′ above is independently a hydroxyl group or a hydrolyzable group.
• R 22 ′′ above is preferably independently at each occurrence a hydrolyzable group.
• Each occurrence of R 23 ′′ above is independently a monovalent organic group.
• Such monovalent organic groups are monovalent organic groups excluding the above hydrolyzable groups.
• the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
• q1′′ is independently at each occurrence an integer from 0 to 3
• the at least one r1′′ is independently at each occurrence an integer from 0 to 3.
• the sum of q1′′ and r1′′ is 3 in units of (SiR 22′′ q1′′ R 23′′ r1′′ ).
• q1′′ is an integer of preferably 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR 22′′ q1′′ R 23′′ r1′′ ) unit.
• R 22′ is independently a hydroxyl group or a hydrolyzable group.
• R 22' is preferably independently at each occurrence a hydrolyzable group.
• R 22′ is preferably independently at each occurrence —OR h , —OCOR h , —ON ⁇ CR h 2 , —NR h 2 , —NHR h , —NCO, or halogen (wherein R h represents a substituted or unsubstituted C 1-4 alkyl group), more preferably —OR h (ie, an alkoxy group).
• R h include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
• an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
• R h is a methyl group, and in another aspect R h is an ethyl group.
• Each occurrence of R 23′ above is independently a monovalent organic group.
• Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
• the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, even more preferably a methyl group.
• p1' is independently an integer of 0 to 3 at each occurrence
• q1' is independently an integer from 0 to 3 at each occurrence
• r1' is independently at each occurrence.
• the sum of p', q1' and r1' is 3 in the (SiR 21' p1' R 22' q1' R 23' r1' ) unit.
• p1' is 0.
• p1' is an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit. may In a preferred embodiment, p1' is 3.
• q1′ is an integer of 1 to 3, preferably an integer of 2 to 3, each independently for each (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ) unit, 3 is more preferable.
• p1' is 0 and q1' is an integer of 1 to 3 independently for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit, preferably is an integer of 2-3, more preferably 3.
• R 22 above is independently a hydroxyl group or a hydrolyzable group.
• R 22 is preferably independently at each occurrence a hydrolyzable group.
• R h include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
• an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
• R h is a methyl group, and in another aspect R h is an ethyl group.
• Each occurrence of R 23 above is independently a monovalent organic group.
• Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
• the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, even more preferably a methyl group.
• p1 above independently at each occurrence is an integer of 0 to 3
• q1 is independently at each occurrence an integer from 0 to 3
• r1 is independently at each occurrence, An integer from 0 to 3.
• the sum of p1, q1 and r1 is 3 in units of (SiR 21 p1 R 22 q1 R 23 r1 ).
• p1 is 0.
• p1 may be an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit. In a preferred embodiment, p1 is 3.
• q1 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3, independently for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
• p1 is 0 and q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit. 3 is preferred.
• each occurrence of R b1 is independently a hydroxyl group or a hydrolyzable group.
• R b1 above is preferably independently at each occurrence a hydrolyzable group.
• R h include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
• an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
• R h is a methyl group, and in another aspect R h is an ethyl group.
• R c1 at each occurrence is independently a monovalent organic group.
• a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
• the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.
• k1 above independently at each occurrence is an integer of 0 to 3
• l1 is independently at each occurrence an integer from 0 to 3
• m1 is independently at each occurrence, An integer from 0 to 3.
• the sum of k1, l1 and m1 is 3 in units of (SiR a1 k1 R b1 l1 R c1 m1 ).
• k1 is independently an integer of 1 to 3, preferably 2 or 3, more preferably 3 for each (SiR a1 k1 R b1 l1 R c1 m1 ) unit. In a preferred embodiment, k1 is 3.
• At least two Si atoms to which hydroxyl groups or hydrolyzable groups are bonded are present at the terminal portion of formula (S2).
• the group represented by formula (S2) is —Z 1 —SiR 22 q1 R 23 r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3 and r1 is an integer of 0 to 2.), —Z 1′ —SiR 22′ q1′ R 23′ r1′ (wherein q1′ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1′ is an integer of 0 to 2), or —Z 1′′ —SiR 22′′ q1′′ R 23′′ r1′′ (wherein q1′′ is 1 to is an integer of 3, preferably 2 or 3, more preferably 3, and r1′′ is an integer of 0 to 2.) Z 1 , Z 1′ , Z 1′′ , R 22 , R 23 , R 22′ , R 23′ , R 22′′ , and R 23′′ are as defined above.
• R 21′ if R 21′ is present, at least one, preferably all R 21′ , q1′′ is an integer from 1 to 3, preferably 2 or 3, or more 3 is preferred.
• R 21 if R 21 is present, at least one, preferably all R 21 , p1′ is 0 and q1′ is an integer of 1 to 3, preferably is 2 or 3, more preferably 3.
• R a1 if R a1 is present, at least one, preferably all R a1 , p1 is 0, q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3.
• k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3, in formula (S2).
• R d1 is independently at each occurrence -Z 2 -CR 31 p2 R 32 q2 R 33 r2 .
• Z 2 is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group.
• the right side is bound to (CR 31 p2 R 32 q2 R 33 r2 ).
• Z 2 is a divalent organic group.
• Z 2 does not contain a siloxane bond.
• the above Z 2 is preferably a C 1-6 alkylene group, —(CH 2 ) z5 —O—(CH 2 ) z6 — (wherein z5 is an integer of 0 to 6, for example an integer of 1 to 6 and z6 is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z7 -phenylene-(CH 2 ) z8 -, wherein z7 is an integer of 0 to 6, For example, an integer from 1 to 6, and z8 is an integer from 0 to 6, such as an integer from 1 to 6).
• Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. is preferably unsubstituted.
• Z 2 is a C 1-6 alkylene group or -(CH 2 ) z7 -phenylene-(CH 2 ) z8 -, preferably -phenylene-(CH 2 ) z8 -.
• Z2 is such a group, it can be more light-resistant, especially UV-resistant.
• Z 2 above is a C 1-3 alkylene group.
• Z 2 can be -CH 2 CH 2 CH 2 -.
• Z 2 can be -CH 2 CH 2 -.
• R 31 is independently at each occurrence -Z 2' -CR 32' q2' R 33' r2' .
• Z 2' at each occurrence is independently a single bond, an oxygen atom or a divalent organic group.
• the right side is bound to (CR 32′ q2′ R 33′ r2′ ).
• Z 2' does not contain a siloxane bond.
• the above Z 2′ is preferably a C 1-6 alkylene group, —(CH 2 ) z5′ —O—(CH 2 ) z6′ — (wherein z5′ is an integer of 0 to 6, for example 1 to is an integer of 6 and z6' is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z7' -phenylene-(CH 2 ) z8' - (wherein z7' is an integer from 0 to 6, such as an integer from 1 to 6, and z8' is an integer from 0 to 6, such as an integer from 1 to 6).
• Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. is preferably unsubstituted.
• Z 2' is a C 1-6 alkylene group or -(CH 2 ) z7' -phenylene-(CH 2 ) z8' -, preferably -phenylene-(CH 2 ) z8' -.
• Z 2′ is such a group, it can be more light-resistant, especially UV-resistant.
• Z 2′ above is a C 1-3 alkylene group.
• Z 2' can be -CH 2 CH 2 CH 2 -.
• Z 2' can be -CH 2 CH 2 -.
• R 32′ is independently —Z 3 —SiR 34 n2 R 35 3-n2 .
• Z 3 is independently a single bond, an oxygen atom, or a divalent organic group.
• the right side is bound to (SiR 34 n2 R 35 3-n2 ).
• Z3 is an oxygen atom.
• Z 3 is a divalent organic group.
• Z3 does not contain a siloxane bond.
• the above Z 3 is preferably a C 1-6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ — (wherein z5′′ is an integer of 0 to 6, such as 1 to 6 and z6′′ is an integer of 0 to 6, such as an integer of 1 to 6) or —(CH 2 ) z7′′ —phenylene-(CH 2 ) z8′′ — (wherein z7′′ is , an integer from 0 to 6, such as an integer from 1 to 6, and z8′′ is an integer from 0 to 6, such as an integer from 1 to 6).
• Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. is preferably unsubstituted.
• Z 3 is a C 1-6 alkylene group or —(CH 2 ) z7′′ -phenylene-(CH 2 ) z8′′ -, preferably -phenylene-(CH 2 ) z8′′ - .
• Z 3 is a C 1-6 alkylene group or —(CH 2 ) z7′′ -phenylene-(CH 2 ) z8′′ -, preferably -phenylene-(CH 2 ) z8′′ - .
• Z 3 above is a C 1-3 alkylene group.
• Z 3 can be -CH 2 CH 2 CH 2 -.
• Z 3 can be -CH 2 CH 2 -.
• R 34 above is independently a hydroxyl group or a hydrolyzable group.
• R 34 is preferably independently at each occurrence a hydrolyzable group.
• R h include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
• an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
• R h is a methyl group, and in another aspect R h is an ethyl group.
• Each occurrence of R 35 above is independently a monovalent organic group.
• Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
• the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.
• n2 is an integer of 0 to 3 independently for each (SiR 34 n2 R 35 3-n2 ) unit. However, at least two (SiR 34 n2 R 35 3-n2 ) units where n2 is 1 to 3 are present in the terminal portion of formula (S3). In other words, there are at least two Si atoms bonded with hydroxyl groups or hydrolyzable groups in the terminal portion of formula (S3).
• n2 is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR 34 n2 R 35 3-n2 ) unit.
• Each occurrence of R 33′ above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group.
• a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
• the monovalent organic group is preferably a C 1-20 alkyl group or —(C s H 2s ) t1 —(O—C s H 2s ) t2 (wherein s is 1 to 6 , preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6 ), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
• R 33' is a hydroxyl group.
• R 33' is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
• Each occurrence of q2' is independently an integer from 0 to 3, and each occurrence of r2' is independently an integer from 0 to 3.
• the sum of q2' and r2' is 3 in the unit of (CR 32' q2' R 33' r2' ).
• q2' is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (CR 32' q2' R 33' r2' ) unit.
• R 32 is independently at each occurrence -Z 3 -SiR 34 n2 R 35 3-n2 .
• Such —Z 3 —SiR 34 n2 R 35 3-n2 has the same meaning as described for R 32′ above.
• Each occurrence of R 33 above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group.
• a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
• the monovalent organic group is preferably a C 1-20 alkyl group or —(C s H 2s ) t1 —(O—C s H 2s ) t2 (wherein s is 1 to 6 an integer, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6 ), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and most preferably a methyl group.
• R 33 is a hydroxyl group.
• R 33 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
• p2 above independently at each occurrence is an integer of 0 to 3
• q2 is independently at each occurrence an integer from 0 to 3
• r2 is independently at each occurrence, An integer from 0 to 3.
• the sum of p2, q2 and r2 is 3 in the unit of (CR 31 p2 R 32 q2 R 33 r2 ).
• p2 is 0.
• p2 may be an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (CR 31 p2 R 32 q2 R 33 r2 ) unit. In preferred embodiments, p2 is three.
• q2 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (CR 31 p2 R 32 q2 R 33 r2 ) unit.
• p2 is 0 and q2 is independently an integer of 1 to 3, preferably an integer of 2 to 3, for each (CR 31 p2 R 32 q2 R 33 r2 ) unit. 3 is preferred.
• R e1 above is independently —Z 3 —SiR 34 n2 R 35 3-n2 .
• Such —Z 3 —SiR 34 n2 R 35 3-n2 has the same meaning as described for R 32′ above.
• Each occurrence of R f1 above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group.
• a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
• the monovalent organic group is preferably a C 1-20 alkyl group or —(C s H 2s ) t1 —(O—C s H 2s ) t2 (wherein s is 1 to 6 an integer, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6 ), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
• R f1 is a hydroxyl group.
• R f1 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
• k2 above independently at each occurrence is an integer of 0 to 3
• l2 is independently at each occurrence an integer from 0 to 3
• m2 is independently at each occurrence, An integer from 0 to 3.
• the sum of k2, l2 and m2 is 3 in units of (CR d1 k2 R e1 l2 R f1 m2 ).
• n2 is 1 to 3, preferably 2 or 3, more preferably 3 is 2 or more at each terminal portion of formula (S3),
• n2 is an integer from 1 to 3, preferably 2 or 3, more preferably is 3.
• n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3 is.
• R e1 if R e1 is present, at least one, preferably all R a1 , n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3 is.
• k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3, in formula (S3).
• R g1 and R h1 are each independently at each occurrence -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , -Z 4 -CR d1 k2 R e1 l2 R f1 m2 .
• R 11 , R 12 , R a1 , R b2 , R c1 , R d1 , R e1 , R f1 , n1, k1, l1, m1, k2, l2, and m2 have the same meanings as above.
• R g1 and R h1 are each independently —Z 4 —SiR 11 n1 R 12 3-n1 .
• Z 4 is independently a single bond, an oxygen atom, or a divalent organic group.
• the right side is bound to (SiR 11 n1 R 12 3-n1 ).
• Z 4 is an oxygen atom.
• Z 4 is a divalent organic group.
• Z 4 does not contain a siloxane bond.
• the above Z 4 is preferably a C 1-6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ — (wherein z5′′ is an integer of 0 to 6, such as 1 to 6 and z6′′ is an integer of 0 to 6, such as an integer of 1 to 6) or —(CH 2 ) z7′′ —phenylene-(CH 2 ) z8′′ — (wherein z7′′ is , an integer from 0 to 6, such as an integer from 1 to 6, and z8′′ is an integer from 0 to 6, such as an integer from 1 to 6).
• Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. is preferably unsubstituted.
• Z 4 is a C 1-6 alkylene group or —(CH 2 ) z7′′ -phenylene-(CH 2 ) z8′′ -, preferably -phenylene-(CH 2 ) z8′′ -.
• Z 3 When is such a group, higher light resistance, especially UV resistance, can be obtained.
• Z 4 above is a C 1-3 alkylene group.
• Z 4 can be -CH 2 CH 2 CH 2 -.
• Z 4 can be -CH 2 CH 2 -.
• formulas (S1), (S2), (S3) and (S4) do not contain a siloxane bond.
• RH is a group represented by formula (S2), (S3) or (S4).
• RH is a group represented by formula (S2) or (S3).
• RH is a group represented by formula (S3) or (S4).
• R 3 H is a group represented by formula (S1).
• formula (S1) is a group represented by formula (S1-b).
• R 13 is a hydrogen atom and X 11 is a single bond or -R 28 -O x -R 29 - (wherein R 28 and R 29 are independently is a single bond or a C 1-20 alkylene group, x is 0 or 1), n1 is 1-3, preferably 2-3, more preferably 3.
• RH is a group represented by formula (S2).
• formula (S3) is -SiR a1 2 R c1 or -SiR a1 3
• R a1 is -Z 1 -SiR 22 q1 R 23 r1
• Z 1 is C 1-6
• R 3 H is a group represented by formula (S3).
• formula (S4) is —CR e1 2 R f1 or —CR e1 3
• R e1 is —Z 3 —SiR 34 n2 R 35 3-n2
• Z 3 is C 1 —6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ —, wherein z5′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z6′′ is 0 -(CH 2 ) z7′′ -phenylene-(CH 2 ) z8′′ - (wherein z7′′ is an integer of 0 to 6, such as 1 to is an integer of 6, z8′′ is an integer of 0 to 6, such as an integer of 1 to 6), preferably a C 1-6 alkylene group, n2 is 1 to 3, preferably 2 to 3, and further 3 is preferred.
• RH is a group represented by formula (S4).
• R g1 and R h1 are —Z 4 —SiR 11 n1 R 12 3-n1
• Z 4 is a C 1-6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ - (wherein z5′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z6′′ is an integer from 0 to 6, such as an integer from 1 to 6) or –( CH 2 ) z7′′ -phenylene-(CH 2 ) z8′′ —, wherein z7′′ is an integer from 0 to 6, such as an integer from 1 to 6, z8′′ is an integer from 0 to 6, such as 1 6), preferably a C 1-6 alkylene group, n1 is 1-3, preferably 2-3, more preferably 3.
• X A is understood as a linker that connects the siloxane portion (R S1 or R S2 ) that mainly provides a function such as fingerprint wiping ability and the portion (R H ) that provides the ability to bond to the substrate. Therefore, XA may be a single bond or any group as long as the compounds represented by formulas (1) and (2) can exist stably.
• ⁇ is an integer of 1-9
• ⁇ is an integer of 1-9.
• ⁇ and ⁇ can vary depending on the valence of XA .
• the sum of ⁇ and ⁇ is the same as the valence of XA .
• X A is a decavalent organic group
• the sum of ⁇ and ⁇ is 10, such as ⁇ being 9 and ⁇ being 1, ⁇ being 5 and ⁇ being 5, or ⁇ being 1 and ⁇ being 9. obtain.
• ⁇ and ⁇ are 1 when X A is a divalent organic group.
• ⁇ is an integer of 1-9. ⁇ can vary depending on the valence of X A. That is, ⁇ is the value obtained by subtracting 1 from the valence of XA .
• Each X A is independently a single bond or a divalent to decavalent organic group.
• the divalent to decavalent organic group in X A above is preferably a divalent to octavalent organic group.
• a divalent to decavalent organic group is preferably a divalent to tetravalent organic group, more preferably a divalent organic group.
• such divalent to decavalent organic groups are preferably trivalent to octavalent organic groups, more preferably trivalent to hexavalent organic groups.
• X A is a single bond or a divalent organic group and ⁇ , ⁇ , and ⁇ are one.
• X A is a tri- to hexavalent organic group, ⁇ is 1, ⁇ is 2-5, and ⁇ is 2-5.
• X A is a trivalent organic group, ⁇ is 1 and ⁇ is 2.
• formulas (1) and (2) are represented by formulas (1') and (2') below.
• X A is a single bond.
• X A is a divalent organic group.
• X A is, for example, a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 -
• R 51 is a single bond, —(CH 2 ) s5 — or an o-, m- or p-phenylene group, preferably —(CH 2 ) s5 —, s5 is an integer from 1 to 20, preferably an integer from 1 to 15, more preferably an integer from 1 to 10, even more preferably an integer from 1 to 6, such as an integer from 1 to 3;
• X 51 is -(X 52 ) l5 -
• X 52 is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -CO-, -C(O)O-, -CONR 54 -, -O a group selected from the group consisting of
• X A (typically the hydrogen atom of X A ) is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. may be In preferred embodiments, X A is not substituted by these groups.
• the left side of X A is bound to R S1 or R S2 .
• the oxyalkylene-containing group having 1 to 10 carbon atoms is a group containing —O—C 1-10 alkylene—, for example, —R 55 —(—O—C 1-10 alkylene) n —R 56 (the formula wherein R 55 is a single bond or a divalent organic group, preferably a C 1-6 alkylene group, n is any integer, preferably an integer of 2 to 10, R 56 is a hydrogen atom or 1 a valent organic group, preferably a C 1-6 alkyl group).
• the above alkylene group may be linear or branched.
• each X A above is independently -(R 51 ) p5 -(X 51 ) q5 -R 52 -.
• R 52 is a single bond, -(CH 2 ) t5 - or an o-, m- or p-phenylene group, preferably -(CH 2 ) t5 -.
• t5 is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3.
• R 52 (typically the hydrogen atom of R 52 ) is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group; may be In preferred embodiments, R 56 is unsubstituted by these groups.
• the above X A are each independently single bond, a C 1-20 alkylene group, —R 51 —X 53 —R 52 —, or [wherein R 51 and R 52 have the same meanings as above, X53 is single bond, -O-, -S-, -CO-, -C(O)O-, -CONR 54- , -O-CONR 54- , —O—(CH 2 ) u5 —CONR 54 —, —O—(CH 2 ) u5 —CO—, or —CONR 54 —(CH 2 ) u5 —N(R 54 )—, (Wherein, R 54 has the same meaning as above, u5 is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3. ). ] can be
• the above X A are each independently single bond, a C 1-20 alkylene group, —(CH 2 ) s5 —X 53 —, —X 53 —(CH 2 ) t5 —, or —(CH 2 ) s5 —X 53 —(CH 2 ) t5 — [In the formula, X 53 , s5 and t5 have the same meanings as above. ] is.
• each of the above X A is independently a single bond C 1-20 alkylene group, —(CH 2 ) s5 —X 53 —, —X 53 —(CH 2 ) t5 — or —(CH 2 ) s5 —X 53 —(CH 2 ) t5 —
• X 53 is a single bond, -O-, -CO-, -CONR 54 -, -O-CONR 54 -, -O-(CH 2 ) u5 -CONR 54 -, or -O-(CH 2 ) u5 - is CO-;
• each occurrence of R 54 is independently a hydrogen atom, a phenyl group, a C 1-6 alkyl group (preferably a methyl group) or an oxyalkylene-containing group having 1 to 10 carbon atoms; s5, t5 and u5 have the same meanings as above. ] can be
• each of the above X A is independently —(CH 2 ) s5 —O—(CH 2 ) t5 —, —(CH 2 ) s5 —CONR 54 —(CH 2 ) t5 —, -(CH 2 ) s5 -O-(CH 2 ) u5 -CO-, or -(CH 2 ) s5 -O-(CH 2 ) u5 -CONR 54 -(CH 2 ) t5 -
• each occurrence of R 54 is independently a hydrogen atom, a phenyl group, a C 1-6 alkyl group (preferably a methyl group) or an oxyalkylene-containing group having 1 to 10 carbon atoms; s5, t5 and u5 have the same meanings as above. ] can be
• X A is each independently one or more 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 substituted by a substituent. In one aspect, X A is unsubstituted.
• each X A can independently be a 3- to 10-valent organic group.
• examples of X A include: [In the formula, X a is a single bond or a divalent organic group. ] A group represented by
• X a above is a single bond or a divalent linking group that directly bonds to the isocyanuric ring.
• X a is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond and a sulfide bond, and An alkylene group of 1 to 10, or a divalent hydrocarbon group of 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond and a sulfide bond is more preferred.
• X a is represented by the following formula: -(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 - (Wherein, X 121 to X 124 are each independently H, OH, or —OSi(OR 121 ) 3 (Wherein, three R 121 are each independently is an alkyl group.)
• the left side of X a is bound to the isocyanuric ring.
• the siloxane group-containing silane compound of the present disclosure is a siloxane group-containing silane compound represented by formula (1).
• the siloxane group-containing silane compound of the present disclosure is a siloxane group-containing silane compound represented by formula (2).
• the siloxane group-containing silane compound represented by formula (1) or (2) is not particularly limited, but may have a number average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 .
• the siloxane group-containing silane compound represented by the above formula (1) or (2) preferably has a number average molecular weight of 1,000 to 30,000, more preferably 1,500 to 10,000. It is preferable from the viewpoint of durability.
• the "number average molecular weight" is a value measured by 1 H-NMR.
• the siloxane group-containing silane compound can be obtained, for example, by reacting a compound having an organosiloxane group with a compound having a hydrolyzable silane group.
• R61 -COOH In the formula, R 61 is an organosiloxane group-containing group.
• the compound represented by the following formula: NH2 - R62 [In the formula, R 62 is an allyl group-containing group. ] is reacted with a compound represented by the following formula: R 61 -CONH-R 63 -R 64 n [In the formula, R 61 is an organosiloxane group-containing group, R 63 is an (n+1) valent linker group, R64 is an allyl group.
• the compound represented by formula (1) can be obtained by obtaining an oxadiazole compound from R 61 —COOH according to the following scheme and using it as a starting material.
• R has an allyl group at its terminal
• the compound represented by formula (1) can be obtained by reacting HSiR 65 m R 66 3-m as described above.
• R 61 is an organosiloxane group-containing group, R is alkyl or aryl, which may contain a terminal functional group;
• the functional groups are carboxylic acid derivatives such as esters (eg, allyls, esters, amides, carboxylic acids, anhydrides, acid chlorides, nitriles), amines, epoxides, benzene rings, alcohols, or unsaturated bonds. ]
• R 61 -CW m X 3-m [In the formula: R 61 is an organosiloxane group-containing group, X is a hydrolyzable group, W is independently at each occurrence a monovalent organic group; m is 1-3. ]
• the compound represented by the following formula: MR 62 [In the formula: M is a metal-containing group such as Li, halogen-Mg, Zn; R62 is an allyl group-containing group.
• R 61 is an organosiloxane group-containing group, R 63 is a divalent group, R 64 is an allyl group, W is independently at each occurrence a monovalent organic group; m is 1-3.
• R 61 is an organosiloxane group-containing group
• R 63 is a divalent group
• R 64 is an allyl group
• W is independently at each occurrence a monovalent organic group
• m 1-3.
• the obtained allyl compound, H SiR 65 m R 66 3-m In the formula, each occurrence of R 65 is independently a hydroxyl group or a hydrolyzable group; R 66 is independently at each occurrence a monovalent organic group; m is 1-3.
• the compound represented by Formula (1) can be obtained by reacting with the compound represented by.
• R61 - COR67 In the formula: R 61 is an organosiloxane group-containing group, R 67 is OH or a hydrolyzable group such as a halogen element, NR 2 , —OCOR′, an alkoxy group, each R is independently a hydrogen atom or an alkyl group, R' is a hydrogen atom or an alkyl group.
• a compound represented by MR 62 [In the formula: M is a metal-containing group such as Li, halogen-Mg, or Zn; R62 is an allyl group-containing group.
• R 61 is an organosiloxane group-containing group
• R 63 is a divalent group
• R64 is an allyl group.
• a compound represented by is obtained.
• the resulting compound is represented by the following formula: LR 62 [In the formula: L is a leaving group; R62 is an allyl group-containing group.
• R 61 is an organosiloxane group-containing group
• R 63 is a divalent group
• R64 is an allyl group.
• a compound represented by is obtained.
• the obtained allyl compound, H SiR 65 m R 66 3-m In the formula, each occurrence of R 65 is independently a hydroxyl group or a hydrolyzable group; R 66 is independently at each occurrence a monovalent organic group; m is 1-3.
• the compound represented by Formula (1) can be obtained by reacting with the compound represented by.
• R61 -CH CH2 [In the formula: R 61 is an organosiloxane group-containing group. ] and a compound represented by the following formula H—SiX 3 [In the formula, X is a hydrolyzable group. ] to give the following formula: R61 - CH2CH2SiX3 _ A compound represented by is obtained. The resulting compound is then MR 62 [In the formula, M is a metal-containing group such as Li, halogen-Mg, or Zn; R62 is an allyl group-containing group.
• R 61 is an organosiloxane group-containing group, R 63 is a divalent group, R64 is an allyl group.
• R 61 is an organosiloxane group-containing group, R 63 is a divalent group, R64 is an allyl group.
• An allyl compound is then obtained.
• the obtained allyl compound H SiR 65 m R 66 3-m
• each occurrence of R 65 is independently a hydroxyl group or a hydrolyzable group; R 66 is independently at each occurrence a monovalent organic group; m is 1-3.
• the compound represented by Formula (1) can be obtained by reacting with the compound represented by.
• R 61 —CH ⁇ CH 2 is reacted with an oxidizing agent to form an epoxy compound, which can be used to obtain a compound represented by Formula (1) of the present disclosure. .
• R 61 —CH ⁇ CH 2 is reacted with a thiol compound represented by HSR to give a thio compound represented by R 61 —CH 2 —CH 2 —SR or R 61 —CH(SR)—CH 3 . and such thio compounds can be used to obtain compounds represented by formula (1) of the present disclosure.
• R is any group.
• each R is independently a hydrocarbon, a hydrogen atom, an oxygen atom, a nitrogen atom, or -COR'.
• R' is an arbitrary group.
• each R is independently a hydrogen atom or a hydrocarbon group.
• R61 - SiW2 -H [In the formula, R 61 is an organosiloxane group-containing group, W is independently at each occurrence a monovalent organic group. ] and a compound represented by the following formula: H 2 C ⁇ CH—R 67 [R 67 is a functional group-containing group such as amide, carboxylic acid, acid anhydride, acid chloride, nitrile, amine, epoxide, benzene ring, and alcohol. ] to give the following formula: R 61 -SiX 2 -CH 2 CH 2 -R 67 A compound represented by can be obtained. The compound represented by the formula (1) can be obtained by using such a compound as a raw material and appropriately utilizing the above reaction.
• R61 - CH2NR68H [In the formula, R 61 is an organosiloxane group-containing group, R 68 is any group. ]
• the compound represented by the following formula HOCO-R 69 [In the formula, R 69 is a double bond group-containing group. ] is reacted with a compound represented by the following formula: R 61 —CH 2 NR 68 CO—R 69 get By using such a compound as a starting material and subjecting the double bond contained in R 69 to the above hydrosilylation reaction, the compound represented by formula (1) can be obtained.
• R61 - CH2NH2 [In the formula, R 61 is an organosiloxane group-containing group. ]
• a compound represented by R70 -COOH [In the formula, R 70 is a functional group-containing group such as double bond, amide, carboxylic acid, acid anhydride, acid chloride, nitrile, amine, epoxide, benzene ring, and alcohol. ]
• R61 - CH2NHCO - R70 By reacting with a compound represented by R61 - CH2NHCO - R70 is obtained, and the compound represented by the formula (1) can be obtained using such a compound as a raw material.
• a compound represented by formula (1) can be obtained using a compound obtained by reacting an epoxy compound with a compound as shown below as a starting material.
• R 61 is an organosiloxane group-containing group
• R 1 is a hydrogen atom or an alkyl group
• R 2 is a hydrogen atom or an alkyl group
• R is a hydrocarbon group that may contain a functional group at the end;
• the functional groups are carboxylic acid derivatives such as esters (eg, esters, amides, carboxylic acids, acid anhydrides, acid chlorides, nitriles), amines, epoxides, benzene rings, alcohols, or unsaturated bonds. ]
• R 61 —CH 2 X reacts with isocyanuric acid in the presence of a suitable base (sodium hydride, sodium carbonate, potassium t-butoxide, metal hexamethyldisilazide, etc.) according to the scheme below.
• a suitable base sodium hydride, sodium carbonate, potassium t-butoxide, metal hexamethyldisilazide, etc.
• X is a leaving functional group, eg chloride, bromide, iodide. paratoluenesulfonate, trifluoromethanesulfonate, carboxylate.
• the above hydrosilylation is preferably carried out using a transition metal catalyst.
• a transition metal catalyst Group 8 to Group 10 transition metal catalysts are preferred, and platinum catalysts, ruthenium catalysts, rhodium catalysts and the like are among them.
• a platinum catalyst is preferred.
• platinum catalysts include Pt/divinyltetramethyldisiloxane complex, Pt/tetramethyltetravinylcyclotetrasiloxane complex, chloroplatinic acid, and platinum oxide. Among them, either a Pt/divinyltetramethyldisiloxane complex or a Pt/tetramethyltetravinylcyclotetrasiloxane complex is preferred.
• the amount of the transition metal catalyst used is preferably 0.1 to 1,000 ppm by mass, particularly preferably 1 to 100 ppm, relative to the compound having a double bond to be reacted. By setting it as said usage-amount, reaction can progress appropriately and coloring resulting from a catalyst can be suppressed.
• the above catalyst particularly a platinum catalyst, and a nitrogen-containing compound or a sulfur-containing compound are used in combination.
• a platinum catalyst and a nitrogen-containing compound or a sulfur-containing compound are used in combination.
• One of these compounds may be used, or two or more thereof may be used.
• nitrogen-containing compounds examples include aliphatic amine compounds, triethylamine, aromatic amine compounds (aniline, pyridine, etc.), phosphoramides (hexamethylphosphoramide, etc.), amide compounds (N,N-diethylacetamide, N,N -diethylformamide, N,N-dimethylacetamide, N-methylformamide, N,N-dimethylformamide, etc.), urea compounds (tetramethylurea, etc.), cyclic amide compounds (N-methylpyrrolidone, etc.), and the like. be done.
• nitrogen-containing compounds compounds having a large number of donors, which will be described later, are preferred, and preferred are aliphatic amine compounds, aromatic amine compounds, phosphoric acid amides, and urea compounds.
• the nitrogen-containing compound has high basicity, side reactions such as hydrolysis and condensation reaction of the hydrolyzable group tend to proceed, so a compound with low basicity or neutrality is preferred.
• aromatic amine compounds, phosphoric acid amides, and urea compounds are preferred.
• sulfur-containing compounds examples include sulfoxide compounds (tetramethylene sulfoxide, dimethyl sulfoxide, etc.).
• one or more of aromatic amine compounds and sulfoxide compounds are preferable, and one or more of tetramethylene sulfoxide and dimethylsulfoxide are particularly preferable.
• Both the above nitrogen-containing compounds and sulfur-containing compounds have a large number of donors.
• the donor number is one of solvent parameters and is a measure of electron (pair) donating ability.
• the compound corresponding to the transition metal in the transition metal catalyst is coordinated, and therefore the coordination of the compound having a double bond to the transition metal is controlled. Conceivable. As a result, a composition having a specific composition is obtained.
• the number of donors is the amount of heat when a nitrogen-containing compound or sulfur-containing compound and SbCl5 form a 1:1 adduct.
• the amount of the nitrogen-containing compound or sulfur-containing compound used is preferably 0.001 to 1,000 parts by mass, particularly preferably 0.01 to 10 parts by mass, with respect to 100 parts by mass of the compound having a double bond. Further, the mass ratio of the amount of the transition metal catalyst and the nitrogen-containing compound or sulfur-containing compound used (nitrogen-containing compound or sulfur-containing compound:transition metal catalyst) is preferably 10:1 to 10,000:1, and 20:1 to 1,000:1 is particularly preferred
• the present disclosure provides an intermediate of the compound represented by formula (1) or (2) above.
• R S1 is independently at each occurrence R 1 -R S -R 2 q -;
• R S2 is —O p —R S —R 2 q —;
• R S is independently at each occurrence a divalent linear organosiloxane group;
• R 1 is a hydrocarbon group;
• R 2 is -SiR 3 2 -;
• R 3 is independently at each occurrence a hydrocarbon group;
• X B are each independently —(CH 2 ) s6 —X 53 —X 54 , -X53- ( CH2 ) t6 - X54 , or -( CH2 ) s6 - X53- ( CH2 ) t6 - X54 (In the formula, X 53 is -O-, -CO-, -CONR 74 -, -O-CONR
• R S1 and R S2 in formulas (1-a) and (2-a) have the same meanings as R S1 and R S2 in formulas (1) and (2).
• X B each independently represents -(CH 2 ) s6 -X 53 -X 54 , -X 53 -(CH 2 ) t6 -X 54 , or -(CH 2 ) s6 -X 53 -(CH 2 ) t6 - X54 .
• X 53 is a single bond, -O-, -CO-, -CONR 74 -, -O-CONR 74 -, -O-(CH 2 ) u6 -CONR 74 -, or -O-(CH 2 ) u6 - CO—, preferably —O—, —CO—, —CONR 74 —, —O—CONR 74 —, —O—(CH 2 ) u6 —CONR 74 —, or —O—(CH 2 ) u6 -CO-, more preferably CONR 74 -.
• Each occurrence of R 74 is independently a hydrogen atom, a phenyl group, a C 1-6 alkyl group, or an oxyalkylene-containing group having 1 to 10 carbon atoms, preferably a hydrogen atom, a C 1-6 alkyl group, or It is an oxyalkylene-containing group having 1 to 10 carbon atoms.
• the oxyalkylene-containing group having 1 to 10 carbon atoms is a group containing —O—C 1-10 alkylene—, for example, —R 55 —(—O—C 1-10 alkylene) n —R 56 (the formula wherein R 55 is a single bond or a divalent organic group, preferably a C 1-6 alkylene group, n is any integer, preferably an integer of 2 to 10, R 56 is a hydrogen atom or 1 a valent organic group, preferably a C 1-6 alkyl group).
• the above alkylene group may be linear or branched.
• R 74 is a hydrogen atom.
• R 74 is an oxyalkylene containing group of 1-10 carbon atoms.
• X 54 is R 75 , —NR 75 2 , —SiR 75 2 R 76 , —SiR 75 3 , —CR 75 2 R 75 , —CR 75 3 , —SiCl 2 R 76 , —SiCl 3 , or and preferably -NR 75 2 , -SiR 75 2 R 76 , -SiR 75 3 , -CR 75 2 R 75 , -CR 75 3 , or is.
• X 54 is R 75 , —NR 75 2 , —SiR 75 2 R 76 , —SiR 75 3 , —CR 75 2 R 75 , or —CR 75 3 , preferably —SiR 75 3 , or —CR 75 3 , more preferably —SiR 75 3 .
• X 54 is is.
• R 76 is a monovalent organic group, preferably a C 1-6 alkylene group, an oxyalkylene-containing group having 1 to 10 carbon atoms.
• the oxyalkylene-containing group having 1 to 10 carbon atoms has the same meaning as above.
• X 54 is —SiR 75 2 R 76 or —CR 75 2 R 75 , preferably the divalent linear organosiloxane group is —(SiR 3 2 -O) a -.
• composition of the present disclosure contains at least one siloxane group-containing silane compound represented by formula (1) or (2).
• the siloxane group-containing silane compound in the composition of the present disclosure is a compound represented by Formula (1).
• the siloxane group-containing silane compound in the composition of the present disclosure is a compound represented by formula (2).
• siloxane group-containing silane compounds in the composition of the present disclosure are the compound represented by Formula (1) and the compound represented by Formula (2).
• the compound represented by formula (2) is preferably 0.1 mol with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) % or more and 35 mol % or less.
• the lower limit of the content of the compound represented by formula (2) with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol%, more preferably It can 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 compound represented by formula (2) with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 35 mol%, more preferably 30 mol %, more preferably 20 mol %, even more preferably 15 mol % or 10 mol %.
• the compound represented by formula (2) with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol% or more and 30 mol% or less, more preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.2 mol% or more and 10 mol% or less, even more preferably 0.5 mol% or more and 10 mol% or less, particularly preferably 1 mol% or more and 10 mol% or less
• it is 2 mol % or more and 10 mol % or less, or 5 mol % or more and 10 mol % or less.
• the content of the compound represented by the above formula (1) or (2) is preferably 0.1 to 50.0% by mass, more preferably 1.0% by mass, based on the total composition. to 30.0% by mass, more preferably 5.0 to 25.0% by mass, particularly preferably 10.0 to 20.0% by mass.
• the content of the compound represented by the above formula (1) or (2) is preferably 0.001 to 30% by mass, more preferably 0.01 to 10% by mass, based on the total composition. % by weight, more preferably 0.05 to 5% by weight, particularly preferably 0.05 to 2% by weight.
• the composition of the present disclosure contains at least one compound consisting of a siloxane-containing silane compound and a condensate in which at least a portion of the siloxane-containing silane compound is condensed.
• compositions of the present disclosure comprise R 71 OR 72 , R 73 n8 C 6 H 6-n8 , R 74 R 75 R 76 Si—(O—SiR 77 R 78 ) m8 -R 79 , and ( OSiR77R78 ) m9
• R 71 to R 79 are each independently a monovalent organic group having 1 to 10 carbon atoms
• m8 is an integer from 1 to 6
• m9 is an integer from 3 to 8
• n8 is an integer of 0-6.
• the monovalent organic group having 1 to 10 carbon atoms may be linear or branched, and may contain a cyclic structure.
• the monovalent organic group having 1 to 10 carbon atoms may contain an oxygen atom, a nitrogen atom, or a halogen atom.
• the monovalent organic group having 1 to 10 carbon atoms does not contain a halogen atom.
• the monovalent organic group having 1 to 10 carbon atoms is a hydrocarbon group optionally substituted with halogen, preferably a hydrocarbon group not substituted with halogen.
• the hydrocarbon group is linear.
• the hydrocarbon group is branched.
• the hydrocarbon group contains a cyclic structure.
• the solvent is R 71 OR 72 .
• R 71 and R 72 may each independently be preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably a C 1-6 alkyl group, or a C 5-8 cycloalkyl group.
• the solvent is R 73 n8 C 6 H 6-n8 .
• C 6 H 6-n8 is an n8-valent benzene ring.
• R 73 n8 C 6 H 6-n8 is benzene substituted with n8 R 73s .
• Each R 73 can be independently a halogen or a C 1-6 alkyl group optionally substituted by halogen.
• n8 is preferably an integer of 1-3.
• the solvent is R 74 R 75 R 76 Si—(O—SiR 77 R 78 ) m8 -R 79 .
• the solvent is (OSiR 77 R 78 ) m9 .
• (OSiR 77 R 78 ) m9 is a cyclic siloxane formed by cyclically bonding a plurality of OSiR 77 R 78 units.
• R 74 to R 79 are each independently a hydrogen atom or a C 1-6 alkyl group, preferably a C 1-6 alkyl group, more preferably a C 1-3 alkyl group, still more preferably a methyl group is.
• m8 is preferably an integer of 1-6, more preferably an integer of 1-5, and still more preferably 1-2.
• m9 is preferably an integer of 3-6, more preferably an integer of 3-5.
• the solvent is hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octaethyltrisiloxane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane. siloxane, decamethylcyclopentasiloxane.
• composition of the present disclosure is preferably a surface treatment agent.
• the surface treatment agent of the present disclosure includes a solvent, a (non-reactive) silicone compound that can be understood as a silicone oil (hereinafter referred to as "silicone oil”), an amine compound, alcohols, a catalyst, a surfactant, and a polymerization inhibitor. , sensitizers and the like.
• solvent examples include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha.
• aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits
• aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha.
• silicone oil is not particularly limited, for example, general formula (3) below: R 1a —(SiR 3a 2 —O) a1 —SiR 3a 2 —R 1a (3)
• each occurrence of R 1a is independently a hydrogen atom or a hydrocarbon group
• each occurrence of R 3a is independently a hydrogen atom or a hydrocarbon group
• a1 is 2 to 3000;
• the compound represented by is mentioned.
• R 3a is independently a hydrogen atom or a hydrocarbon group. Such hydrocarbon groups may be optionally substituted.
• R 3a is independently at each occurrence preferably an unsubstituted hydrocarbon group or a hydrocarbon group substituted by a halogen atom.
• halogen atoms are preferably fluorine atoms.
• R 3a is independently preferably a C 1-6 alkyl or aryl group optionally substituted by a halogen atom, more preferably a C 1-6 alkyl or aryl group.
• the C 1-6 alkyl group may be linear or branched, but is preferably linear.
• the C 1-6 alkyl group is preferably a C 1-3 alkyl group, more preferably a methyl group.
• the aryl group is preferably a phenyl group.
• R 3a is independently at each occurrence a C 1-6 alkyl group, preferably a C 1-3 alkyl group, more preferably a methyl group.
• R 3a is a phenyl group.
• R 3a is a methyl group or a phenyl group, preferably a methyl group.
• R 1a above is independently a hydrogen atom or a hydrocarbon group, and has the same meaning as R 3a above.
• R 1a is independently preferably a C 1-6 alkyl or aryl group optionally substituted by a halogen atom, more preferably a C 1-6 alkyl or aryl group.
• R 1a is independently at each occurrence a C 1-6 alkyl group, preferably a C 1-3 alkyl group, more preferably a methyl group.
• R 1a is a phenyl group.
• R 1a is a methyl group or a phenyl group, preferably a methyl group.
• a1 is 2 to 1500.
• a1 can be preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, for example 30 or more, or 50 or more.
• a1 can be preferably 1000 or less, more preferably 500 or less, even more preferably 200 or less, even more preferably 150 or less, for example 100 or less, or 80 or less.
• a1 can be preferably 5-1000, more preferably 10-500, even more preferably 15-200, still more preferably 15-150.
• the silicone oil may have an average molecular weight of 500-100,000, preferably 1,000-10,000.
• the molecular weight of silicone oil can be measured using GPC.
• silicone oil for example, linear or cyclic silicone oil in which a1 of —(SiR 3a 2 —O) a1 — is 30 or less can be used.
• Linear silicone oils may be so-called straight silicone oils and modified silicone oils.
• straight silicone oils include dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil.
• Modified silicone oils include those obtained by modifying straight silicone oils with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
• Cyclic silicone oil includes, for example, cyclic dimethylsiloxane oil.
• the above silicone oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0.001 to 30% by mass, more preferably 0.1 to 5% by mass, relative to the surface treatment agent of the present disclosure.
• the amount of such silicone oil is, for example, 0 to 100 parts by mass of the siloxane group-containing silane compound of the present disclosure (the sum of these when two or more are used, the same applies hereinafter). 300 parts by weight, preferably 50 to 200 parts by weight.
• Silicone oil contributes to improving the surface lubricity of the surface treatment layer.
• the alcohols include alcohols having 1 to 6 carbon atoms which may be substituted with one or more fluorine atoms, such as methanol, ethanol, iso-propanol, tert-butanol, CF 3 CH 2 OH, CF 3 CF 2 CH 2 OH, (CF 3 ) 2 CHOH.
• the catalyst examples include acids (eg, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc.), bases (eg, sodium hydroxide, potassium hydroxide, ammonia, triethylamine, diethylamine etc.), transition metals (e.g.
• acids eg, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc.
• bases eg, sodium hydroxide, potassium hydroxide, ammonia, triethylamine, diethylamine etc.
• transition metals e.g.
• Examples of the aliphatic amine compound include diethylamine and triethylamine.
• Examples of the aromatic amine compound include aniline and pyridine.
• the transition metal is contained as a transition metal compound represented by MR (wherein M is a transition metal atom and R is a hydrolyzable group).
• M is a transition metal atom and R is a hydrolyzable group.
• the hydrolyzable group means a group capable of undergoing a hydrolysis reaction, in the same manner as the hydrolyzable group related to the silane compound containing a siloxane group. means.
• the hydrolyzable group is -OR m , preferably methoxy or ethoxy.
• an alkoxy group as the hydrolyzable group, transition metal atoms can be contained in the surface treatment layer more efficiently, and the friction durability and chemical resistance of the surface treatment layer can be further improved.
• the hydrolyzable group may be the same as the hydrolyzable group contained in the siloxane group-containing silane compound described above.
• the hydrolyzable group in the siloxane group-containing silane compound and the transition metal compound even if such hydrolyzable groups are mutually exchanged, the effect thereof can be reduced.
• the hydrolyzable group may be different from the hydrolyzable group contained in the silane compound containing the siloxane group described above.
• the reactivity of hydrolysis can be controlled.
• the hydrolyzable group and the hydrolyzable group contained in the siloxane group-containing silane compound may be replaced with each other in the surface treatment agent.
• the transition metal compound is Ta(OR m ) 5 , preferably Ta(OCH 2 CH 3 ) 5 .
• the catalyst may be contained, for example, at 0.0002% by mass or more with respect to the entire surface treatment agent.
• the content of the catalyst is preferably 0.02% by mass or more, more preferably 0.04% by mass or more, relative to the entire surface treatment agent.
• the catalyst may be contained in an amount of, for example, 10% by mass or less, particularly 1% by mass or less, relative to the entire surface treatment agent.
• the surface treatment agent of the present disclosure can contribute to the formation of a surface treatment layer with better durability by including the above concentration of the catalyst.
• the content of the catalyst is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass, relative to the siloxane group-containing silane compound of the present disclosure.
• the catalyst promotes hydrolysis and dehydration condensation of the siloxane group-containing silane compound of the present disclosure and promotes formation of a layer formed by the surface treatment agent of the present disclosure.
• Other components include, in addition to the above, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.
• the surface treatment agent of the present disclosure contains trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates. obtain.
• the surface treatment agent of the present disclosure provides a surface with a surface free energy of 18 to 35 mN/m calculated from the contact angle between water and n-hexadecane when the substrate is treated.
• the surface free energy is preferably 20 mN/m or more, more preferably 22 mN/m or more, still more preferably 24 mN/m or more, preferably 33 mN/m or less, more preferably 30 mN/m or less, and still more preferably 28 mN. /m or less, and more preferably 26 mN/m or less.
• the surface free energy is obtained by measuring the respective contact angles ( ⁇ 1 and ⁇ 2) of the substrate surface with a contact angle meter using water and n-hexadecane, and then using the following formula to calculate the contact angle value and water and n ⁇ Sd and ⁇ Sp are obtained by substituting the values of the surface free energy of hexadecane and solving the simultaneous equations consisting of the two obtained equations.
• the sum of ⁇ Sd and ⁇ Sp is the surface free energy ⁇ S of the substrate surface.
• the surface treatment agent of the present disclosure is a dry coating method, preferably applied over vacuum.
• the surface treatment agent of the present disclosure is for wet coating methods, preferably dip coating.
• the surface treatment agent of the present disclosure can be made into pellets by impregnating a porous material, such as a porous ceramic material, metal fiber, such as steel wool, into a flocculated material.
• a porous material such as a porous ceramic material, metal fiber, such as steel wool
• the pellet can be used, for example, for vacuum deposition.
• the article of the present disclosure includes a base material and a layer (surface treatment layer) formed on the surface of the base material from the surface treatment agent of the present disclosure.
• Substrates that can be used in the present disclosure include, for example, glass, resins (natural or synthetic resins, such as common plastic materials), metals, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, non-woven fabrics etc.), fur, leather, wood, ceramics, stone, etc., construction members, etc., sanitary products, and any suitable material.
• resins natural or synthetic resins, such as common plastic materials
• metals such as common plastic materials
• ceramics such as common plastic materials
• semiconductors silicon, germanium, etc.
• fibers woven fabrics, non-woven fabrics etc.
• fur leather, wood, ceramics, stone, etc., construction members, etc., sanitary products, and any suitable material.
• the material forming the surface of the substrate may be a material for optical members, such as glass or transparent plastic.
• some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate.
• the antireflection layer may be either a single antireflection layer or a multi-layer antireflection layer. Examples of inorganic materials that can be used for the antireflection layer include SiO2 , SiO, ZrO2 , TiO2 , TiO , Ti2O3 , Ti2O5 , Al2O3 , Ta2O5 , Ta3O5 .
• the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on part of the surface of the substrate (glass).
• a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on part of the surface of the substrate (glass).
• the substrate may be an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase retardation film, and a liquid crystal display module.
• I-CON decorative frame layer
• the shape of the base material is not particularly limited, and may be, for example, plate-like, film, or other forms.
• the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the application and specific specifications of the article to be manufactured.
• At least the surface portion of such a substrate may consist of a material that originally has hydroxyl groups.
• materials include glass, metals (particularly base metals), ceramics, and semiconductors on which a natural oxide film or thermal oxide film is formed.
• hydroxyl groups are introduced onto the surface of the base material by subjecting the base material to some pretreatment. can be increased or increased.
• pretreatment include plasma treatment (eg, corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface, and can also be suitably used to clean the substrate surface (remove foreign matter and the like).
• an interfacial adsorbent having a carbon-carbon unsaturated bond group is preliminarily formed on the substrate surface by a monomolecular film by the LB method (Langmuir-Blodgett method), a chemical adsorption method, or the like.
• LB method Liuir-Blodgett method
• a chemical adsorption method or the like.
• such a substrate may comprise, at least a portion of its surface, another reactive group, such as a silicone compound having one or more Si—H groups, or a material comprising an alkoxysilane. .
• the substrate is glass.
• glass sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, and chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glasses are particularly preferred.
• the article of the present disclosure is produced by forming a layer of the surface treatment agent of the present disclosure on the surface of the substrate, and post-treating this layer as necessary, thereby forming a layer from the surface treatment agent of the present disclosure. It can be manufactured by forming.
• the layer formation of the surface treatment agent of the present disclosure can be carried out by applying the surface treatment agent to the surface of the substrate so as to coat the surface.
• a coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.
• wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, wipe coating, squeegee coating, die coating, inkjet, casting, Langmuir-Blodgett and similar methods. mentioned.
• Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD and similar methods.
• vapor deposition methods usually vacuum vapor deposition methods
• Specific examples of vapor deposition methods include resistance heating, electron beams, high-frequency heating using microwaves, ion beams, and similar methods.
• Examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.
• the surface treatment agents of the present disclosure may be diluted with a solvent prior to application to the substrate surface.
• a solvent preferably used: aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits.
• Aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, Carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 2-hydroxy esters such as methyl isobutyrate and ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobut
• solvents can be used alone or as a mixture of two or more.
• hydrofluoroethers are preferred, and perfluorobutyl methyl ether ( C4F9OCH3 ) and/or perfluorobutylethyl ether ( C4F9OC2H5 ) and siloxanes are particularly preferred .
• Hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, or decamethylcyclopentasiloxane are more preferred.
• the surface treatment agent of the present disclosure may be subjected to the dry coating method as it is, or may be subjected to the dry coating method after being diluted with the solvent described above.
• the layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent of the present disclosure is present in the layer together with the catalyst for hydrolysis and dehydration condensation.
• the catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure after the surface treatment agent of the present disclosure has been diluted with a solvent, just prior to application to the substrate surface.
• the surface treatment agent of the present disclosure to which the catalyst has been added is vapor-deposited (usually, vacuum deposition) as it is, or the surface treatment agent of the present disclosure to which the catalyst is added is applied to a metal porous body such as iron or copper.
• a vapor deposition (usually vacuum vapor deposition) process may be performed using a pellet-shaped material impregnated with .
• Catalysts include any suitable acid or base, transition metals (e.g. Ti, Ni, Sn, Zr, Al, B, etc.), sulfur-containing compounds having a lone pair of electrons in their molecular structure, or nitrogen-containing compounds (e.g. sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphoramide compounds, amide compounds, urea compounds) and the like can be used.
• transition metals e.g. Ti, Ni, Sn, Zr, Al, B, etc.
• sulfur-containing compounds having a lone pair of electrons in their molecular structure e.g. sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphoramide compounds, amide compounds, urea compounds
• nitrogen-containing compounds e.g. sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphoramide compounds, amide compounds, urea compounds
• acid catalysts that can be used include
• a base catalyst for example, ammonia, organic amines such as sodium hydroxide, potassium hydroxide, triethylamine, diethylamine, and the like can be used.
• organic amines such as sodium hydroxide, potassium hydroxide, triethylamine, diethylamine, and the like can be used.
• transition metals, aliphatic amine compounds, and aromatic amine compounds are the same as those described above.
• the surface treatment layer included in the article of the present disclosure has both high abrasion resistance.
• the surface treatment layer has water repellency, oil repellency, and antifouling properties (for example, it prevents the adhesion of stains such as fingerprints), depending on the composition of the surface treatment agent used.
• Waterproofness prevents water from penetrating into electronic parts, etc.
• surface slipperiness or lubricity, such as wiping off of fingerprints and other stains, excellent touch feeling on fingers
• chemical resistance etc. It can be suitably used as a functional thin film.
• the present disclosure also relates to an optical material having the surface treatment layer as the outermost layer.
• optical materials in addition to optical materials related to displays and the like as exemplified later, a wide variety of optical materials are preferably exemplified: for example, cathode ray tubes (CRT; e.g., personal computer monitors), liquid crystal displays, plasma displays, organic EL. Displays such as displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), field emission displays (FED; Field Emission Display), protective plates for these displays, or antireflection films on their surfaces processed.
• CTR cathode ray tubes
• LCD liquid crystal displays
• plasma displays organic EL.
• Displays such as displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), field emission displays (FED; Field Emission Display), protective plates for these displays, or antireflection films on their surfaces processed.
• VFD fluorescent display tubes
• FED Field Emission Display
• optical members include the following: lenses for eyeglasses; front protective plates, antireflection plates, polarizing plates, anti-glare plates for displays such as PDP and LCD; touch panel sheets; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers;
• the articles of the present disclosure may be medical devices or medical materials.
• An article having a layer obtained by the present disclosure may also be an automobile interior or exterior member.
• exterior materials include: windows, light covers, exterior camera covers.
• interior materials include: instrument panel covers, navigation system touch panels, decorative interior materials.
• the thickness of the layer is not particularly limited. In the case of optical members, the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, preferably 1 to 15 nm, from the viewpoint of optical performance, abrasion resistance and antifouling properties.
• Example 2 R-CON(CH 2 CH ⁇ CH 2 ) 2 (2 g), toluene (10 mL), Karstedt's catalyst in xylene (2%, 0.20 mL), aniline (32 mg), and trimethoxysilane (1.00 mL) ), stirred overnight at room temperature, and concentrated under reduced pressure to give R-CON ⁇ CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ⁇ 2 (2.23 g).
• R is (CH 3 ) 3 Si—(OSi(CH 3 ) 2 ) n —(CH 2 ) 10 —.
• the average number of repeating units n is 19.
• Synthesis example 4 R—CH 2 OH (201 g, X-22-170DX, Shin-Etsu Chemical Co., Ltd.), acetone (400 mL) and saturated aqueous sodium hydrogencarbonate solution (100 mL) were mixed and cooled to 0° C. with ice water. Potassium bromide (1.02 g) and TEMPO (0.210 g) were added while the mixture was stirred at 0°C. After stirring for 10 minutes, trichloroisocyanuric acid (19.9 g) was added. The temperature was gradually raised to room temperature and the mixture was stirred overnight. Isopropyl alcohol (200 mL) was added to the mixture and the volatile components were concentrated under reduced pressure.
• R-COOH (180 g).
• R is CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 —(OSi(CH 3 ) 2 ) n —(CH 2 ) 3 —OCH 2 —.
• the average number of repeating units n is 57.
• R is CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 —(OSi(CH 3 ) 2 ) n —(CH 2 ) 3 —OCH 2 —, and the average number of repeating units n is , 57.
• Example 5 R-CONH-CH 2 C(CH 2 CH ⁇ CH 2 ) 3 (1 g) obtained in Synthesis Example 5, toluene (5 mL), xylene solution of Karstedt's catalyst (2%, 94 ⁇ L), (CH 3 COO ) 3 SiCH 3 (3.6 mg) and trichlorosisilane (0.25 mL) were mixed. The mixture was stirred at 60° C. for 4 hours and then concentrated under reduced pressure to give R—CONH—CH 2 C ⁇ CH 2 CH 2 CH 2 SiCl 3 ⁇ 3 (0.9 g). R is CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 ) n —(CH 2 ) 3 —OCH 2 —, and the average number of repeating units n is 57; be.
• Synthesis example 6 R—CH ⁇ CH 2 (5 g, Gelest, MCR-V21), toluene (5 g), trichlorosilane (0.31 g), and a xylene solution of Karstedt's catalyst (2%, 32 ⁇ L) were mixed and heated at 60° C. Stirred for 4 hours. After allowing to cool to room temperature and distilling off the solvent under reduced pressure, the residue was dissolved in tetrahydrofuran (5 g), and allylmagnesium chloride (1.0 mol/L, 4.4 mL) was added under ice-cooling. After the temperature was raised to room temperature and the mixture was stirred for 17 hours, a saturated aqueous sodium chloride solution was added.
• R--CH 2 CH 2 Si(CH 2 CH ⁇ CH 2 ) 3 (4.7 g).
• R is CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 ) n —, and the average number of repeating units n is 57.
• Example 6 R—CH 2 CH 2 Si(CH 2 CH ⁇ CH 2 ) 3 (2.5 g) obtained in Synthesis Example 6, toluene (2.5 mL), xylene solution of Karstedt catalyst (2%, 0.10 mL ), aniline (16 mg), and trimethoxysisilane (0.52 mL) were mixed. The mixture was stirred overnight at room temperature and then concentrated under reduced pressure to give R—CH 2 CH 2 Si(CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ) 3 (2.5 g). R is CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 ) n —, and the average number of repeating units n is 57.
• Synthesis example 7 R—CH ⁇ CH 2 (5 g, Gelest, MCR-V25), toluene (5 g), trichlorosilane (0.27 g), and a xylene solution of Karstedt's catalyst (2%, 76 ⁇ L) were mixed and heated at 60° C. Stirred for 4 hours. After allowing to cool to room temperature and distilling off the solvent under reduced pressure, the residue was dissolved in tetrahydrofuran (5 g), and allylmagnesium chloride (1.0 mol/L, 2.2 mL) was added under ice-cooling. After the temperature was raised to room temperature and the mixture was stirred for 17 hours, a saturated aqueous sodium chloride solution was added.
• R--CH 2 CH 2 Si(CH 2 CH ⁇ CH 2 ) 3 (4.2 g).
• R is CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 ) n —, and the average number of repeating units n is 200.
• Example 7 R—CH 2 CH 2 Si(CH 2 CH ⁇ CH 2 ) 3 (3.6 g) obtained in Synthesis Example 7, toluene (4 mL), xylene solution of Karstedt catalyst (2%, 54 ⁇ L), aniline ( 9 mg), and trimethoxysisilane (0.27 mL) were mixed. The mixture was stirred overnight at room temperature and then concentrated under reduced pressure to give R—CH 2 CH 2 Si(CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ) 3 (3.3 g). R is CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 ) n —, and the average number of repeating units n is 200.
• R-[CH 2 CH 2 Si ⁇ CH 2 CH CH 2 ⁇ 3 ] 2 (4.4 g).
• R is -Si(CH 3 ) 2 (OSi(CH 3 ) 2 ) n -, and the average number of repeating units n is 52.
• Synthesis example 9 2,2-diallyl-4-penten-1-amine (2 g), triethylene glycol 2-bromoethyl methyl ether (8.9 g), 1,8-diazabicyclo[5.4.0]-7-undecene (5 .0 g) was dissolved in cyclopentyl methyl ether (6 mL) and stirred at 80° C. for 6 hours. After cooling to about room temperature, the mixture was washed with an aqueous sodium hydrogencarbonate solution and water, and concentrated under reduced pressure to obtain PG-NHCH 2 C(CH 2 CH ⁇ CH 2 ) 3 (2.9 g). PG is CH 3 (OCH 2 CH 2 ) 4 —.
• R is CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 —(OSi(CH 3 ) 2 ) n —(CH 2 ) 3 —OCH 2 —
• PG is CH 3 (OCH 2 CH 2 ) 4 —, and the average number of repeating units n is 57.
• R is CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 ) n —(CH 2 ) 3 —OCH 2 —, and PG is CH 3 (OCH 2 CH 2 ) 4- , and the average number of repeating units n is 57;
• R is CH 3 (CH 2 ) 3 —(Si(CH 3 )O) n —Si(CH 3 ) 2 —(CH 2 ) 3 —O—(CH 2 ) 2 —.
• the average number of repeating units n is 78.
• Example 10 The compound (5 g) obtained in Synthesis Example 11, toluene (30 mL), a xylene solution of Karstedt's catalyst (2%, 0.17 mL), aniline (29 mg), and trimethoxysilane (0.9 mL) were mixed. , and the mixture was stirred overnight at room temperature, and then concentrated under reduced pressure to obtain the following compound.
• the average number of repeating units n is 78.
• R is -SiPh 2 (OSiPh 2 ) m -(OSi(CH 3 ) 2 ) n -, and the average values of the number of repeating units m and n are 26 and 87, respectively.
• Example 11 R-(CH 2 CH 2 Si(CH 2 CH ⁇ CH 2 ) 3 ) 2 (3 g) obtained in Synthesis Example 12, toluene (6 mL), xylene solution of Karstedt's catalyst (2%, 0.11 mL) , aniline (18 mg), and trimethoxysisilane (0.55 mL) were mixed. The mixture was stirred overnight at room temperature and then concentrated under reduced pressure to give R-[CH 2 CH 2 Si ⁇ CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ⁇ 3 ] 2 (2.8 g). R is -SiPh 2 (OSiPh 2 ) m -(OSi(CH 3 ) 2 ) n -, and the average values of the number of repeating units m and n are 26 and 87, respectively.
• Example 12 R-CON(CH 2 CH ⁇ CH 2 ) 2 (1.7 g) obtained in Synthesis Example 13, toluene (1.7 g), Karstedt's catalyst xylene solution (2%, 0.20 mL), pyridine ( 10 mg) and trimethoxysilane (0.32 mL) were mixed, stirred overnight at room temperature, and concentrated under reduced pressure to give R-CON ⁇ CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ⁇ 2 (1. 97 g).
• R is CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 —(OSi(CH 3 ) 2 ) n —(CH 2 ) 3 —OCH 2 —.
• the average number of repeating units n is 57.
• Comparative example 1 The following compounds were synthesized according to the method described in JP-A-2019-44179. CH 3 O(CH 2 CH 2 O) n ⁇ 1 CH 2 C(O)NHCH 2 C ⁇ CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ⁇ 3 The average number of repeating units n is 22.
• Comparative example 3 (CH 3 ) 3 Si—(OSi(CH 3 ) 2 ) n —(CH 2 ) 10 —CONH—CH 2 CH ⁇ CH 2 obtained in Synthesis Example 13 above according to the method described in JP-A-2014-84405. (The average value of the repeating unit number n is 19) was used to synthesize the following compounds.
• R is (CH 3 ) 3 Si—(OSi(CH 3 ) 2 ) n —(CH 2 ) 10 —.
• the average number of repeating units n is 19.
• the contact angle was measured using a fully automatic contact angle meter DropMaster 700 (manufactured by Kyowa Interface Science Co., Ltd.) in an environment of 25°C. Specifically, the base material having the surface treatment layer to be measured is placed horizontally, water is dropped on the surface from a microsyringe, and a still image is taken with a video microscope 1 second after the drop. contact angle was measured. The static contact angle was measured at five different points on the surface treatment layer of the base material, and a value obtained by calculating the average value was used. The contact angle of oleic acid was measured with a liquid volume of 2 ⁇ L 4 seconds after the liquid was applied.
• ⁇ Fingerprint wiping off evaluation> After forming a surface treatment layer by the method described in ⁇ Formation of surface treatment layer> using surface treatment agents 5, 6, and 11 to 13, the surplus on the substrate surface was wiped off and used as an evaluation sample. bottom. Sebum was attached to the evaluation sample with a force of 27N. Next, the fingerprint mark on the surface layer of the evaluation sample was attached to a 1 kg cylindrical weight with Bencoat M-3II, and was reciprocated 10 times in one direction under the following conditions to wipe off the fingerprint on the surface layer. was measured with a Haze meter. The results are shown in Table 4 below.
• Wiping cloth Bemcot M-3II (product name, manufactured by Asahi Kasei Corporation) Travel distance (one way): 60mm Movement speed: 8,400 mm/min Load: 1000 g/3 cm 2 ⁇ (Excellent): Fingerprints are hardly visible ⁇ (Good): Fingerprints are slightly visible ⁇ (Acceptable): Fingerprints are faint but clearly visible. x (defective): clearly visible.
• the surface treatment agent of the present disclosure can be suitably used for various applications.

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