Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • 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
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
• • 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
  • 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

• k1 is a number from 1 to 600.
• Each R3 is independently a hydrocarbon group;
• Each k1 is independently a number of 1 or more, p1 is an integer of 1 or more, A 11 is a (p1+1)-valent linking group,
• Each R2 is independently a hydrocarbon group;
• L each independently represents a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group;
• n is an integer from 0 to 2.
• B 11 is a monovalent group containing at least one selected from the group consisting of Si, Ge, and Sn to which a hydroxyl group or a hydrolyzable group is not directly bonded; or a monovalent group containing a branched alkyl group, with the proviso that B 11 does not contain a reactive silyl group, u1 is an integer of 1 or more, A 15 is a (u1+1)-valent linking group, Each R2 is independently a hydrocarbon group; Each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; Each n is independently an integer of 0 to 2.
• Each R3 is independently a hydrocarbon group;
• Each k1 is independently a number of 1 or more, p1 is an integer of 1 or more, A 12 is a (p1+q1)-valent linking group, q1 is an integer of 2 or more,
• Each R2 is independently a hydrocarbon group;
• Each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group;
• Each n is independently an integer of 0 to 2.
• Each L2 independently represents a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; Among L2 , at least four L2 are a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; Each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides, Each r1 is independently an integer from 1 to 3; The definitions of B 11 , u1, A 16 and q1 are the same as those in formula (C2-3).
• q1 is an integer of 2 to 4.
• R 4 is independently a hydrocarbon group or T 11 -B r -(SiR 3 2 -O) k1 -;
• T 11 is independently a monovalent group;
• Each r is independently 0 or 1;
• Each R3 is independently a hydrocarbon group;
• Each k1 is independently a number of 1 or more,
• Each A 13 independently represents a divalent linking group,
• Each R2 is independently a hydrocarbon group;
• Each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group;
• Each n is independently an integer of 0 to 2.
• Each L2 independently represents a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; Among L2 , at least four L2 are a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; Each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides, Each r1 is independently an integer from 1 to 3; The definitions of R 4 , k1, and A 13 are the same as those in formula (C3).
• a reactive silyl group linked to a linear organo(poly)siloxane residue means a reactive silyl group that is linked to the linear organo(poly)siloxane residue directly or indirectly via another chemical structure.
• “Me” may refer to a methyl group.
• the explanation of the "third compound” also applies when the “third compound” is read as "a compound having a linear organo(poly)siloxane residue and one reactive silyl group linked to each of both ends of the linear organo(poly)siloxane residue” unless there is a contradiction.
• the explanation of the "fourth compound” also applies when the “fourth compound” is read as "a compound having a linear organo(poly)siloxane residue and two or more reactive silyl groups linked to each of both ends of the linear organo(poly)siloxane residue", unless there is a contradiction.
• the composition of the present disclosure can form a surface treatment layer having excellent light resistance when applied to a substrate as a surface treatment agent.
• the first compound has one reactive silyl group at one end of a divalent chain group (e.g., a chain organo(poly)siloxane residue), and the second compound has two or more reactive silyl groups at one end of a divalent chain group (e.g., a chain organo(poly)siloxane residue).
• the third compound has one reactive silyl group at each end of a divalent chain group (e.g., a chain organo(poly)siloxane residue), and the fourth compound has two or more reactive silyl groups at each end of a divalent chain group (e.g., a chain organo(poly)siloxane residue).
• R d is a hydrogen atom or an alkyl group (preferably having
• the first compound contains two or more linear organo(poly)siloxane residues
• the second compound contains two or more linear organo(poly)siloxane residues, there is no linear organo(poly)siloxane residue having reactive silyl groups linked to both terminal sides, and at least one linear organo(poly)siloxane residue has two or more reactive silyl groups linked to one terminal side.
• k1 is a number of 1 or more, preferably a number from 1 to 600, more preferably a number from 1 to 500, even more preferably a number from 3 to 500, particularly preferably a number from 9 to 50, extremely preferably a number from 11 to 30, and most preferably a number from 11 to 25.
• T 11 is each independently a monovalent group, and specific embodiments are the same as T 11 in formulas (C1), (C1-2), (C2), and (C2-2) described later.
• Specific embodiments of B and r are the same as those of B and r in the formulae (C1), (C1-2), (C2), and (C2-2) described later.
• the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.
• the aryloxy group is preferably an aryloxy group having 3 to 10 carbon atoms. However, the aryl group of the aryloxy group includes a heteroaryl group.
• the halogen atom is preferably a chlorine atom.
• the acyl group is preferably an acyl group having 1 to 6 carbon atoms.
• the acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.
• Each R r is independently an alkyl group having 1 to 10 carbon atoms.
• L2 is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably an ethoxy group or a methoxy group.
• the hydrocarbon group represented by L2 include an alkyl group, a cycloalkyl group, an alkenyl group, an allyl group, etc., and from the viewpoint of ease of synthesis, etc., a saturated hydrocarbon group is preferable, and an alkyl group is more preferable.
• the number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.
• T 11 -B r -[Si(R 3 ) 2 -O] k1 -Si(R 3 ) 2 may be the same or different from each other.
• T 11 is a monovalent group.
• T 11 include an alkyl group, T 1 3 M 1 - (wherein M 1 is Si, Sn, or Ge, and each T 1 is independently a hydrocarbon group or a trialkylsilyloxy group), T 1 3 M 1 -R 1 - (wherein M 1 is Si, Sn, or Ge, and each T 1 is independently a hydrocarbon group or a trialkylsilyloxy group, and R 1 is an alkylene group), a monovalent cyclic polysiloxane residue or a monovalent cage polysiloxane residue, and a combination of a monovalent cyclic polysiloxane residue or a monovalent cage polysiloxane residue with a divalent hydrocarbon group.
• Si is preferable.
• T 1 in T 1 3 M 1 - and T 1 3 M 1 -R 1 - is preferably an alkyl group or a trialkylsilyloxy group, more preferably a methyl group, a butyldimethylsilyloxy group, a trimethylsilyloxy group or a triethylsilyloxy group.
• the alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferred.
• the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 4.
• the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and more preferably a methyl group.
• Examples of the hydrocarbon group contained in the hydrocarbon group having a substituent represented by R T include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
• the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group.
• the alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferred.
• the number of carbon atoms in the alkyl group contained in the substituted alkyl group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 2 to 4.
• the monovalent cage-shaped polysiloxane residue is preferably a group represented by the following formula (T2).
• T2 Each R5 is independently a hydrocarbon group or a trialkylsilyloxy group.
• the alkyl group contained in the trialkylsilyloxy group represented by R5 may be any one of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but is preferably a linear alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and even more preferably a methyl group.
• R5 is a trialkylsilyloxy group
• the three alkylsilyloxy groups may be the same or different from each other, but are preferably the same from the viewpoint of ease of production.
• p1 is an integer of 1 or more, preferably an integer from 1 to 3, more preferably 1 or 2, and even more preferably 1.
• Each L2 independently represents a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; Among L2 , at least four L2 are a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; Each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides, r1 is an integer from 1 to 3; The definitions of T 11 , B, r, R 3 , k1, p1, and A 11 are the same as those in formula (C1).
• T 11 , B, r, R 3 , k1, p1, and A 11 are the same as those in formula (C1).
• specific embodiments of L 2 , P and r1 are the same as those of L 2 , P and r1 in formula (S3).
• the first compound is preferably a compound represented by the following formula (C1-3).
• B11 is a monovalent group containing at least one selected from the group consisting of Si, Ge, and Sn to which a hydroxyl group or a hydrolyzable group is not directly bonded; or a monovalent group containing a branched alkyl group.
• the monovalent group containing at least one selected from the group consisting of Si, Ge, and Sn to which a hydroxyl group or a hydrolyzable group is not directly bonded may or may not contain Si, Ge, or Sn to which a hydroxyl group or a hydrolyzable group is directly bonded.
• the alkylene group having 1 to 6 carbon atoms in R 61 may be a straight chain or a branched chain.
• the alkylene group having 1 to 6 carbon atoms is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
• the chain hydrocarbon group may be a straight-chain or branched chain hydrocarbon group having 2 to 100 carbon atoms, preferably 5 to 90 carbon atoms, and more preferably 10 to 80 carbon atoms.
• the chain hydrocarbon group is preferably an alkylene group, and from the viewpoint of forming a surface treatment layer having excellent acid resistance, hot water resistance, abrasion resistance, etc., the chain hydrocarbon group is preferably an alkylene group having 13 or more carbon atoms.
• M 31 is Sn or Ge.
• M 31 is preferably Ge because Ge has a larger atomic size than Sn, can reduce the surface free energy more, and can form a surface treatment layer with excellent fingerprint removability.
• R 31 is a hydrocarbon group or a trialkylsilyloxy group.
• the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group, and from the viewpoint of ease of synthesis, a saturated hydrocarbon group is preferable, and an alkyl group is more preferable.
• the number of carbon atoms in R 31 is preferably 1 to 6, more preferably 1 to 3, and among these, -CH 3 or -CH 2 CH 3 is preferable.
• the trialkylsilyloxy group is preferably a group represented by -O-SiR 40 3. Each R 40 is independently a hydrocarbon group.
• the hydrocarbon group in R 40 is preferably an alkyl group or an aryl group, more preferably an alkyl group.
• the number of carbon atoms in R 40 is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.
• Specific examples of the hydrocarbon group in R 40 include -CH 3 , -CH 2 CH 3 , and -C(CH 3 ) 3 .
• linear organo(poly)siloxane residue examples include the examples described above as the linear organo(poly)siloxane residues in the first compound and the second compound.
• B 11 may be a monovalent group containing a branched alkyl group.
• the branched alkyl group is preferably unsubstituted.
• the branched alkyl group is preferably a tert-butyl group or contains a tert-butyl group.
• the branched alkyl group may contain one branch or may contain multiple branches.
• the number of branches in the branched alkyl group may be 1 to 30, 1 to 20, 1 to 10, or 1 to 5.
• Examples of the monovalent group containing a branched alkyl group include groups in which a chain group is linked to the carbon atom that is the branch point of the branched alkyl group.
• linear organo(poly)siloxane residue examples include the examples described above as the linear organo(poly)siloxane residues in the first compound and the second compound.
• Each L2 independently represents a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; Among L2 , at least four L2 are a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; Each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides, r1 is an integer from 1 to 3; The definitions of B 11 , u1, and A 15 are the same as those in formula (C1-3).
• the second compound is preferably a compound represented by the following formula (C2).
• q1 is preferably 2 to 18, more preferably 2 to 12, even more preferably 2 to 8, particularly preferably 2 to 6, extremely preferably 2 to 4, and most preferably 2 or 3.
• the second compound is preferably a compound represented by the following formula (C2-3).
• R 2 , L, and n are the same as R 2 , L, and n in formula (S1).
• q1 is the same as q1 in formula (C2).
• B 11 and u1 are the same as B 11 and u1 in formula (C1-3).
• a 16 is a (q1+u1)-valent linking group. Specific examples of A 16 include the same as those of A 12 in formula (C2).
• compound (C2-3) include the following compounds.
• sa is preferably 1 to 30, more preferably 4 to 20, and even more preferably 5 to 15.
• the molecular weights of the first compound and the second compound may be relatively close.
• the Mn of both the first compound and the second compound is preferably 500 to 20,000, more preferably 600 to 18,000, and even more preferably 700 to 15,000.
• the Mn of both the first compound and the second compound may be 800 to 5,500, 900 to 4,000, or 1,000 to 2,500.
• the molecular weight of the first compound may be smaller than the molecular weight of the second compound.
• the Mn of the first compound and the second compound are preferably 500 to 20,000 and 1,000 to 40,000, more preferably 600 to 18,000 and 1,200 to 36,000, and even more preferably 700 to 15,000 and 1,400 to 30,000.
• the Mn of the first compound and the second compound may be 800 to 5,500 and 1,600 to 11,000, 900 to 4,000 and 1,800 to 8,000, or 1,000 to 2,500 and 2,000 to 5,000, respectively.
• the third compound is preferably a compound represented by the following formula (C3).
• R4 is preferably a methyl group. It is preferable that k1 is a number from 1 to 100.
• a 13 is preferably an alkylene group having 1 to 30 carbon atoms.
• Each L2 independently represents a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; Among L2 , at least four L2 are a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; Each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides, Each r1 is independently an integer from 1 to 3; The definitions of R 4 , k1, and A 13 are the same as those in formula (C3).
• the fourth compound is preferably a compound represented by the following formula (C4).
• R4 and k1 are the same as R4 and k1 in formula (B2).
• R 2 , L, and n are the same as R 2 , L, and n in formula (S1).
• a 14 examples include A in the group represented by A(Si(R 2 ) n L 3-n ) q described below, where q is an integer of 2 or more.
• a 14 includes a group obtained by removing Si(R 2 ) n L 3-n from formula (3-1A) (wherein h is an integer of 2 or more), a group obtained by removing Si(R 2 ) n L 3-n from formula (3-1B) (wherein y is an integer of 2 or more), a group obtained by removing Si(R 2 ) n L 3-n from group (3-1A-2), a group obtained by removing Si(R 2 ) n L 3-n from group (3-1A-3), a group obtained by removing Si(R 2 ) n L 3-n from group (3-1A- 4 ) (wherein w1 is 0 or 1), a group obtained by removing Si(R 2 ) n L 3-n from group (3-1A-5), a group obtained by removing Si(R 2 ) n L 3-n from
• each q1 is independently preferably 2 to 18, more preferably 2 to 12, even more preferably 2 to 8, particularly preferably 2 to 6, extremely preferably 2 to 4, and most preferably 2 or 3.
• the fourth compound is preferably a compound represented by the following formula (C4-2).
• the molecular weights of the third compound and the fourth compound may be relatively close to each other.
• the Mn of both the third compound and the fourth compound is preferably 500 to 20,000, more preferably 600 to 18,000, and even more preferably 700 to 15,000.
• the Mn of both the third compound and the fourth compound may be 800 to 5,500, 900 to 4,000, or 1,000 to 2,500.
• the molecular weight of the third compound may be greater than the molecular weight of the fourth compound.
• the Mn of the fourth compound and the third compound are preferably 500 to 20,000 and 1,000 to 40,000, more preferably 600 to 18,000 and 1,200 to 36,000, and even more preferably 700 to 15,000 and 1,400 to 30,000.
• composition of the present disclosure may contain impurities such as by-products produced during the manufacturing process of the third compound and/or the fourth compound.
• the total content of the third compound and the fourth compound is preferably 0.001 to 50 mass%, more preferably 0.01 to 20 mass%, and even more preferably 0.1 to 10 mass%, based on the total amount of the composition of the present disclosure.
• the total content of the third compound and the fourth compound may be 0.01 to 10 mass%, 0.02 to 5 mass%, 0.03 to 3 mass%, or 0.05 to 2 mass%, based on the total amount of the composition of the present disclosure.
• the ratio of the third compound to the total content of the third compound and the fourth compound is preferably 3 to 50 mass%, and more preferably 10 to 40 mass%.
• the ratio of the fourth compound to the total content of the third compound and the fourth compound is preferably 50 to 97 mass%, and more preferably 60 to 90 mass%.
• a 11 (Si(R 2 ) n L 3-n ) in formula (C1), A 15 (Si(R 2 ) n L 3-n ) in formula (C1-3), A 12 (Si(R 2 ) n L 3-n ) q1 in formula (C2), A 16 (Si(R 2 ) n L 3-n ) q1 in formula (C2-3), A 13 (Si(R 2 ) n L 3-n ) in formula (C3 ), and A 14 (Si(R 2 ) n L 3-n ) q1 in formula (C4) are described in detail below.
• groups combining two or more of these groups include -OC(O)-, -C(O)O-, -C(O)S-, -C(O)N(R d )-, -N(R d )C(O)-, -N(R d )C(O)N(R d )-, -N(R d )C( O )O-, -OC(O)N(R d )-, -SO 2 N(R d )-, -N(R d )SO 2 -, an alkylene group having -C(O)N(R d )-, an alkylene group having -N(R d )C(O)-, -OC(O)N(R d )-, an alkylene group having an etheric oxygen atom, an alkylene group having -S-, an alkylene group having -OC(O)-, an alkylene group having -C(O
• X 31 is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organo(poly)siloxane residue, or a group having a (h+i+1)-valent ring.
• the alkylene group may have -O-, a silphenylene skeleton group, a divalent organo(poly)siloxane residue, or a dialkylsilylene group.
• the alkylene group may have a plurality of groups selected from the group consisting of -O-, a silphenylene skeleton group, a divalent organo(poly)siloxane residue, and a dialkylsilylene group.
• the alkylene group represented by X 31 preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms.
• Examples of the divalent to octavalent organo(poly)siloxane residue include a divalent organo(poly)siloxane residue and a (w2+1)-valent organo(poly)siloxane residue described below.
• bridged ring a bridged ring having a 5- or 6-membered ring as the maximum ring is preferred, and as the spiro ring, a spiro ring consisting of two 4- to 6-membered rings is preferred.
• assembled polycyclic ring an assembled polycyclic ring in which two or three rings selected from a 5-membered ring and a 6-membered ring are bonded via a single bond, 1 to 3 carbon atoms, or one heteroatom having a valence of 2 or 3 is preferred.
• Preferred rings are a benzene ring, a 5- or 6-membered aliphatic ring, a 5- or 6-membered heterocycle having a nitrogen atom or an oxygen atom, and a condensed ring of a 5- or 6-membered carbocycle and a 4- to 6-membered heterocycle.
• the bond of an atom constituting a ring in X 31 that is not constituting a ring is a bond bonded to Q a , (-Q b -Si(R 2 ) n L 3-n ) or R 31.
• the remaining bond is bonded to a hydrogen atom or a substituent.
• the substituent include a halogen atom, an alkyl group (which may contain an etheric oxygen atom between the carbon-carbon atom), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, an oxo group ( ⁇ O), and the like.
• Q a and (-Q b -Si(R 2 ) n L 3-n ) may be bonded to that one carbon atom, or two (-Q b -Si(R 2 ) n L 3-n ) may be bonded to that one carbon atom. It is preferable that Q a is bonded to a ring-constituting atom other than (-Q b -Si(R 2 ) n L 3-n ) or R 31 .
• the h (-Q b -Si(R 2 ) n L 3-n ) may each be bonded to a different ring-constituting atom, two of which may be bonded to one ring-constituting carbon atom, and there may be two or more ring-constituting carbon atoms to which two (-Q b -Si(R 2 ) n L 3-n ) are bonded.
• the i R 31 may each be bonded to a different ring-constituting atom, two of which may be bonded to one ring-constituting carbon atom, and there may be two or more ring-constituting carbon atoms to which two R 31 are bonded.
• X 31 is preferably a carbon atom, a nitrogen atom, a silicon atom, a 4-8 valent organo(poly)siloxane residue, or a group having a (h+i+1) valent ring, and more preferably a carbon atom.
• Q b is preferably an alkylene group which may have an etheric oxygen atom.
• the number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 20, and may be 2 to 10, 2 to 6, or 2 to 5. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may be 1 to 10.
• X 31 is a group having a (h+i+1)-valent ring
• h is an integer of 1 to 7
• i is an integer of 0 to 6
• the two or more (-Q b -Si(R) n L 3-n ) may be the same or different.
• the two or more (-R 31 ) may be the same or different.
• i 0.
• Q c is a single bond or a divalent linking group.
• the divalent linking group is the same as that explained above in relation to Qa .
• R 32 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom in terms of ease of production of the compound.
• the alkyl group is preferably a methyl group.
• R 33 is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom in terms of ease of production of the compound.
• groups (3-1A-1) to (3-1A-7) are preferred.
• group (3-1A) is preferably group (3-1A-4).
• X 32 is —O—, —S—, —N(R d )—, —C(O)—, —C(O)O—, —C(O)S—, —SO 2 N(R d )—, —N(R d )SO 2 —, —N(R d )C(O)—, —N ( R d )C(O)N(R d )—, —OC(O)N(R d )—, or —C(O)N(R d )—; or a combination of these with a divalent linking group (wherein N in the formula is bonded to Q b1 ).
• the definition of Rd is as described above. s1 is 0 or 1.
• Q b1 is a single bond or an alkylene group.
• the alkylene group may have -O-, a silphenylene skeleton group, or a dialkylsilylene group.
• the alkylene group may have a plurality of groups selected from the group consisting of -O-, a silphenylene skeleton group, a divalent organo(poly)siloxane residue, and a dialkylsilylene group.
• the alkylene group has --O--, a silphenylene skeleton group, a divalent organo(poly)siloxane residue or a dialkylsilylene group, it is preferable that such a group be present between carbon atoms.
• the alkylene group represented by Q b1 has preferably 1 to 30 carbon atoms, more preferably 1 to 20, further preferably 2 to 20, and particularly preferably 2 to 6. The number of carbon atoms may be 1 to 10.
• X 33 is —O—, —S—, —N(R d )—, —C(O)—, —C(O)O—, —C(O)S—, —SO 2 N(R d )—, —N(R d )SO 2 —, —N(R d )C(O)—, —N(R d )C(O)N(R d )—, —OC(O)N(R d )—, or —C(O)N(R d )—; or a combination of these with a divalent linking group.
• Rd is as described above.
• s2 is 0 or 1.
• s2 is preferably 0 from the viewpoint of ease of production of the compound.
• divalent linking group is bonded to Si(R 3 ) 2 or Si(R 4 ) 2 of formulas (C1) to (C4), or to B 11 of formula (C1-3) or (C2-3).
• Divalent linking groups include alkylene groups, organo(poly)siloxane residues, polyalkylene oxide groups, and combinations thereof.
• Q a2 is a single bond, an alkylene group, -C(O)-, or an alkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon atoms, -C(O)-, -C(O)O-, -OC(O)-, -C(O)N(R d )-, -N( R d )C(O)-, -N(R d )C(O)N(R d )-, -N(R d )C(O)O-, -OC(O)N(R d )-, -SO 2 N(R d )-, -N(R d )SO 2 -, -C(O)N(R d )-, or -NH-.
• the alkylene group represented by Q a2 preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
• Q a2 is preferably a single bond from the viewpoint of ease of production of the compound.
• the alkylene group having 2 or more carbon atoms represented by Q b2 preferably has 2 to 10 carbon atoms, and more preferably has 2 to 6 carbon atoms, in the divalent organo(poly)siloxane residue, the etheric oxygen atom, or the group having -NH- between carbon atoms.
• Q a3 is a single bond or an alkylene group which may have an etheric oxygen atom. From the viewpoint of ease of production of the compound, Q a3 is preferably a single bond.
• the alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, and particularly preferably has 2 to 6 carbon atoms.
• Rg is a hydrogen atom, a hydroxyl group or an alkyl group. From the viewpoint of ease of production of the compound, Rg is preferably a hydrogen atom or an alkyl group.
• the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably is a methyl group.
• the number of carbon atoms in the group having an ether oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms, represented by Q b3 , is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 6.
• Q b3 is preferably -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, or -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 - from the viewpoint of ease of production of the compound.
• Q e is —C(O)O—, —SO 2 N(R d )—, —N(R d )SO 2 —, —N(R d )C(O)—, or —C(O)N(R d )—; or a combination of these with a divalent linking group.
• R 31 is preferably a hydrogen atom.
• s4 is 0 or 1.
• Q a4 is a single bond or an alkylene group which may have an etheric oxygen atom.
• the alkylene group which may have an etheric oxygen atom preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
• t4 is 0 or 1 (provided that when Q a4 is a single bond, t4 is 0).
• Q a5 is an alkylene group which may have an etheric oxygen atom.
• the alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, and particularly preferably has 2 to 6 carbon atoms.
• Q a5 from the viewpoint of ease of production of the compound, -OCH 2 CH 2 CH 2 -, -OCH 2 CH 2 OCH 2 CH 2 CH 2 -, -CH 2 CH 2 - and -CH 2 CH 2 CH 2 - are preferred (wherein the right side is bonded to Si).
• Q b5 is an alkylene group or a group having an ether oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms in an alkylene group having 2 or more carbon atoms.
• the number of carbon atoms in the alkylene group represented by Q b5 is preferably 1 to 30, more preferably 1 to 20, and still more preferably 2 to 20, and may be 2 to 10 or may be 2 to 6. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may be 1 to 10.
• the number of carbon atoms in the group having an ether oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms, represented by Q b5 is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 6.
• Q b5 from the viewpoint of ease of production of the compound, --CH 2 CH 2 CH 2 -- and --CH 2 CH 2 OCH 2 CH 2 CH 2 -- are preferred (wherein the right side is bonded to Si(R 2 ) n L 3-n ).
• the three [-Q b5 -Si(R 2 ) n L 3-n ] may be the same or different.
• Q b6 is an alkylene group or a group having an ether oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms in an alkylene group having 2 or more carbon atoms.
• the number of carbon atoms in the alkylene group represented by Q b6 is preferably 1 to 30, more preferably 1 to 20, and still more preferably 2 to 20, and may be 2 to 10 or may be 2 to 6. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may be 1 to 10.
• Zc is a (w3+w4+1)-valent hydrocarbon group.
• w3 is an integer of 4 or greater.
• w4 is an integer of 0 or greater.
• the definitions and preferred ranges of Q e , s4, Q a4 , t4, Q b4 and u4 are the same as those of each symbol in the group (3-1A-4).
• A1 is bonded to Si(R 3 ) 2 , Si(R 4 ) 2 or B 11 , and Q 22 , Q 23 , Q 24 , Q 25 or Q 26 is bonded to [—Si(R 2 ) n L 3-n ].
• a 1 is a single bond, —C(O)NR 6 —, —C(O)—, —OC(O)O—, —NHC(O)O—, —NHC(O)NR 6 —, —O— or SO 2 NR 6 —.
• Q 11 is a single bond, —O—, an alkylene group, or an alkylene group having 2 or more carbon atoms which has —C(O)NR 6 —, —C(O)—, —NR 6 — or O— between carbon atoms.
• Q12 is a single bond, an alkylene group, or a group having -C(O) NR6- , -C(O)-, -NR6- or O- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and when A has 2 or more Q12 , the 2 or more Q12 may be the same or different.
• Q13 is a single bond (with the proviso that A1 is -C(O)-), an alkylene group, an alkylene group having 2 or more carbon atoms having -C(O) NR6- , -C(O)-, -NR6- or O- between carbon atoms, or an alkylene group having -C(O)- at the N-terminal.
• Q14 is Q12 when the atom in Z4 to which Q14 is bonded is a carbon atom, and is Q13 when the atom in Z4 to which Q14 is bonded is a nitrogen atom.
• the two or more Q14s may be the same or different.
• Q 15 is an alkylene group or a group having -C(O)NR 6 -, -C(O)-, -NR 6 - or O- between carbon atoms of an alkylene group having 2 or more carbon atoms, and when A has 2 or more Q 15 , the 2 or more Q 15 may be the same or different.
• Q 22 is an alkylene group, a group having -C(O)NR 6 -, -C(O)-, -NR 6 - or O- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, a group having -C(O)NR 6 -, -C(O)-, -NR 6 - or O- at the end of the alkylene group not connected to Si, or a group having -C(O)NR 6 -, -C(O)-, -NR 6 - or O- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms and having -C(O)NR 6 -, -C(O)-, -NR 6 - or O- at the end of the side not connected to Si, and when A has 2 or more Q 22 , the 2 or more Q 22 may be the same or different.
• Q 23 is an alkylene group or a group having --C(O)NR 6 --, --C(O)--, --NR 6 -- or O-- between carbon atoms of an alkylene group having 2 or more carbon atoms, and two Q 23 's may be the same or different.
• Q24 is Q22 when the atom in Z4 to which Q24 is bonded is a carbon atom, and is Q23 when the atom in Z4 to which Q24 is bonded is a nitrogen atom.
• the two or more Q24s may be the same or different.
• Q25 is an alkylene group or a group having -C(O) NR6- , -C(O)-, -NR6- or O- between carbon atoms in an alkylene group having 2 or more carbon atoms, and when A has 2 or more Q25s , the 2 or more Q25s may be the same or different.
• Q 26 is an alkylene group or an alkylene group having 2 or more carbon atoms having --C(O)NR 6 --, --C(O)--, --NR 6 -- or O-- between carbon atoms.
• R e2 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group.
• R e3 is an alkyl group.
• R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
• h1 is an integer of 1 or more, and is preferably 1 or 2.
• h2 is an integer of 1 or more, and is preferably 2 or 3.
• i1+i2 is 3 or 4.
• i1 is an integer of 1 to 3, and is preferably 1 or 2.
• i2 is an integer of 1 to 3, and is preferably 2 or 3.
• i3 is 2 or 3.
• the number of carbon atoms in the alkyl group of R e1 , R e2 or R e3 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of the compound.
• the number of carbon atoms in the alkyl group portion of the acyloxy group for R e2 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of the compound.
• h1 is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 1, from the viewpoints of ease of production of the compound and of further improving the abrasion resistance of the surface treatment layer.
• 2 to 6 are preferable, 2 to 4 are more preferable, and 2 or 3 is particularly preferable.
• L x1 and L x2 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, and a methylene group (-CH 2 -) contained in the divalent hydrocarbon group may be replaced by -O- or -O-Si(R x7 ) 2 -.
• R x1 to R x7 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
• Each X a1 independently represents a hydrolyzable group, a group having a hydrolyzable group, or a trialkoxysilyloxy group.
• M1 is Si, Sn, or Ge;
• T1 is independently a hydrocarbon group or a trialkylsilyloxy group;
• r is 0 or 1;
• Z1 's are each independently an alkylene chain or a polyalkylene oxide chain, or a combination of an alkylene chain and a divalent linear organo(poly)siloxane residue,
• A is a single bond or a (p1+q)-valent linking group,
• Each R2 is independently a monovalent hydrocarbon group;
• Each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group;
• n is independently an integer from 0 to 2, p1 and q each independently represent an integer of 1 or more.
• A is a (p1+q)-valent linking group containing a linear organo(poly)siloxane residue.
• Ak1 and Ak2 each independently represent an alkylene chain.
• R3 is the same as R3 in formula (B1).
• k11 is a number of 1 or more.
• k12 is 0 or 1.
• Ak3 represents an alkylene chain.
• R3 is the same as R3 in formula (B1).
• k21 and k22 each independently represent a number of 1 or more.
• Ak4 represents an alkylene chain.
• R3 is the same as R3 in formula (B1).
• k31 is a number of 1 or more.
• *1 is linked to the group 1a side
• *2 is linked to the group 1b side.
• A may be any group that does not impair the effects of the present disclosure, and examples thereof include an alkylene group which may have an ethereal oxygen atom or a divalent linear organo(poly)siloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organo(poly)siloxane residue, and groups obtained by excluding Si(R 2 ) n L 3-n from the above groups (3-1A), (3-1B), and (3-1A-1) to (3-1A-7).
• A may contain a triptycene structure.
• the triptycene structure refers to a partial structure in which two or more hydrogen atoms are removed from triptycene.
• T 1 is the same as T 1 in group 1a.
• R3 is the same as R3 in formula (B1).
• k31 is the same as k31 in formula (D3).
• the group represented by A(Si(R 2 ) n L 3-n ) q is the same as the group represented by A(Si(R 2 ) n L 3-n ) q in formula (1A).
• Ak4 is the same as Ak4 in formula (D3).
• compound (1) include the following compounds:
• n10 is a number equal to or greater than 1, and n10 is preferably a number from 1 to 60, may be a number from 3 to 50, may be a number from 5 to 30, or may be a number from 7 to 25.
• the alkyl group means an unsubstituted alkyl group.
• the alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group or a branched alkyl group is preferable.
• the number of carbon atoms in the alkyl group is preferably 2 to 30, more preferably 3 to 28, and further preferably 4 to 22.
• the compound may contain only one alkyl group, or may contain two or more alkyl groups. Since the alkyl group is a monovalent group, it is located at the terminal of the compound.
• the compound (2) is preferably a compound represented by the following formula (2A).
• T2 is an alkyl group having 2 or more carbon atoms;
• Z2 is a divalent linear organo(poly)siloxane residue;
• A is a single bond or a (p+q)-valent linking group,
• Each R2 is independently a monovalent hydrocarbon group;
• Each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group;
• n is an integer from 0 to 2, p1 and q each independently represent an integer of 1 or more.
• the divalent linear organo(poly)siloxane residue represented by Z2 is preferably a group represented by the above formula (B1).
• R 2 , L, and n are the same as R 2 , L, and n in the above formula (S1).
• the group represented by A(Si(R 2 ) n L 3-n ) q is the same as the group represented by A(Si(R 2 ) n L 3-n ) q in formula (1A) above, except for the details shown below.
• p1 and q are the same as p1 and q in the above formula (1A).
• the group represented by A(Si(R 2 ) n L 3-n ) q is preferably the group (3-1A) or the group (3-1B), and more preferably the group (3-1A).
• Q a represents a single bond or a divalent linking group. However, the end of Qa bonding to Z2 is not an oxysilyl group.
• X 31 is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organo(poly)siloxane residue, or a group having a (h+i+1)-valent ring.
• Q a is a single bond
• the end of X 31 on the side bonding to Z 2 is not an oxysilyl group. In cases other than the above, the end of X 31 may be an oxysilyl group.
• Q b is a single bond or a divalent linking group.
• the terminal of Qb on the side bonding to Z2 is not an oxysilyl group.
• the terminal of Qb may be an oxysilyl group.
• the Q b side terminal of Q a -X 31 is not an alkylene group.
• Q c is a single bond or a divalent linking group. However, the end of Qc bonding to Z2 is not an oxysilyl group.
• X 32 is preferably —O—, —S—, —N(R d )—, —C(O)O—, —C(O)S—, —N(R d )C(O)N(R d )—, —OC(O)N(R d )— or —C(O)N(R d )—, and more preferably —C(O)O— or —C(O)N(R d )—.
• s1 is preferably 0, and Q b1 is preferably an alkylene group having 2 to 6 carbon atoms.
• X 33 is preferably —O—, —C(O)O—, or —C(O)N(R d )—.
• a in formula (2A) may be any of the groups (g2-1) to (g2-7).
• R 51 is an alkyl group having 2 or more carbon atoms.
• R 52 and R 54 each independently represent an alkylene group.
• R 53 is -C(O)O-, -SO 2 N(R d )-, -N(R d )SO 2 -, -N(R d )C(O)- or -C(O)N(R d )-.
• R3 is the same as R3 in formula (B1).
• k1 is the same as k1 in formula (B1).
• X32 is preferably -C(O)-, -C(O)O-, -C(O)S-, -SO2N ( Rd )- or -C(O)N( Rd )-, and more preferably -C(O)-.
• a in formula (3A) may be any of groups (g2-1) to (g2-7).
• R 54 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an oxyalkylene-containing group having 1 to 10 carbon atoms; s7 is an integer from 1 to 20, t7 is an integer from 1 to 20, u7 is an integer from 1 to 20.
• compound (4A) include the following compounds. ⁇ ( CH3 ) 3Si- ( OSi( CH3 ) 2 ) 19- ( CH2 ) 10- CONH- CH2C ⁇ CH2CH2CH2Si ( OCH3 ) 3 ⁇ 3
• the number of elements in the siloxane skeleton-containing group in R k1 and X k1 is less than the number of elements in the trialkylsilyl group-containing molecular chain represented by (R a9 ) 3 Si-Z-(Si(R s1 ) 2 -O-) n9 -Y- of compound (5), and the number of carbon atoms in the longest linear hydrocarbon chain contained in the hydrocarbon chain-containing group in R k1 and X k1 is less than the number of elements in the trialkylsilyl group-containing molecular chain represented by (R a9 ) 3 Si-Z-(Si(R s1 ) 2 -O-) n9 -Y- of compound (5).
• the liquid medium is preferably an organic solvent.
• organic solvents include compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms.
• Specific examples of organic solvents include hydrocarbon organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, glycol organic solvents, and alcohol organic solvents.
• hydrocarbon organic solvent examples include pentane, hexane, heptane, octane, hexadecane, isohexane, isooctane, isononane, cycloheptane, cyclohexane, bicyclohexyl, benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene.
• ester-based organic solvent examples include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, propylene glycol monomethyl acetate, propylene glycol dimethyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol Cholesterol monoethyl ether acetate,
• glycol-based organic solvents include ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, dipropyl
• the alcohol-based organic solvent include methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, diacetone alcohol, isobutanol, sec-butanol, tert-butanol, pentanol, 3-methyl-1,3-butanediol, 1,3-butanediol, 1,3-butylene glycol, octanediol, 2,4-diethylpentanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, isodecanol, isotridecanol, 3-methoxy-3-methyl-1-butanol, 2-methoxybutanol, 3-methoxybutanol, cyclohexanol,
• organic solvents include halogen-based organic solvents, nitrogen-containing compounds, sulfur-containing compounds, siloxane compounds, and fluorine-containing organic solvents.
• Nitrogen-containing compounds include nitrobenzene, acetonitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.
• Sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.
• fluorine-containing organic solvent examples include polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C 6 F 13 CH 2 CH 3 (e.g., Asahiklin (registered trademark) AC-6000 manufactured by AGC Corporation), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorora (registered trademark) H manufactured by Zeon Corporation); hydrofluoroethers (HFEs) (e.g., perfluoropropyl methyl ether (C 3 F 7 OCH 3 ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl
• HFOs hydrofluoroolefins
• HCFO-1233yd 1-chloro-2,3,3-trifluoro-1-propene
• Opteon registered trademark
• the content of the liquid medium is preferably 50 to 99.999% by mass, more preferably 80 to 99.99% by mass, and even more preferably 90 to 99.9% by mass, based on the total amount of the composition of the present disclosure.
• the content of the liquid medium may be 90 to 99.99% by mass, 95 to 99.98% by mass, 97 to 99.97% by mass, or 98 to 99.95% by mass, based on the total amount of the composition of the present disclosure.
• composition of the present disclosure may contain other components in addition to the liquid medium, as long as the effects of the present disclosure are not impaired.
• other components include known additives such as acid catalysts and base catalysts that promote the hydrolysis and condensation reaction of reactive silyl groups.
• any appropriate acid or base e.g., a transition metal (e.g., Ti, Ni, Sn, Zr, Al, B, etc.), a sulfur-containing compound having an unshared electron pair in the molecular structure, a nitrogen-containing compound (e.g., a sulfoxide compound, an aliphatic amine compound, an aromatic amine compound, a phosphoric acid amide compound, an amide compound, a urea compound), etc.
• a transition metal e.g., Ti, Ni, Sn, Zr, Al, B, etc.
• a sulfur-containing compound having an unshared electron pair in the molecular structure e.g., a sulfur-containing compound having an unshared electron pair in the molecular structure
• a nitrogen-containing compound e.g., a sulfoxide compound, an aliphatic amine compound, an aromatic amine compound, a phosphoric acid amide compound, an amide compound, a urea compound
• Acid catalysts include, for example, acetic acid, formic acid, trifluoroacetic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid.
• Examples of the base catalyst include ammonia, sodium hydroxide, potassium hydroxide, and organic amines such as triethylamine and diethylamine.
• metal compounds having hydrolyzable groups are also referred to as "specific metal compounds"
• specific metal compounds include those represented by the following formulas (M1) to (M3).
• M represents a trivalent or tetravalent metal atom.
• Each X b1 independently represents a hydrolyzable group.
• Each X b2 independently represents a siloxane skeleton-containing group.
• Each X b3 independently represents a hydrocarbon chain-containing group.
• m11 is an integer from 2 to 4
• m12 and m13 each independently represent an integer of 0 to 2
• When M is a trivalent metal atom, m11 + m12 + m13 is 3, and when M is a tetravalent metal atom, m11 + m12 + m13 is 4.
• X b4 represents a hydrolyzable silane oligomer residue.
• Each X b5 independently represents a hydrolyzable group or an alkyl group having 1 to 4 carbon atoms.
• X b6 and X b7 each independently represent a hydrolyzable group or a hydroxyl group.
• Y b1 represents a divalent organic group.
• the siloxane skeleton-containing group represented by X b2 has a siloxane unit (-Si-O-) and may be linear or branched.
• a dialkylsilyloxy group is preferable, and examples thereof include a dimethylsilyloxy group and a diethylsilyloxy group.
• the number of repetitions of the siloxane unit in the siloxane skeleton-containing group is 1 or more, preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.
• the siloxane skeleton-containing group may contain a divalent hydrocarbon group in a part of the siloxane skeleton.
• the hydrocarbon chain-containing group represented by X b3 may be a group consisting of only a hydrocarbon chain, or may be a group having an etheric oxygen atom between carbon atoms in the hydrocarbon chain.
• the hydrocarbon chain may be a straight chain or a branched chain, and is preferably a straight chain.
• the hydrocarbon chain may be a saturated hydrocarbon chain or an unsaturated hydrocarbon chain, and is preferably a saturated hydrocarbon chain.
• the number of carbon atoms in the hydrocarbon chain-containing group is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
• the hydrocarbon chain-containing group is preferably an alkyl group, and more preferably a methyl group, an ethyl group, or a propyl group.
• the hydrolyzable silane oligomer residue may have one or more of these alkoxy groups, and preferably has one.
• Examples of hydrolyzable silane oligomer residues include (C 2 H 5 O) 3 Si-(OSi(OC 2 H 5 ) 2 ) 4 O- * , where * represents a bond site with an adjacent atom.
• the content of other components that may be included in the composition of the present disclosure is preferably 10% by mass or less, and more preferably 1% by mass or less, based on the total amount of the composition of the present disclosure.
• the content of the specific metal compound is preferably 0.01 to 30% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.05 to 5% by mass, based on the total amount of the composition of the present disclosure.
• the total content of the first compound and the second compound, or the third compound and the fourth compound, and other components is preferably 0.001 to 40 mass%, more preferably 0.01 to 20 mass%, and even more preferably 0.1 to 10 mass%, relative to the total amount of the composition of the present disclosure.
• the solid content concentration of the composition of the present disclosure is a value calculated from the mass before heating and the mass after heating for 4 hours in a convection dryer at 120°C.
• the surface treatment agent of the present disclosure is composed of the composition of the present disclosure.
• the surface treatment agent of the present disclosure is applied to the surface of a substrate and used to form a surface treatment layer. Details of each component contained in the surface treatment agent are the same as those of each component contained in the composition.
• the surface treatment agent of the present disclosure is preferably used for forming an antifouling layer.
• the surface treatment agent of the present disclosure is preferably used for forming an antifouling layer formed on the outermost surface of an article.
• the article of the present disclosure includes a substrate and a surface treatment layer disposed on the substrate and surface-treated with the surface treatment agent of the present disclosure.
• the surface treatment layer is preferably an antifouling layer.
• the surface treatment layer is preferably an antifouling layer formed on the outermost surface of the article.
• the substrate may be a building material, a decorative building material, an interior item, a transport device (e.g., an automobile), a sign, a bulletin board, a drinking vessel, a tableware, an aquarium, an ornamental device (e.g., a frame, a box), a laboratory device, a furniture, a textile product, a packaging container; a glass or a resin used in art, sports, a game, etc.; a glass or a resin used in the exterior part (excluding the display part) of a device such as a mobile phone (e.g., a smartphone), a personal digital assistant, a game machine, a remote control, etc.
• the shape of the substrate may be a plate or a film.
• the substrate may be a substrate having one or both surfaces subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment.
• a substrate having been subjected to a surface treatment has better adhesion to the surface treatment layer, and the abrasion resistance of the surface treatment layer is improved. For this reason, it is preferable to perform a surface treatment on the surface of the substrate that comes into contact with the surface treatment layer.
• a base layer which will be described later, is provided on the substrate having been subjected to a surface treatment, the adhesion to the base layer is better, and the abrasion resistance of the surface treatment layer is improved. For this reason, when a base layer is provided, it is preferable to perform a surface treatment on the surface of the substrate that comes into contact with the base layer.
• the surface treatment layer may be provided directly on the surface of the substrate, or a base layer may be provided between the substrate and the surface treatment layer. From the viewpoint of further improving the water repellency and abrasion resistance of the surface treatment layer, it is preferable that the article of the present disclosure includes a substrate, a base layer disposed on the substrate, and a surface treatment layer that is surface-treated with the surface treatment agent of the present disclosure and disposed on the base layer.
• the underlayer is preferably a layer containing an oxide containing silicon and at least one specific element selected from the group consisting of Group 1 elements, Group 2 elements, Group 4 elements, Group 5 elements, Group 13 elements, and Group 15 elements of the periodic table.
• Group 2 elements of the periodic table refer to beryllium, magnesium, calcium, strontium, and barium.
• magnesium, calcium, and barium are preferred, and magnesium and calcium are more preferred, from the viewpoint of being able to form a surface treatment layer on the underlayer more uniformly without defects, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples.
• the underlayer may contain two or more types of Group 2 elements.
• Group 4 elements of the periodic table refer to titanium, zirconium, and hafnium.
• Group 4 elements titanium and zirconium are preferred, and titanium is more preferred, from the viewpoint of being able to form a surface treatment layer on the underlayer more uniformly without defects, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples.
• the underlayer may contain two or more types of Group 4 elements.
• Group 5 elements of the periodic table refer to vanadium, niobium, and tantalum.
• Group 5 element vanadium is particularly preferred from the viewpoint of providing a surface treatment layer with superior abrasion resistance.
• the undercoat layer may contain two or more Group 5 elements.
• the Group 15 elements of the periodic table (hereinafter also referred to as "Group 15 elements") refer to nitrogen, phosphorus, arsenic, antimony, and bismuth.
• Group 15 elements from the viewpoint of being able to form a surface treatment layer on the underlayer more uniformly without defects, or from the viewpoint of further suppressing the variation in the composition of the underlayer between samples, phosphorus, antimony, and bismuth are preferred, and phosphorus and bismuth are more preferred.
• the underlayer may contain two or more types of Group 15 elements.
• Group 1 elements, Group 2 elements, and Group 13 elements are preferred because they provide a surface treatment layer with superior abrasion resistance, Group 1 elements and Group 2 elements are more preferred, and Group 1 elements are even more preferred.
• the specific element may be one type of element or two or more types of elements.
• the underlayer may be a single layer or multiple layers.
• the underlayer may have an uneven surface.
• the thickness of the underlayer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and even more preferably 2 to 20 nm. If the thickness of the underlayer is equal to or greater than the lower limit, the adhesion of the underlayer to the surface treatment layer is improved, and the surface treatment layer has better abrasion resistance. If the thickness of the underlayer is equal to or less than the upper limit, the underlayer itself has better abrasion resistance. The thickness of the underlayer is measured by observing a cross section of the underlayer with a transmission electron microscope (TEM).
• TEM transmission electron microscope
• the deposition material used in the deposition method preferably contains an oxide containing silicon and a specific element.
• Specific examples of the form of the deposition material include powder, melt, sintered body, granulated body, and crushed body, and from the viewpoint of handleability, the melt, sintered body, and granulated body are preferred.
• the melt means a solid obtained by melting the powder of the deposition material at a high temperature and then cooling and solidifying it.
• the sintered body means a solid obtained by firing the powder of the deposition material, and if necessary, a molded body may be used by pressing the powder instead of the powder of the deposition material.
• the granulated body means a solid obtained by kneading the powder of the deposition material with a liquid medium (e.g., water, organic solvent) to obtain particles, and then drying the particles.
• a liquid medium e.g., water, organic solvent
• the deposition material can be produced, for example, by the following method.
• a method of mixing a powder containing silicon e.g., powder made of silicon oxide, silica sand, silica gel
• a powder containing a specific element e.g., powder of an oxide, carbonate, sulfate, nitrate, oxalate, hydroxide of a specific element
• water e.g., water, drying the mixture, and then firing the dried mixture or a compact obtained by pressing the mixture to obtain a sintered body.
• the evaporation method of the deposition material include a resistance heating method in which the deposition material is melted and evaporated on a resistance heating boat made of a high melting point metal, and an electron gun method in which the deposition material is irradiated with an electron beam to directly heat the deposition material to melt and evaporate the surface.
• the electron gun method is preferred as the evaporation method of the deposition material because it can evaporate high melting point substances because it can heat locally, and because the areas not hit by the electron beam are at low temperature, there is no risk of reaction with the container or contamination with impurities.
• the evaporation method of the deposition materials may use multiple boats, or may use a single boat containing all the deposition materials.
• the deposition method may be co-deposition or alternating deposition.
• silicon compounds include silicon oxide, silicic acid, partial condensates of silicic acid, alkoxysilanes, and partial hydrolysis condensates of alkoxysilanes.
• the liquid medium may be the same as the liquid medium that may be contained in the composition of the present disclosure.
• the content of the liquid medium is preferably 80 to 99.99% by mass, and more preferably 90 to 99.9% by mass, based on the total amount of the coating liquid used to form the undercoat layer.
• wet coating methods for forming the underlayer include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, the Langmuir-Blodgett method, and gravure coating.
• the drying temperature for the coating film is preferably 20 to 200°C, and more preferably 80 to 160°C.
• the article of the present disclosure may be an optical material having a surface treatment layer as the outermost layer.
• Preferred examples of the optical material include optical materials related to displays and the like, as well as a wide variety of other optical materials.
• optical materials include displays such as cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), and field emission displays (FEDs; Field Emission Displays), or protective plates for such displays, or displays whose surfaces have been treated with an anti-reflection film.
• the article of the present disclosure is preferably an optical member, such as a car navigation system, a mobile phone, a smartphone, a digital camera, a digital video camera, a PDA, a portable audio player, a car audio, a game machine, an eyeglass lens, a camera lens, a lens filter, sunglasses, a medical device such as a gastroscope, a copier, a PC, a display (e.g., a liquid crystal display, an organic electroluminescence display, a plasma display, a touch panel display), a touch panel, a protective film, and an anti-reflection film.
• the material constituting the surface of the substrate is a material for optical members, for example, glass or transparent plastic.
• the surface (outermost layer) of the substrate may have a functional layer such as a hard coat layer or an antireflection layer formed thereon.
• the antireflection layer may be either a single-layer antireflection layer or a multi-layer antireflection layer.
• a transparent electrode for example, a thin film using indium tin oxide (ITO) or indium zinc oxide
• ITO indium tin oxide
• the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, etc., depending on the specific specifications, etc.
• the method for producing an article according to the present disclosure is, for example, a method for producing an article having a surface treatment layer formed on a substrate by performing a surface treatment on a substrate using the surface treatment agent according to the present disclosure.
• Examples of the surface treatment include a dry coating method and a wet coating method.
• Dry coating methods include vacuum deposition, CVD, sputtering, and the like.
• vacuum deposition is preferred from the viewpoint of suppressing decomposition of the compound and the simplicity of the device.
• a pellet-shaped material in which a metal porous body such as iron or steel is impregnated with the compound of the present disclosure may be used.
• a composition containing the compound of the present disclosure and a liquid medium may be impregnated into a metal porous body such as iron or steel, the liquid medium may be dried, and a pellet-shaped material impregnated with the compound of the present disclosure may be used.
• Wet coating methods include, for example, spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.
• an operation for promoting the reaction between the compound of the present disclosure and the substrate may be carried out.
• Such an operation may include heating, humidification, light irradiation, etc.
• by heating a substrate on which a surface treatment layer has been formed in an atmosphere containing moisture it is possible to promote reactions such as hydrolysis reaction of hydrolyzable groups, reaction between hydroxyl groups or the like on the substrate surface and silanol groups, and generation of siloxane bonds through condensation reaction of silanol groups.
• compounds in the surface treatment layer that are not chemically bonded to other compounds or the substrate may be removed as necessary. Examples of the method for removing the compounds include pouring a solvent onto the surface treatment layer and wiping the compounds off with a cloth soaked in the solvent.
• Examples 2 to 11 are examples, and Example 1 is a comparative example.
• the substrate on which the silicon oxide layer was formed was placed on the sample stage of a spray coater (API-90RS manufactured by Apiros Co., Ltd.) so that the silicon oxide layer was on the surface.
• a spray coater API-90RS manufactured by Apiros Co., Ltd.
• 13 g of the prepared surface treatment agent was placed in a syringe in the spray coater, and spray-coated at an atomization pressure of 130 kPa, a nozzle-to-sample surface distance of 50 mm, and a scanning speed of 300 mm/sec.
• the coated substrate was then heat-treated at 140° C. for 30 minutes. As a result, an article having a surface treatment layer on the surface of the silicon oxide layer was obtained.
• the surface treatment layer of the obtained article was evaluated as follows.
• a uniform light irradiation unit (Ushio) was attached to a mercury lamp (SP-9 250DB, Ushio Inc.), and a sample was placed at a distance of 17.5 cm from the lens.
• the light intensity at 200 to 800 nm was measured using an intensity meter (VEGA, OPHIR Inc.), and found to be 200 mW/ cm2 .
• the sample was irradiated with the mercury lamp for 6 hours in an atmospheric environment with a temperature of 20 to 40°C and a humidity of 30 to 75%.
• Table 1 shows the evaluation results of the water contact angle (initial water contact angle) before the light resistance test and the water contact angle after the light resistance test, as well as the contact angle change rate.
• the ratio of compound (I) indicates the mass ratio of compound (I) to the total amount of compound (I) and compound (II).
• the ratio of compound (II) indicates the mass ratio of compound (II) to the total amount of compound (I) and compound (II).
• the ratio of compound (III) indicates the mass ratio of compound (III) to the total amount of compound (III) and compound (IV).
• the ratio of compound (IV) indicates the mass ratio of compound (IV) to the total amount of compound (III) and compound (IV).
• the ratio of compound (V) indicates the mass ratio of compound (V) to the total amount of compound (V) and compound (VI).
• the ratio of compound (VI) indicates the mass ratio of compound (VI) to the total amount of compound (V) and compound (VI).
• the surface treatment layers obtained in Examples 2 to 11 have a small rate of change in water contact angle after the light resistance test, and are excellent in light resistance.
• composition and the surface treatment agent can also be used for car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, displays (e.g., liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, anti-reflection films, and other optical components.
• displays e.g., liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, anti-reflection films, and other optical components.
• a composition comprising: a first compound having a linear organo(poly)siloxane residue and one reactive silyl group linked to only one end of the linear organo(poly)siloxane residue; and a second compound having a linear organo(poly)siloxane residue and two or more reactive silyl groups linked to only one end of the linear organo(poly)siloxane residue; or a third compound having a linear organo(poly)siloxane residue and a reactive silyl group linked to each of both ends of the linear organo(poly)siloxane residue; and a fourth compound having a linear organo(poly)siloxane residue and two or more reactive silyl groups linked to each of both ends of the linear organo(poly)siloxane residue.
• composition according to ⁇ 1> or ⁇ 2>, wherein the chain organo(poly)siloxane residues in the first compound, the second compound, the third compound, and the fourth compound are each independently represented by the following formula (B1) or (B2):
• formula (B1) Each R3 is independently a hydrocarbon group; k1 is a number equal to or greater than 1, * indicates a bonding site with an adjacent atom.
• q1 is independently an integer of 2 to 4.
• the amount of the second compound is 50 to 97 mass% with respect to the total amount of the first compound and the second compound
• the amount of the fourth compound is 50 to 97% by mass relative to the total amount of the third compound and the fourth compound.
• ⁇ 12> The composition according to any one of ⁇ 1> to ⁇ 11>, further comprising a liquid medium.
• a surface treatment agent comprising the composition according to any one of ⁇ 1> to ⁇ 12>.

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• 2024
  • 2024-10-07 JP JP2025550399A patent/JPWO2025075201A1/ja active Pending
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