[go: up one dir, main page]

WO2024262633A1 - Composé, composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci - Google Patents

Composé, composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci Download PDF

Info

Publication number
WO2024262633A1
WO2024262633A1 PCT/JP2024/022685 JP2024022685W WO2024262633A1 WO 2024262633 A1 WO2024262633 A1 WO 2024262633A1 JP 2024022685 W JP2024022685 W JP 2024022685W WO 2024262633 A1 WO2024262633 A1 WO 2024262633A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
surface treatment
compound
article
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/022685
Other languages
English (en)
Japanese (ja)
Inventor
弘毅 渡邉
英一郎 安樂
大介 小林
能仁 徳永
豊和 遠田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2024262633A1 publication Critical patent/WO2024262633A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

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
    • 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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • 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
    • 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
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • 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
    • 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
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • 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
    • 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
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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

  • the present disclosure relates to compounds, compositions, surface treatment agents, articles, and methods for manufacturing articles.
  • a specific method known is to perform a surface treatment on the surface of the article using a surface treatment agent.
  • Patent Documents 1 and 2 describe silane compounds having specific siloxane groups that are used in the above-mentioned surface treatment agents.
  • an object of one embodiment of the present invention is to provide a novel compound and composition that are useful as a surface treatment agent capable of forming a surface treatment layer having excellent light resistance and abrasion resistance on a substrate.
  • An object of one embodiment of the present invention is to provide a surface treatment agent capable of forming a surface treatment layer having excellent light resistance and abrasion resistance on a substrate.
  • An object of one embodiment of the present invention is to provide an article having a surface treatment layer that is excellent in light resistance and abrasion resistance, and a method for manufacturing the article.
  • T is independently (R 1 ) 3 Si—, a monovalent cyclic polysiloxane residue or a monovalent cage-shaped polysiloxane residue
  • Each R 1 is independently a hydrogen atom, a hydrocarbon group, or a trialkylsilyloxy group
  • R 2 , R 3 and R 5 each independently represent a hydrogen atom or a hydrocarbon group
  • R4 is -L1 -Si(R) nL3 -n
  • L1 is -O- or an alkylene group
  • Each R is independently a hydrocarbon group
  • Each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group
  • R 6 is —O—(Si(R 2
  • a composition comprising the compound according to any one of [1] to [4] above and a liquid medium.
  • a surface treatment agent comprising the compound according to any one of [1] to [4] above.
  • a surface treatment agent comprising the compound according to any one of [1] to [4] above and a liquid medium.
  • a method for producing an article comprising: performing a surface treatment on a substrate using the surface treatment agent described in [6] above; and producing an article having a surface treatment layer formed on the substrate.
  • An article comprising a substrate and a surface treatment layer disposed on the substrate and surface-treated with the surface treatment agent according to [6] above.
  • a novel compound and composition useful as a surface treatment agent capable of forming a surface treatment layer having excellent light resistance and abrasion resistance on a substrate there is provided a surface treatment agent capable of forming a surface treatment layer having excellent light resistance and abrasion resistance on a substrate.
  • a surface treatment agent capable of forming a surface treatment layer having excellent light resistance and abrasion resistance on a substrate there are provided an article having a surface treatment layer with excellent light resistance and abrasion resistance, and a method for manufacturing the article.
  • the numerical range indicated using “to” includes the numerical values before and after “to” as the minimum and maximum values, respectively.
  • the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range.
  • the upper or lower limit of the numerical range may be replaced with a value shown in the examples.
  • the term "surface treatment layer” refers to a layer formed on the surface of a substrate by surface treatment.
  • the compound or group represented by the formula (X) may be referred to as compound (X) or compound X, and group (X) or group X, respectively.
  • Me means a methyl group
  • Et means an ethyl group.
  • the compound of the present disclosure is a compound represented by formula (1) described below.
  • a surface treatment layer having excellent light resistance and abrasion resistance can be formed.
  • each unit of the compound is bonded by a siloxane bond having a relatively high bond energy, so it is considered that a surface treatment layer having excellent light resistance can be formed.
  • the repeating unit containing a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group is 2 or more, it is considered that a surface treatment layer having excellent abrasion resistance can be formed.
  • the compound of the present disclosure is a compound represented by the following formula (1).
  • T-O-(Si(R 2 ) 2 -O) p -(SiR 3 R 4 -O) q -(SiR 5 R 6 -O) r -T Each T is independently (R 1 ) 3 Si—, a monovalent cyclic polysiloxane residue, or a monovalent cage-shaped polysiloxane residue;
  • Each R 1 is independently a hydrogen atom, a hydrocarbon group, or a trialkylsilyloxy group;
  • R 2 , R 3 and R 5 each independently represent a hydrogen atom or a hydrocarbon group;
  • R4 is -L1 -Si(R) nL3 -n ;
  • L1 is -O- or an alkylene group;
  • Each R is independently a hydrocarbon group;
  • Each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a
  • the numbers p, q, r, and s in formula (1) are each average values calculated from data obtained by measuring the compound by nuclear magnetic resonance (NMR) spectroscopy.
  • each T is independently (R 1 ) 3 Si-, a monovalent cyclic polysiloxane residue, or a monovalent cage-shaped polysiloxane residue.
  • T in formula (1) may be different from each other or may represent the same group.
  • Examples of the hydrocarbon group represented by R1 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 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.
  • the alkyl group contained in the trialkylsilyloxy group represented by R1 may be any one of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group.
  • a linear alkyl group is preferable, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group is more preferable, and a methyl group is further preferable.
  • a plurality of R 1s may be the same or different from each other, and from the viewpoint of ease of production, they are preferably the same.
  • Examples of the group represented by (R 1 ) 3 Si- include a methyldiethylsilyl group, a methylethylpropylsilyl group, a methylethylbutylsilyl group, a methyldipropylsilyl group, a methylpropylbutylsilyl group, a methyldibutylsilyl group, a dimethylethylsilyl group, a dimethylpropylsilyl group, a dimethylbutylsilyl group, a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a tri-isopropylsilyl group, and a trialkylsilyloxy group having any of these groups.
  • R 1 is preferably a trialkylsilyloxy group, more preferably a trimethylsilyloxy group or
  • the monovalent cyclic polysiloxane residue is preferably a group represented by formula (T1).
  • R 3 's each independently represent a hydrocarbon group, a hydrocarbon group having a substituent, or a group represented by -O-SiR 51 3 ; s is an integer from 1 to 4; Each R 51 independently represents a hydrocarbon group or a trialkylsilyloxy group; * indicates the bond position.
  • hydrocarbon group represented by R3 examples 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 as one embodiment of the hydrocarbon group represented by R3 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 represented by R3 is preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, or a heptyl group, and more preferably a methyl group.
  • Examples of the hydrocarbon group contained in the hydrocarbon group having a substituent represented by R3 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.
  • Examples of the substituent in the substituted hydrocarbon group represented by R 3 include a halogen atom, a hydroxyl group, an alkoxy group, a trialkylsilyl ether group, a trialkylsilyl group, an amino group, a nitro group, a cyano group, a sulfonyl group, a trifluoromethyl group, and a group represented by -SiR 52 3.
  • Each R 52 is independently a hydrocarbon group or a trialkylsilyloxy group.
  • Examples of the hydrocarbon group represented by R52 include the same as the hydrocarbon group represented by R3 .
  • the alkyl group contained in the trialkylsilyloxy group represented by R52 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, still more preferably 1 to 4, and particularly preferably 1.
  • the three alkyl groups contained in the trialkylsilyloxy group may be the same or different from each other.
  • the three R 52 may be the same or different from each other, but from the viewpoint of ease of production, it is preferable that they are the same.
  • each R 51 is independently a hydrocarbon group or a trialkylsilyloxy group.
  • the hydrocarbon group represented by R 51 include the same as the hydrocarbon group represented by R 3.
  • the trialkylsilyloxy group represented by R 51 include the same as the trialkylsilyloxy group represented by R 52 .
  • the multiple R3s may be the same or different from one another, but from the viewpoint of ease of production, they are preferably the same.
  • Examples of monovalent cyclic polysiloxane residues include the following groups. * indicates the bond position.
  • the monovalent cage polysiloxane residue is preferably a group represented by formula (T2).
  • Each R4 is independently a hydrocarbon group or a trialkylsilyloxy group; * indicates the bond position.
  • Examples of the hydrocarbon group represented by R4 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 is preferably a linear alkyl group or a branched alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or an isobutyl group, and even more preferably an isobutyl group.
  • the alkyl group contained in the trialkylsilyloxy group represented by R4 may be any one of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group.
  • a linear alkyl group is preferable, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group is more preferable, and a methyl group is even more preferable.
  • a plurality of R 4s may be the same or different from each other, and from the viewpoint of ease of production, they are preferably the same.
  • Examples of monovalent cage-shaped polysiloxane residues include the following groups. * indicates the bonding position.
  • R 2 , R 3 and R 5 each independently represent a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group represented by R 2 , R 3 , and R 5 include the hydrocarbon group represented by R 1.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group, 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 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.
  • R 2 , R 3 and R 5 each preferably have 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms.
  • R 2 , R 3 and R 5 may be the same group or different groups.
  • p is a number of 1 or more. p is preferably a number from 2 to 600, more preferably a number from 3 to 500, still more preferably a number from 4 to 50, particularly preferably a number from 5 to 30, and most preferably a number from 6 to 25.
  • R 4 is -L 1 -Si(R) n L 3-n .
  • a plurality of R 4s in formula (1) may be the same or different from each other.
  • L1 is --O-- or an alkylene group.
  • the number of carbon atoms in the alkylene group is preferably 1 to 60, more preferably 1 to 40, and still more preferably 1 to 30.
  • the number of carbon atoms in the alkylene group may be 1 to 10, 1 to 5, 1 to 3, or 1 or 2.
  • L1 is preferably —O— from the viewpoint of better light resistance.
  • each R is independently a hydrocarbon group.
  • Examples of the hydrocarbon group represented by R include the hydrocarbon group represented by R1 .
  • each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.
  • a hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, a hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH through a hydrolysis reaction. The silanol groups further react with each other to form Si-O-Si bonds. In addition, the silanol groups can undergo a dehydration condensation reaction with silanol groups derived from oxides present on the surface of the substrate to form Si-O-Si bonds.
  • hydrolyzable groups examples include alkoxy groups, aryloxy groups, halogen atoms, acyl groups, acyloxy groups, and isocyanato groups (-NCO).
  • 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.
  • 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.
  • the group having a hydrolyzable group may be, for example, any of the groups having a hydrolyzable group exemplified above.
  • the group having a hydrolyzable group is preferably -OL A -LB .
  • LA is an alkylene group
  • LB is a hydrolyzable group.
  • the alkylene group preferably has 1 to 10 carbon atoms.
  • the hydrolyzable group represented by LB has the same meaning as the hydrolyzable group represented by L described above, and the preferred embodiments are also the same.
  • L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom.
  • L is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably an ethoxy group or a methoxy group, from the viewpoint of less outgassing during application and better storage stability of the compound.
  • n is independently an integer of 0 to 2. n is preferably 0 or 1, and more preferably 0.
  • n is preferably 0 or 1, and more preferably 0.
  • the adhesion of the surface treatment layer to the substrate is strengthened.
  • n is 1 or less, the multiple Ls present in one molecule may be the same or different from each other. From the viewpoint of availability of raw materials and ease of manufacturing the compound, it is preferable that the multiple Ls are the same.
  • n is 2, the multiple Rs present in one molecule may be the same or different from each other. From the viewpoint of availability of raw materials and ease of manufacturing the compound, it is preferable that the multiple Rs are the same.
  • q is a number of 2 or more. In view of superior abrasion resistance of the surface treatment layer, q is preferably a number from 2 to 30, more preferably a number from 3 to 20, further preferably a number from 4 to 15, and particularly preferably a number from 4 to 10.
  • a plurality of [SiR 3 R 4 —O] may be the same or different from each other.
  • R 6 is —O—(Si(R 7 ) 2 —O) s —Si(R 8 ) 3 or —O—Si(R 9 ) 3 .
  • R7 is each independently a hydrogen atom or a hydrocarbon group.
  • R7 include the hydrocarbon groups represented by R1 .
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group, 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 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.
  • R 7 preferably has 1 to 6 carbon atoms, more preferably has 1 to 3 carbon atoms, and further preferably has 1 or 2 carbon atoms.
  • R 8 and R 9 each independently represent a hydrogen atom, a hydrocarbon group, or a trialkylsilyloxy group.
  • the hydrocarbon group represented by R8 include the hydrocarbon group represented by R7 , and preferred embodiments are also the same as those of R7 .
  • a plurality of R 8 s may be the same or different from one another, and from the viewpoint of ease of production, they are preferably the same.
  • the hydrocarbon group represented by R 9 include the hydrocarbon group represented by R 7.
  • a plurality of R 8 may be the same or different from each other.
  • R 9 is a hydrocarbon group
  • two of the hydrocarbon groups represented by R 9 are preferred embodiments of the hydrocarbon group represented by R 7
  • one of the hydrocarbon groups is a linear alkyl group having 2 to 30 carbon atoms or a branched alkyl group having 2 to 30 carbon atoms.
  • the one hydrocarbon group represents a linear alkyl group or a branched alkyl group
  • the number of carbon atoms is preferably 3 to 30, and more preferably 4 to 20.
  • Examples of the trialkylsilyloxy group represented by R 8 and R 9 include the group represented by ((R 1 ) 3 Si—O—) in which —O— is linked to the bond of the above-mentioned (R 1 ) 3 Si—.
  • s is a number of 1 or more. In order to provide a surface treatment layer with better fingerprint resistance, s is preferably a number from 2 to 40, more preferably a number from 3 to 30, further preferably a number from 4 to 25, and particularly preferably a number from 5 to 20.
  • the multiple [Si(R 7 ) 2 —O] may be the same or different from each other.
  • r is a number of 0 or more.
  • r is preferably a number of 1 or more, more preferably a number from 1 to 20, even more preferably a number from 2 to 15, still more preferably a number from 2 to 10, and particularly preferably a number from 2 to 5.
  • R 6 is —O—(Si(R 7 ) 2 —O) s —Si(R 8 ) 3 .
  • R 6 is —O—Si(R 9 ) 3 .
  • the ratio of the number of repeating units in which R 6 is —O—(Si(R 7 ) 2 —O) s —Si(R 8 ) 3 to r is 0.2 to 0.8.
  • the multiple [SiR 5 R 6 -O] may be the same or different from each other.
  • At least one R 6 is -O-(Si(R 7 ) 2 -O) s -Si(R 8 ) 3 and at least one R 6 is -O-Si(R 9 ) 3 .
  • repeating unit represented by -(SiR 5 R 6 -O)- examples include the following.
  • s is defined as above.
  • t represents an integer of 0 to 28.
  • the same type of repeating units may be bonded consecutively, different types of repeating units may be bonded alternately, or each repeating unit may be bonded in a random order.
  • the compound represented by formula (1) is an alternating copolymer in which different types of repeating units are bonded alternately, or a random copolymer in which each repeating unit is bonded in a random order.
  • the number average molecular weight (Mn) of the compound of the present disclosure is preferably from 500 to 20,000, more preferably from 600 to 18,000, and even more preferably from 700 to 15,000.
  • Mn is 500 or more
  • the abrasion resistance of the surface treatment layer is more excellent.
  • Mn is 20,000 or less
  • the viscosity can be easily adjusted within an appropriate range, and the solubility is improved, so that the handling property during film formation is excellent.
  • composition of the present disclosure may contain the compound of the present disclosure, and the components other than the compound of the present disclosure are not particularly limited.
  • the composition of the present disclosure preferably contains the compound of the present disclosure and a liquid medium.
  • the composition of the present disclosure may be liquid, and may be a solution or a dispersion.
  • the composition of the present disclosure may contain the compound of the present disclosure, and may contain impurities such as by-products produced in the production process of the compound of the present disclosure.
  • the content of the compound of the present disclosure is preferably 0.001 to 40 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 content of the compound of the present disclosure is preferably 0.01 to 10 mass%, more preferably 0.02 to 5 mass%, even more preferably 0.03 to 3 mass%, and particularly preferably 0.05 to 2 mass%, based on the total amount of the composition of the present disclosure.
  • the liquid medium contained in the composition of the present disclosure may be only one type, or may be two or more types.
  • the liquid medium is preferably an organic solvent.
  • the organic solvents include compounds consisting of only hydrogen atoms and carbon atoms, and compounds consisting of only hydrogen atoms, carbon atoms, and oxygen atoms. Specific examples include hydrocarbon organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, glycol organic solvents, and alcohol organic solvents. Of these, the organic solvent is preferably a hydrocarbon organic solvent or an ester organic solvent.
  • 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.
  • ketone organic solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 4-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, and isophorone.
  • ether-based organic solvent examples include diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane.
  • 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 monoethyl ether, Examples of the monoisobutyl
  • 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
  • ethylene glycol dimethyl ether examples include glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, 1,3-butylene glycol, propylene glycol n-propyl ether, propylene glycol n-butyl ether, diethylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl
  • 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, fluorine-containing organic solvents, nitrogen-containing compounds, sulfur-containing compounds, and siloxane compounds other than the compounds disclosed herein.
  • halogen-based organic solvents include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, and 1,2,3-trichloropropane.
  • fluorine-containing organic solvents 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 ethy
  • 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.
  • siloxane compounds other than those disclosed herein include hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octaethyltrisiloxane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, and decamethyltetrasiloxane.
  • the content of the liquid medium is preferably 60 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 is preferably 90 to 99.99% by mass, more preferably 95 to 99.98% by mass, even more preferably 97 to 99.97% by mass, and particularly preferably 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 compound and liquid medium of the present disclosure, as long as the effects of the present disclosure are not impaired.
  • the other components include additives, and specifically, catalysts 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 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.
  • composition of the present disclosure contains a specific metal compound, the slip properties and antifouling properties of the surface treatment layer can be further improved.
  • specific metal compounds include metal compounds represented by any of formulas (M1) to (M3).
  • M is a trivalent or tetravalent metal atom;
  • Each X b1 is independently a hydrolyzable group;
  • Each X b2 independently represents a siloxane skeleton-containing group,
  • Each X b3 is independently a hydrocarbon chain-containing group;
  • m1 is an integer from 2 to 4,
  • m2 and m3 each independently represent an integer of 0 to 2;
  • M is a trivalent metal atom, m1+m2+m3 is 3, and when M is a tetravalent metal atom, m1+m2+m3 is 4.
  • X b4 is 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 is a divalent organic group.
  • the metal represented by M includes semimetals such as Si and Ge.
  • M is preferably a trivalent metal or a tetravalent metal, more preferably Al, Fe, In, Hf, Si, Ti, Sn, or Zr, even more preferably Al, Si, Ti, or Zr, and particularly preferably Si.
  • the hydrolyzable group represented by X b1 has the same meaning as the hydrolyzable group represented by L in formula (1) above, and preferred embodiments are also the same.
  • the siloxane skeleton-containing group represented by X b2 has a siloxane unit (-Si-O-) and may be either 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.
  • some of the oxygen atoms in the siloxane skeleton may be replaced with a divalent hydrocarbon group.
  • the divalent hydrocarbon group include alkylene groups such as methylene, ethylene, propylene, and butylene.
  • the terminal silicon atom of the siloxane skeleton-containing group may have a hydrolyzable group, a hydrocarbon group (preferably an alkyl group) or the like bonded thereto.
  • the number of elements in the siloxane skeleton-containing group is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less. The upper limit of the number of elements is preferably 10 or more.
  • the siloxane skeleton-containing group is preferably a group represented by *-(O-Si(CH 3 ) 2 ) n CH 3 , where n is an integer of 1 to 5, and * represents a bonding site with an adjacent atom.
  • 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 linear or branched, with linear being preferred.
  • the hydrocarbon chain may be a saturated or unsaturated hydrocarbon chain, with saturated hydrocarbon chain being preferred.
  • 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.
  • m1 is 3 or 4.
  • the compound represented by formula (M1) a compound represented by any one of formulas (M1-1) to (M1-5) in which M is Si is preferred, and a compound represented by formula (M1-1) is more preferred.
  • the compound represented by formula (M1-1) tetraethoxysilane, tetramethoxysilane, or triethoxymethylsilane is preferred.
  • the number of silicon atoms contained in the hydrolyzable silane oligomer residue represented by Xb4 is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more.
  • the number of silicon atoms is preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less.
  • the hydrolyzable silane oligomer residue may have an alkoxy group bonded to a silicon atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and the methoxy group or the ethoxy group is preferred.
  • 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.
  • examples of the hydrolyzable group represented by X b5 include the same hydrolyzable group represented by L in formula (1) above, a cyano group, a hydrogen atom, and an allyl group, and an alkoxy group or an isocyanato group is preferable.
  • the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.
  • X b5 is preferably a hydrolyzable group.
  • Examples of the compound represented by formula (M2) include (H 5 C 2 O) 3 —Si—(OSi(OC 2 H 5 ) 2 ) 4 OC 2 H 5 and the like.
  • the compound represented by formula (M3) is a compound having reactive silyl groups at both ends of a divalent organic group, that is, a bissilane.
  • examples of the hydrolyzable group represented by X b6 and X b7 include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanato group, and a halogen atom, and an alkoxy group or an isocyanato group is preferable.
  • the alkoxy group an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.
  • X b6 and X b7 may be the same group or different groups. From the viewpoint of availability, X b6 and X b7 are preferably the same group.
  • Y b1 is a divalent organic group linking the reactive silyl groups at both ends.
  • the divalent organic group Y b1 preferably has 1 to 8 carbon atoms, and more preferably has 1 to 3 carbon atoms.
  • Examples of Y b1 include an alkylene group, a phenylene group, and an alkylene group having an ether oxygen atom between carbon atoms.
  • Examples of compounds represented by formula (M3) include ( CH3O ) 3Si ( CH2 ) 2Si ( OCH3 ) 3 , ( C2H5O)3Si(CH2)2Si(OC2H5)3, (OCN)3Si(CH2)2Si(NCO)3 , Cl3Si ( CH2 ) 2SiCl3 , ( CH3O ) 3Si ( CH2 ) 6Si ( OCH3 ) 3 , and ( C2H5O ) 3Si ( CH2 ) 6Si (OC2H5 ) 3 .
  • 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 compound of the present disclosure 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 of the composition before heating and the mass after heating for 4 hours in a convection dryer at 120°C.
  • composition disclosed herein is useful for coating applications because it contains a liquid medium, and can be used as a coating liquid.
  • the composition of the present disclosure may contain other components other than compound 1 and 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 hydrolyzable silyl groups.
  • the content of other components in the composition of the present disclosure is preferably 10% by mass or less, and more preferably 1% by mass or less.
  • the other components include a compound represented by the following formula (2).
  • Y 1 is Si, Sn, or Ge;
  • Each Y 1 is independently a hydrocarbon group or a trialkylsilyloxy group;
  • s1 is 0 or 1;
  • Each Y3 is independently an alkylene chain or a polyalkylene oxide chain, or a combination of an alkylene chain and a divalent polysiloxane residue,
  • Y4 is a single bond or a linking group having a valence of (s2+s4);
  • Each Y5 is independently a hydrocarbon group;
  • Each Y6 is independently a hydrolyzable group or a hydroxyl group;
  • Each s3 independently represents an integer of 0 to 2, s2 and s4 each independently represent an integer of 1 or more.
  • a compound in which Y3 is an alkylene chain or a polyalkylene oxide chain is preferable.
  • Specific examples of compound (2) include the following compounds: In the formula, ⁇ is preferably 9 to 50, more preferably 11 to 30, and particularly preferably 11 to 25.
  • the content of compound (2) is preferably 50% by mass or less, and more preferably 40% by mass or less.
  • the surface treatment agent of the present disclosure comprises the compound of the present disclosure.
  • the surface treatment agent of the present disclosure may also comprise the compound of the present disclosure and a liquid medium.
  • the surface treatment agent of the present disclosure may also be the composition of the present disclosure.
  • the preferred embodiment of the liquid medium contained in the surface treatment agent of the present disclosure is the same as the preferred embodiment of the liquid medium contained in the composition of the present disclosure.
  • 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 may be formed on a part of the surface of the substrate, or may be formed on the entire surface of the substrate.
  • the surface treatment layer may be spread on the surface of the substrate in the form of a film, or may be scattered in the form of dots.
  • the compound of the present disclosure is contained in a state in which partial or total hydrolysis of reactive silyl groups ((Si(R) n L 3-n )) has progressed and dehydration condensation reaction of silanol groups has progressed.
  • the thickness of the surface treatment layer is preferably 1 to 100 nm, and more preferably 1 to 50 nm. If the thickness of the surface treatment layer is 1 nm or more, the effect of the surface treatment is likely to be sufficient. If the thickness of the surface treatment layer is 100 nm or less, the utilization efficiency is high.
  • the thickness of the surface treatment layer can be calculated from the vibration period of the interference pattern obtained by obtaining an interference pattern of reflected X-rays by X-ray reflectivity method using a thin film analysis X-ray diffractometer (product name "ATX-G", manufactured by RIGAKU Corporation).
  • the type of the substrate is not particularly limited, and may be, for example, a substrate that is required to be imparted with water repellency.
  • the substrate include a substrate that may be used by contacting with other articles (e.g., a stylus) or human fingers; a substrate that may be held by human fingers during operation; and a substrate that may be placed on top of other articles (e.g., a mounting table).
  • the material of the substrate include metal, resin, glass, sapphire, ceramic, semiconductor, stone, fiber, nonwoven fabric, paper, wood, fur, natural leather, artificial leather, ceramics, and composite materials thereof. Glass may be chemically strengthened.
  • 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.
  • a substrate for a touch panel As the substrate, a substrate for a touch panel, a substrate for a display, or a lens for glasses is suitable, and a substrate for a touch panel is particularly suitable.
  • a substrate for a touch panel As the material for the substrate for a touch panel, glass or a transparent resin is preferred.
  • 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 1 elements of the periodic table refer to lithium, sodium, potassium, rubidium, and cesium.
  • Group 1 elements lithium, sodium, and potassium are preferred, and sodium and potassium are more preferred, from the viewpoint of being able to form a surface treatment layer on the underlayer more uniformly without defects, or of further suppressing variation in the composition of the underlayer between samples.
  • the underlayer may contain two or more types of Group 1 elements.
  • 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.
  • Group 13 elements of the periodic table refer to boron, aluminum, gallium, and indium.
  • Group 13 elements boron, aluminum, and gallium are preferred, and boron and aluminum are more preferred, from the viewpoint of being able to form a surface treatment layer on the underlayer more uniformly without defects, or of further suppressing variation in the composition of the underlayer between samples.
  • the underlayer may contain two or more types of Group 13 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 oxide contained in the underlayer may be a mixture of oxides of the above elements (silicon and the specific element) alone (for example, a mixture of silicon oxide and an oxide of the specific element), a composite oxide containing two or more of the above elements, or a mixture of an oxide of the above elements alone and a composite oxide.
  • the ratio of the total molar concentration of the specific elements in the underlayer to the molar concentration of silicon in the underlayer (specific elements/silicon) is preferably 0.02 to 2.90, more preferably 0.10 to 2.00, and even more preferably 0.20 to 1.80, from the viewpoint of achieving better abrasion resistance of the surface treatment layer.
  • the molar concentration (mol %) of each element in the underlayer can be measured, for example, by depth profile analysis using X-ray photoelectron spectroscopy (XPS) using ion sputtering.
  • 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 undercoat layer can be formed, for example, by a deposition method using a deposition material or a wet coating method.
  • 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.
  • silicon e.g., powder made of silicon oxide, silica sand, silica gel
  • a specific element e.g., powder of an oxide, carbonate, sulfate, nitrate, oxalate, hydroxide of a specific element
  • a specific example of a deposition method using a deposition material is a vacuum deposition method, in which a deposition material is evaporated in a vacuum chamber and attached to the surface of a substrate.
  • the temperature during deposition (for example, the temperature of a boat in which a deposition material is placed when a vacuum deposition apparatus is used) is preferably 100 to 3,000°C, and more preferably 500 to 3,000°C.
  • the pressure during deposition (for example, the pressure inside a tank in which a deposition material is placed when a vacuum deposition apparatus is used) is preferably 1 Pa or less, and more preferably 0.1 Pa or less.
  • one deposition material may be used, or two or more deposition materials containing different elements may be used.
  • 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.
  • examples include a case where silica and a specific source are mixed in the same boat and used, a case where silica and a specific element source are placed in separate boats and co-deposited, and a case where they are placed in separate boats and alternately deposited.
  • the deposition conditions, order, etc. are appropriately selected depending on the configuration of the underlayer.
  • a base layer on a substrate it is preferable to form a base layer on a substrate by a wet coating method using a coating liquid that contains a silicon-containing compound, a compound containing a specific element, and a liquid medium.
  • silicon compounds include silicon oxide, silicic acid, partial condensates of silicic acid, alkoxysilanes, and partial hydrolysis condensates of alkoxysilanes.
  • Specific examples of compounds containing a specific element include oxides of a specific element, alkoxides of a specific element, carbonates of a specific element, sulfates of a specific element, nitrates of a specific element, oxalates of a specific element, and hydroxides of a specific element.
  • the liquid medium may be the same as the liquid medium contained in the composition of the present disclosure.
  • the content of the liquid medium is preferably 0.01 to 20 mass % relative to the total amount of the coating liquid used to form the undercoat layer, and more preferably 0.1 to 10 mass %.
  • 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.
  • optical members examples include front protective plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDPs and LCDs; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and display surfaces of clocks.
  • the article of the present disclosure is preferably a display or a touch panel.
  • the article of the present disclosure may be a medical device or medical material.
  • the article of the present disclosure may also be an automobile interior or exterior component.
  • exterior materials include windows, light covers, and exterior camera covers.
  • interior materials include instrument panel covers, navigation system touch panels, and decorative interior materials.
  • 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.
  • Tetrahydrofuran (THF) 101 g was added to hexamethylcyclotrisiloxane (76 g) and stirred until dissolved, then a solution of lithium salt of trimethylsilanol (5.1 g) suspended in THF (20 g) was added and stirred at 25 ° C. for 2 hours. Then, chlorodimethylsilane (10.5 g) was added and stirred at 25 ° C. for 1 hour.
  • the substrate was surface-treated using the above compound.
  • the surface treatment method was a dry coating method. Chemically strengthened glass was used as the substrate.
  • Dry coating was performed using a vacuum deposition apparatus (product name "VTR-350M", manufactured by ULVAC).
  • a 20 mass % ethyl acetate solution (0.5 g) of each compound was filled into a molybdenum boat in the vacuum deposition apparatus, and the pressure in the vacuum deposition apparatus was evacuated to 1 ⁇ 10 ⁇ 3 Pa or less.
  • the boat was heated at a temperature increase rate of 10° C./min or less, and when the deposition rate measured by a quartz crystal oscillation film thickness meter exceeded 1 nm/sec, the shutter was opened to start film formation on the surface of the substrate. When the film thickness reached about 50 nm, the shutter was closed to end film formation on the surface of the substrate.
  • the substrate on which the compound was deposited was heat-treated at 200° C. for 30 minutes to obtain an article having a surface treatment layer on the surface of the substrate.
  • ⁇ Water repellency> Approximately 2 ⁇ L of distilled water was dropped onto the surface treatment layer of the article, and the initial water contact angle was measured using a contact angle measuring device (product name "DM-500", manufactured by Kyowa Interface Science Co., Ltd.). The average value of measurements at five points on the surface treatment layer was taken as the water contact angle. The 2 ⁇ method was used to calculate the water contact angle.
  • the evaluation criteria are as follows. A is a level that is not problematic for practical use. A: The water contact angle is 105° or more. B: The water contact angle is less than 105°.
  • ⁇ Wear resistance> The surface treatment layer of the article was subjected to a reciprocating traverse tester (manufactured by KNT Co., Ltd.) in accordance with JIS L0849:2013 (corresponding to ISO:105-X12:2001), and steel wool Bonstar (#0000) was reciprocated 10,000 times at a pressure of 98.07 kPa and a speed of 320 cm/min, and then the water contact angle after the friction test was measured.
  • the method for measuring the water contact angle after the friction test is the same as the method for measuring the initial water contact angle in the above-mentioned evaluation method for water repellency.
  • the abrasion resistance was evaluated based on the degree of decrease in the water contact angle due to the friction test.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Optics & Photonics (AREA)

Abstract

L'invention fournit un nouveau composé utile en tant qu'agent de traitement de surface permettant de former une couche traitée en surface d'une excellente résistance à la lumière et à l'usure, sur un substrat.　Plus précisément, l'invention concerne un composé représenté par la formule (1).　Ｔ－Ｏ－（Ｓｉ（Ｒ２）２－Ｏ）ｐ－（ＳｉＲ３Ｒ４－Ｏ）ｑ－（ＳｉＲ５Ｒ６－Ｏ）ｒ－Ｔ　（１）　T représente （Ｒ１）３Ｓｉ－, un résidu de polysiloxane cyclique monovalent, ou un résidu de polysiloxane de type cage monovalent, Ｒ１ représente un atome d'hydrogène, un groupe hydrocarbure ou un groupe trialkylsilyloxy, Ｒ２, Ｒ３ et Ｒ５ représentent un atome d'hydrogène ou un groupe hydrocarbure, Ｒ４ représente －Ｌ１－Ｓｉ（Ｒ）ｎＬ３－ｎ, Ｌ１ représente －Ｏ－ ou un groupe alkylène, R représente un groupe hydrocarbure, L représente un groupe hydrolysable, un groupe possédant un groupe hydrolysable, ou un groupe hydroxyl, Ｒ６ représente un groupe prédéfini, n représente un nombre entier de 0 à 2, p représente un nombre supérieur ou égal à 1, q représente un nombre supérieur ou égal à 2, r représente un nombre supérieur ou égal à 0, et s représente un nombre supérieur ou égal à 1.
PCT/JP2024/022685 2023-06-23 2024-06-21 Composé, composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci Pending WO2024262633A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023-103333 2023-06-23
JP2023103333 2023-06-23

Publications (1)

Publication Number Publication Date
WO2024262633A1 true WO2024262633A1 (fr) 2024-12-26

Family

ID=93935867

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/022685 Pending WO2024262633A1 (fr) 2023-06-23 2024-06-21 Composé, composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci

Country Status (1)

Country Link
WO (1) WO2024262633A1 (fr)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53135936A (en) * 1977-04-28 1978-11-28 Olin Corp Alkoxysilane double cluster having silicon bridge process for preparing same and application thereof
JPS55160093A (en) * 1979-04-27 1980-12-12 Olin Mathieson Silicone oil composition containing silicate cluster compound
JPH05105761A (ja) * 1991-09-30 1993-04-27 Kanegafuchi Chem Ind Co Ltd ケイ素系ハイブリツド材料
JPH05194930A (ja) * 1992-01-21 1993-08-03 Shin Etsu Chem Co Ltd シリコーンゴム接着剤組成物
JPH05239218A (ja) * 1992-02-26 1993-09-17 Nippon Dow Corning Kk 分岐ポリシロキサンの製造方法
JPH07252472A (ja) * 1994-01-31 1995-10-03 Shin Etsu Chem Co Ltd 撥水処理剤
JPH08209118A (ja) * 1994-08-12 1996-08-13 Shin Etsu Chem Co Ltd 撥水処理剤
JPH0940910A (ja) * 1995-07-27 1997-02-10 Shin Etsu Chem Co Ltd 撥水処理剤
JP2006299266A (ja) * 2005-04-21 2006-11-02 Wacker Chemie Ag トリオルガノシロキシ基を有するオルガノポリシロキサンの製造法
JP2013520429A (ja) * 2010-02-19 2013-06-06 ボード・オブ・リージエンツ，ザ・ユニバーシテイ・オブ・テキサス・システム 有枝鎖シロキサンおよび合成のための方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53135936A (en) * 1977-04-28 1978-11-28 Olin Corp Alkoxysilane double cluster having silicon bridge process for preparing same and application thereof
JPS55160093A (en) * 1979-04-27 1980-12-12 Olin Mathieson Silicone oil composition containing silicate cluster compound
JPH05105761A (ja) * 1991-09-30 1993-04-27 Kanegafuchi Chem Ind Co Ltd ケイ素系ハイブリツド材料
JPH05194930A (ja) * 1992-01-21 1993-08-03 Shin Etsu Chem Co Ltd シリコーンゴム接着剤組成物
JPH05239218A (ja) * 1992-02-26 1993-09-17 Nippon Dow Corning Kk 分岐ポリシロキサンの製造方法
JPH07252472A (ja) * 1994-01-31 1995-10-03 Shin Etsu Chem Co Ltd 撥水処理剤
JPH08209118A (ja) * 1994-08-12 1996-08-13 Shin Etsu Chem Co Ltd 撥水処理剤
JPH0940910A (ja) * 1995-07-27 1997-02-10 Shin Etsu Chem Co Ltd 撥水処理剤
JP2006299266A (ja) * 2005-04-21 2006-11-02 Wacker Chemie Ag トリオルガノシロキシ基を有するオルガノポリシロキサンの製造法
JP2013520429A (ja) * 2010-02-19 2013-06-06 ボード・オブ・リージエンツ，ザ・ユニバーシテイ・オブ・テキサス・システム 有枝鎖シロキサンおよび合成のための方法

Similar Documents

Publication Publication Date Title
JP7726377B2 (ja) 化合物、組成物、表面処理剤、物品、及び物品の製造方法
TW202344575A (zh) 化合物、組成物、表面處理劑、物品、及物品之製造方法
WO2023181867A1 (fr) Composé, composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci
WO2024262627A1 (fr) Composé ainsi que procédé de fabrication de celui-ci, composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci
WO2023181864A1 (fr) Composé, composition, agent de traitement de surface, article et procédé de production d'article
CN118974064A (zh) 化合物、组合物、表面处理剂、物品的制造方法、及物品
JP2025064763A (ja) 組成物、表面処理剤、物品、物品の製造方法、及びｕｖ吸収剤
WO2023210378A1 (fr) Composé, composition, agent de traitement de surface, procédé de fabrication d'article et article
WO2024262633A1 (fr) Composé, composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci
WO2025033510A1 (fr) Composé, composition, agent de traitement de surface, article et procédé de production d'article
WO2025070360A1 (fr) Composé, composition, agent de traitement de surface, article, procédé de production d'article et intermédiaire
WO2025110181A1 (fr) Composé, composition, agent de traitement de surface, article et procédé de production d'article
WO2025075200A1 (fr) Composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci
WO2025075198A1 (fr) Composition, agent de traitement de surface, article et procédé de production d'article
WO2025009614A1 (fr) Composé, composition, agent de traitement de surface, article et procédé de production d'article
WO2025033353A1 (fr) Composé, composition, agent de traitement de surface, article et procédé de production d'article
WO2024262632A1 (fr) Composé, composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci
WO2025033446A1 (fr) Composé, composition, agent de traitement de surface, article et procédé de production d'article
WO2025075203A1 (fr) Article et procédé de fabrication d'article
WO2025018316A1 (fr) Composé, composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci
WO2025100477A1 (fr) Composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci
WO2025058055A1 (fr) Composé, composition, agent de traitement de surface, granulé, article et procédé de production d'article
WO2025009612A1 (fr) Composé, composition, agent de traitement de surface, article et procédé de production d'article
WO2025075201A1 (fr) Composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci
WO2025013911A1 (fr) Composé, composition, agent de traitement de surface, et article ainsi que procédé de fabrication de celui-ci

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24826034

Country of ref document: EP

Kind code of ref document: A1