WO2023153450A1 - Agent de traitement de surface, liquide de revêtement, article et procédé de production d'un article - Google Patents

Agent de traitement de surface, liquide de revêtement, article et procédé de production d'un article Download PDF

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WO2023153450A1
WO2023153450A1 PCT/JP2023/004226 JP2023004226W WO2023153450A1 WO 2023153450 A1 WO2023153450 A1 WO 2023153450A1 JP 2023004226 W JP2023004226 W JP 2023004226W WO 2023153450 A1 WO2023153450 A1 WO 2023153450A1
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group
mass
ions
treatment agent
compound
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PCT/JP2023/004226
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Japanese (ja)
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大介 小林
啓吾 松浦
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Ａｇｃ株式会社
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    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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

Definitions

  • the present invention relates to a surface treatment agent, a coating liquid, an article, and a method for manufacturing an article.
  • the surface of the substrate is treated with a fluorine-containing ether compound having a fluoropolyether chain and a reactive silyl group. It is known to form a surface layer composed of a condensate of a fluorine-containing ether compound (Patent Document 1).
  • an object of the present invention is to provide a surface treatment agent, a coating liquid, an article, and a method for manufacturing an article that can form a surface layer with excellent lubricity.
  • a surface layer formed on a substrate using a surface treatment agent can be analyzed using a tandem mass spectrometer capable of time-of-flight mass spectrometry. It was found that the surface treatment agent is capable of forming a surface layer with excellent lubricity when specific requirements regarding the ratio of peak area intensities of product ions obtained by analysis are satisfied. Arrived.
  • the fluoropolyether chain comprises units represented by (OCF 2 ), units represented by (OC 2 F 4 ), and units represented by (OC 3 F 6 ), [ 1] The surface treatment agent according to any one of [3].
  • a coating liquid comprising the surface treatment agent according to any one of [1] to [4] and a liquid medium.
  • the fluoropolyether chain comprises units represented by (OCF 2 ), units represented by (OC 2 F 4 ), and units represented by (OC 3 F 6 ), [ 7] or the article according to [8].
  • the present invention it is possible to provide a surface treatment agent, a coating liquid, an article, and a method for manufacturing an article that can form a surface layer with excellent lubricity.
  • a fluoroalkyl group is a collective term for a perfluoroalkyl group and a partial fluoroalkyl group.
  • a perfluoroalkyl group means a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms.
  • a partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms are substituted with fluorine atoms and which has one or more hydrogen atoms.
  • a fluoroalkyl group is an alkyl group having one or more fluorine atoms.
  • "Reactive silyl group” is a general term for hydrolyzable silyl groups and silanol groups (Si-OH), and "hydrolyzable silyl group” is a group that can be hydrolyzed to form a silanol group.
  • Organic group means a hydrocarbon group which may have a substituent and which may have a heteroatom or other bond in the carbon chain.
  • the “hydrocarbon group” is a group consisting of a carbon atom and a hydrogen atom, and is an aliphatic hydrocarbon group (for example, a divalent aliphatic hydrocarbon group includes a linear alkylene group, a branched alkylene group, a cyclo alkylene groups, etc.), aromatic hydrocarbon groups (for example, divalent aromatic hydrocarbon groups such as phenylene groups, etc.), and groups consisting of combinations thereof.
  • a "surface layer” means a layer formed on a substrate.
  • the "molecular weight" of the fluoropolyether chain and the compound is a number average molecular weight calculated by determining the number (average value) of oxyfluoroalkylene units based on the terminal group by 1 H-NMR and 19 F-NMR. be. " ⁇ " indicating a numerical range means that the numerical values before and after it are included as lower and upper limits.
  • the surface treatment agent of the present invention (hereinafter also referred to as "this treatment agent”) contains a fluorine-containing ether compound having a fluoropolyether chain and a reactive group, and satisfies Requirement 1 below.
  • Requirement 1 generating negative secondary ions by irradiating pulsed primary ions to a surface layer formed on a substrate using a surface treatment agent; separating the generated negative secondary ions based on their mass-to-charge ratio using a first time-of-flight secondary ion mass spectrometer; Selecting negative secondary ions having a mass-to-charge ratio of 348 u as precursor ions from the separated negative secondary ions using an ion selection device, introducing selected precursor ions into a collision cell for cleavage by high-energy collision-induced dissociation to produce product ions; In a mass spectrum showing the relationship between the mass-to-charge ratio and area intensity of product ions obtained from the generated product ions using a second mass spectrometer, The sum of the area intensities of each peak corresponding to product ions with mass-to-charge ratios of 66u, 166u, 182u and 282u with respect to the total IA of the area intensities of each peak corresponding to product ions with mass-to-
  • this treatment agent that satisfies Requirement 1 above, a surface layer with excellent lubricity can be formed.
  • this treatment agent is suitable as a surface treatment agent for forming a surface layer imparting water/oil repellency, abrasion resistance, and fingerprint stain removability on a substrate.
  • the evaluation method for Requirement 1 will be described in detail below.
  • Requirement 1 is determined based on the analysis results obtained by forming a surface layer on a substrate using a surface treatment agent, analyzing the surface layer using the following mass spectrometer.
  • Methods of forming a surface layer on a substrate using a surface treatment agent include a method of forming a surface treatment agent by a dry coating method, and a method of forming a coating liquid containing a surface treatment agent and a liquid medium by a wet coating method. method. Examples of the method for forming the surface layer on the base material include the method described in [Method for producing article] described later. Further, examples of the substrate include substrates described in [Articles] described later.
  • a primary ion source For analysis of the surface layer, a primary ion source, a first time-of-flight mass spectrometer (hereinafter also referred to as "first mass spectrometer") for detecting secondary ions, and an ion selection device. , a collision cell, and a second mass spectrometer for detecting product ions is used.
  • the ion selection device is placed between the analyzer (separation section) and the detection section of a known time-of-flight secondary ion mass spectrometer (TOF-SIMS), and specific ions are introduced into the collision cell. configuration.
  • TOF-SIMS performs mass separation by utilizing the time-of-flight difference due to the difference in the mass-to-charge ratio of generated secondary ions.
  • the ion selection device selects ions having a specific mass-to-charge ratio from among the secondary ions with different flight times, introduces them into the collision cell, and obtains a mass spectrum using these ions as precursor
  • a primary ion source bombards the surface layer with pulsed primary ions. More specifically, the ion source irradiates the surface layer with Bi 3 ++ as primary ions. As a result, negative secondary ions derived from the compound forming the surface layer are generated.
  • the first mass spectrometer includes, for example, a separation section that spatially separates negative secondary ions based on their mass-to-charge ratio, and a detection section that detects the separated negative secondary ions.
  • the separation section of the first mass spectrometer spatially separates the negative secondary ions generated from the surface layer and taken into the separation section based on the mass-to-charge ratio.
  • the ion selector selects negative secondary ions having a mass-to-charge ratio of 348 u as precursor ions from the negative secondary ions separated by the first mass spectrometer, and guides them to the collision cell.
  • the ion selection device is arranged, for example, between the separation section and the detection section provided in the first mass spectrometer, and includes a plurality of electrodes. When a voltage is applied between the electrodes at the timing at which the precursor ions enter the ion selector, the traveling direction of the precursor ions trying to pass between the electrodes is changed to the direction in which the precursor ions are directed toward the collision cell. On the other hand, when no voltage is applied between the electrodes, the negative secondary ions that have entered the ion selector pass through the electrodes without changing their traveling direction and reach the detector of the first mass spectrometer.
  • a collision cell for example, comprises a chamber and a collision gas enclosed in the chamber.
  • a precursor ion enters the collision cell, it collides with the collision gas in the chamber and undergoes high-energy Collisional Organic Dissociation (CID) in which the precursor ion is fragmented into product ions.
  • CID Collisional Organic Dissociation
  • Ar is selected as the collision gas.
  • a second mass spectrometer detects the product ions produced in the collision cell, and the detection results provide a mass spectrum showing the relationship between the mass-to-charge ratio of the product ions and the amount detected.
  • the second mass spectrometer includes, for example, a time-of-flight mass spectrometer, a quadrupole mass spectrometer, and an ion trap mass spectrometer.
  • the time-of-flight mass spectrometer is selected. . Further specific examples of the analysis apparatus and analysis method for the surface layer are described in Japanese Patent Publication No. 2015-514300.
  • the peak area intensities of product ions having mass-to-charge ratios of 66u, 116u, 166u, 182u, 232u and 282u are determined from the mass spectrum obtained by the second mass spectrometer.
  • total area intensity I A the total I A of peak area intensities corresponding to product ions with mass-to-charge ratios of 116u and 232u
  • mass-to-charge ratios of 66u, 166u, 182u and A total I B of peak area intensities corresponding to product ions of 282u (hereinafter also referred to as “total area intensity I B ”) is calculated, and a ratio I B / IA is determined.
  • the total area intensity IA and IB from the viewpoint of reliability, for example, the total area intensity IA should be 100000 counts or more, or the total area intensity IB should be 1000 counts or more.
  • precursor ions with a mass-to-charge ratio of 348u product ions with a mass-to-charge ratio of either 116u or 232u (hereinafter also referred to as “product ions A”), mass-to-charge ratios of 66u, 166u, 182u and 282u (hereinafter also referred to as “product ion B”) and the ratio I B / IA .
  • product ions A product ions with a mass-to-charge ratio of 348u
  • product ion B mass-to-charge ratios of 66u, 166u, 182u and 282u
  • the ratio I B / IA ratio
  • the precursor ion with a mass-to-charge ratio of 348 u is derived from a fluoropolyether chain that constitutes a part of the surface treatment agent, and corresponds to a negative secondary ion represented by the composition formula “C 6 F 12 O 3 ⁇ ”.
  • this precursor ion can have structures represented by the following structural formulas (1) to (4), the ether bond of the precursor ion is cut by fragmentation in the collision cell, resulting in a mass-to-charge ratio of at least 66u. , 116u, 166u, 182u, 232u and 282u in total six product ions can be generated.
  • the structural site (1) consisting only of (C 2 F 4 O) units produces a product ion A with a mass-to-charge ratio of 116u or 232u.
  • structural sites (2) to (4) have (CF 2 O) units, (C 2 F 4 O) units, and (C 3 F 6 O) units, so the mass-to-charge ratio is 116 u or 232 u.
  • product ions A which have mass-to-charge ratios of 66u, 166u, 182u, or 282u, product ions B are also produced.
  • the ratio I B /IA of the total area intensity I B of product ion B to the total area intensity I A corresponding to product ion A which is obtained by fragmenting precursor ions having a mass-to-charge ratio of 348 u , is , can be said to be a parameter indicating the continuity of the same unit. That is, the higher the ratio I B / IA obtained by the above method, the lower the continuity of the same units in the fluoropolyether chain contained in the surface layer.
  • a surface layer having excellent lubricity can be formed by a treatment agent having a ratio I B / IA of 0.025 or more has not been clarified in detail, but the reason is presumed as follows.
  • this treatment agent that contains a fluorine-containing ether compound having a fluoropolyether chain and a reactive group and satisfies Requirement 1
  • the fluoropolyether chain contained in the surface layer has 1 carbon atom. or 2
  • the continuity of the fluoroalkylene units tends to decrease, and the packing property of the fluoropolyether chains in the surface layer tends to decrease.
  • the degree of freedom of the fluoropolyether chain was improved and the lubricity of the surface layer was enhanced.
  • the ratio I B /I A is preferably 0.040 or more, more preferably 0.090 or more, so that a surface layer with better lubricity can be formed.
  • the upper limit of the ratio I B / IA is preferably 0.610 or less, more preferably 0.400 or less, and even more preferably 0.160 or less.
  • the ratio I B /I A is, for example, the perfluoropolyether compound ( It can be adjusted by controlling the molecular weight of PFPE).
  • a fluorine-containing ether compound has a fluoropolyether chain and a reactive group.
  • the fluorine-containing ether compound contained in the present processing agent has a fluoropolyether chain
  • the surface layer obtained using the present processing agent is excellent in water and oil repellency and fingerprint stain removability.
  • the fluorine-containing ether compound has a reactive group. Since the reactive groups are strongly chemically bonded to the substrate, the resulting surface layer is excellent in durability such as abrasion resistance.
  • a fluoropolyether chain is a group having two or more oxyfluoroalkylene units.
  • the fluoropolyether chain may have hydrogen atoms.
  • the proportion of fluorine atoms in the fluoropolyether chain represented by the following formula (I) is preferably 60% or more, more preferably 80% or more. , substantially 100%, ie perfluoropolyether chains, are more preferred. If the fluorine atom content is 60% or more, the amount of fluorine in the fluoropolyether chain increases, and the lubricity and fingerprint removability are further improved.
  • Formula (I): Percentage of fluorine atoms (%) (number of fluorine atoms) / ⁇ (number of fluorine atoms) + (number of hydrogen atoms) ⁇ x 100
  • the molecular weight per fluoropolyether chain is preferably 2,000 to 20,000, more preferably 2,500 to 15,000, from the viewpoint of achieving both fingerprint stain removal and lubricity on the surface layer. ,000 to 10,000 is more preferred. If the molecular weight of the fluoropolyether chain is 2,000 or more, the flexibility of the fluoropolyether chain is improved, and the fluorine content in the molecule is increased, thereby further improving the lubricity and fingerprint removability. On the other hand, if the molecular weight of the fluoropolyether chain is 20,000 or less, the abrasion resistance of the surface layer is more excellent.
  • the fluoropolyether chain is preferably structure (f1). (OR f ) y (f1)
  • R f is a fluoroalkylene group having 1 to 6 carbon atoms, and a plurality of R f may be the same or different. y may be an integer of 2 or more, preferably 2-200.
  • (OR f ) y preferably has a structure represented by the following formula (f2). - [(OG f1 ) m1 (OG f2 ) m2 (OG f3 ) m3 (OG f4 ) m4 (OG f5 ) m5 (OG f6 ) m6 ]- ...(f2) however, G f1 is a fluoroalkylene group having 1 carbon atoms, G f2 is a fluoroalkylene group having 2 carbon atoms, G f3 is a fluoroalkylene group having 3 carbon atoms, G f4 is a fluoroalkylene group having 4 carbon atoms, G f5 is a fluoroalkylene group having 5 carbon atoms, G f6 is a fluoroalkylene group having 6 carbon atoms, m1, m2, m3, m4, m5 and m6 each independently represents an integer of 0 or 1 or more, and
  • the bonding order of (OG f1 ) to (OG f6 ) in formula (f2) is arbitrary.
  • m1 to m6 in the formula (f2) represent the number of (OG f1 ) to (OG f6 ), respectively, and do not represent the arrangement.
  • (OG f5 ) m5 indicates that the number of (OG f5 ) is m5, and does not indicate the block arrangement structure of (OG f5 ) m5 .
  • the order of (OG f1 ) to (OG f6 ) does not represent the order of bonding of the respective units.
  • the fluoroalkylene group having 3 to 6 carbon atoms may be a linear fluoroalkylene group or a fluoroalkylene group having a branched or ring structure.
  • G f1 examples include -CF 2 - and -CHF-.
  • G f2 examples include -CF 2 CF 2 -, -CHFCF 2 -, -CHFCHF-, -CH 2 CF 2 -, -CH 2 CHF- and the like.
  • G f3 include -CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 -, -CF 2 CH 2 CF 2 -, -CHFCF 2 CF 2 -, -CHFCHFCF 2 -, -CHFCHFCHF-, - CHFCH2CF2- , -CH2CF2CF2- , -CH2CHFCF2- , -CH2CH2CF2- , -CH2CF2CHF- , -CH2CHFCHF- , -CH2CH2 _ _ CHF-, -CF(CF 3 )-CF 2 -, -CF(CHF 2 )-CF 2 -, -CF(CH 2 F)-CF 2 -, -CF(CH 3 )-CF 2 -, -CF (CF 3 )-CHF-, -CF(CHF 2 )-CHF-, -CF(CH 2 F)-CHF-, -CF(CH 3 )-CF
  • G f4 include -CF 2 CF 2 CF 2 -, -CHFCF 2 CF 2 CF 2 -, -CH 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 -, -CHFCHFCF 2CF2- , -CH2CHFCF2CF2- , -CF2CH2CF2CF2- , -CHFCH2CF2CF2- , -CH2CH2CF2CF2- , -CHFCF2CHFCF2 _ _ _ _ _ _ _ _ - - -, -CH 2 CF 2 CHFCF 2 -, -CF 2 CHFCHFCF 2 -, -CHFCHFCHFCF 2 -, -CH 2 CHFCHFCF 2 -, -CF 2 CH 2 CHFCF 2 -, -CHFCH 2 CHFCF 2 -, -CH 2 CH 2CHFCF2- , -CF2CH2CH2CF2- , -
  • G f5 examples include -CF 2 CF 2 CF 2 CF 2 CF 2 -, -CHFCF 2 CF 2 CF 2 -, -CH 2 CHFCF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 —, —CHFCHFCF 2 CF 2 CF 2 —, —CF 2 CH 2 CF 2 CF 2 —, —CHFCH 2 CF 2 CF 2 CF 2 —, —CH 2 CH 2 CF 2 CF 2 CF 2 —, -CF2CF2CHFCF2CF2- , -CHFCF2CHFCF2CF2- , -CH2CF2CHFCF2CF2- , -CH2CF2CF2CF2CH2- , -cycloC5F8- _ _ _ _ _ _ _ _ etc.
  • G f6 include -CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CHFCHFCF 2 CF 2 -, -CHFCF 2 CF 2 CF 2 CF 2 CF 2 -, -CHFCHFCHFCHFCHFCHF- , -CHFCF 2 CF 2 CF 2 CH 2 -, -CH 2 CF 2 CF 2 CF 2 CH 2 -, -cycloC 6 F 10 - and the like.
  • -cycloC 4 F 6 - means a perfluorocyclobutanediyl group, a specific example of which is a perfluorocyclobutane-1,2-diyl group.
  • -cycloC 5 F 8 - means a perfluorocyclopentanediyl group, and specific examples thereof include a perfluorocyclopentane-1,3-diyl group.
  • -cycloC 6 F 10 - means a perfluorocyclohexanediyl group, a specific example of which is a perfluorocyclohexane-1,4-diyl group.
  • (OR f ) y preferably has any one of the structures represented by the following formulas (f3) to (f6) from the viewpoint of being superior in water and oil repellency, abrasion resistance, and fingerprint stain removability.
  • the following formulas (f3) and (f4) are more preferred, and the following formula (f4) is even more preferred from the viewpoint of superior lubricity.
  • m1 is preferably 1 to 60, more preferably 1 to 40, even more preferably 1 to 30, and particularly preferably 1 to 20.
  • m2 is preferably 1-30, more preferably 1-20.
  • m3 is preferably 1-30, more preferably 1-20.
  • the ratio of m3 in the formula (f4) [m3/(m1+m2+m3)] is preferably 0.025 to 0.110, more preferably 0.040 to 0.090, from the viewpoint of further improving the lubricity of the surface layer.
  • the ratio [m3/m2] of m3 to m2 is preferably 0.06 to 0.25, more preferably 0.08 to 0.20, from the viewpoint of further improving the lubricity of the surface layer.
  • m2 is preferably 1-30, more preferably 1-20.
  • m4 is preferably 1-30, more preferably 1-20.
  • m3 is preferably 1-30, more preferably 1-20.
  • the fluoropolyether chain preferably contains units represented by (OCF 2 ), units represented by (OC 2 F 4 ), and units represented by (OC 3 F 6 ).
  • the fluoropolyether chain preferably contains a structure represented by the following formula (f7).
  • ( OC2F4 ) m22 .( OC3F6 ) m23 (f7) In formula (f7), m21 is preferably 1-60, more preferably 1-40, even more preferably 1-30, and particularly preferably 1-20.
  • m22 is preferably 1-30, more preferably 1-20.
  • m23 is preferably 1-30, more preferably 1-20.
  • the ratio of m23 in the formula (f7) [m23/(m21+m22+m23)] is preferably 0.025 to 0.110, more preferably 0.040 to 0.090, from the viewpoint of further improving the lubricity of the surface layer.
  • the ratio [m23/m22] of m23 and m22 is preferably 0.06 to 0.25, more preferably 0.08 to 0.20, from the viewpoint of further improving the lubricity of the surface layer.
  • (OCF 2 ), (OC 2 F 4 ) and (OC 3 F 6 ) may be combined in any order.
  • (OCF 2 ), (OC 2 F 4 ) and (OC 3 F 6 ) may be randomly arranged in formula (f6), and (OCF 2 ), (OC 2 F 4 ) and (OC 3 F 6 ) may be arranged in each block, or a block in which (OCF 2 ) and (OC 2 F 4 ) are alternately arranged and a block of (OC 3 F 6 ) may be arranged.
  • the fluoropolyether chain may contain oxyfluoroalkylene units other than (OCF 2 ), (OC 2 F 4 ) and (OC 3 F 6 ) (hereinafter also referred to as “other oxyfluoroalkylene units”). good.
  • oxyfluoroalkylene units include (OG f1 ) m1 (except when G f1 is —CF 2 —), (OG f2 ) m2 (provided that G Except when f2 is -CF 2 CF 2 -), (OG f3 ) m3 (However, except when G f3 is -CF 2 CF 2 CF 2 -), (OG f4 ) m4 , ( OG f5 ) m5 and (OG f6 ) m6 .
  • the ratio of fluorine atoms in the fluoropolyether chain (OR f ) y [ ⁇ number of fluorine atoms / (number of fluorine atoms + number of hydrogen atoms) ⁇ ⁇ 100 (%)] is excellent in water and oil repellency and fingerprint removability From the point of view, 60% or more is preferable, 70% or more is more preferable, and 80% or more is still more preferable. The upper limit of the above ratio is usually 100%. Further, the molecular weight of the fluoropolyether chain (OR f ) y portion is preferably from 2,000 to 20,000, more preferably from 2,500 to 15,000, more preferably from 3,000 to 10,000, from the viewpoint of abrasion resistance. 000 is more preferred.
  • the reactive group possessed by the fluorine-containing ether compound is a general term for groups having functional groups that chemically bond with the material constituting the substrate.
  • Reactive groups include reactive silyl groups, ethylenically unsaturated groups (e.g., (meth)acryloyl groups, allyl groups, styryl groups, etc.), cyclic ether groups (e.g., epoxy groups, oxetanyl groups, etc.), and isocyanate groups. , a carboxy group, a hydroxyl group, a mercapto group, an amino group, and the like.
  • a reactive silyl group or a polymerizable unsaturated group is preferable, and a reactive silyl group is more preferable, from the viewpoint of adhesion to the substrate.
  • the reactive silyl group is preferably the group (g1). —SiR a1 z1 R a2 3-z1 (g1) however, R a1 is a hydroxyl group or a hydrolyzable group, and when there are multiple R a1 s , the multiple R a1s may be the same or different, R a2 is a non-hydrolyzable group, and when there are multiple R a2 s, the multiple R a2s may be the same or different, z1 is an integer of 1-3.
  • R a1 When R a1 is a hydroxyl group, it constitutes a silanol (Si—OH) group together with the Si atom.
  • a hydrolyzable group is a group that becomes a hydroxyl group (that is, a silanol group) by a hydrolysis reaction.
  • the silanol groups further react intermolecularly to form Si--O--Si bonds.
  • the silanol group undergoes a dehydration condensation reaction with the hydroxyl group (substrate (or underlying layer) —OH) on the surface of the substrate (or underlying layer) to form a chemical bond (substrate (or underlying layer) —O—Si).
  • the fluorine-containing ether compound has one or more groups (g1), it has excellent abrasion resistance after forming the surface layer.
  • the hydrolyzable group of R a1 includes an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, an isocyanate group (--NCO) and the like.
  • alkoxy group an alkoxy group having 1 to 4 carbon atoms is preferable.
  • acyl group an acyl group having 1 to 6 carbon atoms is preferred.
  • acyloxy group an acyloxy group having 1 to 6 carbon atoms is preferred.
  • R a1 is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of ease of production of the fluorine-containing ether compound.
  • the alkoxy group for R a1 is preferably an alkoxy group having 1 to 4 carbon atoms because the storage stability of the fluorine-containing ether compound is excellent and outgassing during the reaction is suppressed, and from the viewpoint of long-term storage stability.
  • the halogen atom a chlorine atom is particularly preferable.
  • Examples of the non-hydrolyzable group for R a2 include a hydrogen atom and a monovalent hydrocarbon group.
  • the hydrocarbon group includes an alkyl group, a cycloalkyl group, an alkenyl group, an allyl group and the like, and an alkyl group is preferable from the viewpoint of ease of production. From the standpoint of ease of production, etc., the number of carbon atoms in the hydrocarbon group is preferably 1-6, more preferably 1-3, even more preferably 1-2.
  • z1 may be an integer of 1 to 3, preferably 2 or 3, more preferably 3, from the viewpoint of adhesion to the substrate (or underlying layer).
  • Specific examples of the group (g1) include -Si(OCH 3 ) 3 , -SiCH 3 (OCH 3 ) 2 , -Si(OCH 2 CH 3 ) 3 , -SiCl 3 , -Si(OCOCH 3 ) 3 , - Si(NCO) 3 and the like.
  • -Si(OCH 3 ) 3 is preferred from the viewpoint of ease of handling in production.
  • the multiple groups (g1) may be the same or different.
  • the fluorine-containing ether compound In the fluorine-containing ether compound, the fluoropolyether chain and the reactive group are bonded directly or via a linking group.
  • the fluorine-containing ether compound is preferably a compound in which the fluoropolyether chain and the group (g1) are bonded directly or via a linking group.
  • Examples of the linking group include divalent or higher organic groups.
  • the number of fluoropolyether chains in one molecule of the fluorine-containing ether compound may be one or two or more.
  • the number of fluoropolyether chains in one molecule is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 4, from the viewpoint of ease of synthesis and the like.
  • the number of reactive groups in one molecule of the fluorine-containing ether compound may be one or two or more.
  • the number of groups (g1) is preferably 1 to 32, more preferably 1 to 18, from the viewpoint of achieving both abrasion resistance and water/oil repellency. ⁇ 12 is more preferred.
  • the plurality of fluoropolyether chains may be the same or different.
  • each reactive group may be the same or different.
  • Any fluorine-containing ether compound may be used as long as it satisfies the above constitution.
  • Compounds represented by the following formula (A1), (A2), or (A3) are particularly preferred from the viewpoints of easiness of synthesis, easiness of handling of the compound, and the like.
  • R f1 is a fluoroalkyl group having 1 to 20 carbon atoms, and when there are a plurality of R f1 , the plurality of R f1 may be the same or different; R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are a plurality of R f11 , the plurality of R f11 may be the same or different,
  • Compound (A1) has a structure represented by the following formula (A1). [R f1 ⁇ (OR f11 ) y1 ⁇ OR 1 ] j ⁇ L 1 ⁇ (R 11 ⁇ T 11 ) x1 (A1) However, each symbol in the formula (A1) is as described above.
  • R f1 is a fluoroalkyl group having 1 to 20 carbon atoms.
  • the fluoroalkyl group may be linear, branched and/or have a cyclic structure.
  • a straight-chain fluoroalkyl group is preferable from the viewpoint of abrasion resistance, and the number of carbon atoms in the fluoroalkyl group is preferably 1 to 6, more preferably 1 to 3, from the viewpoint of ease of synthesis.
  • R f11 and y1 in (OR f11 ) y1 are the same as R f and y in formula (f1) above, and preferred embodiments are also the same.
  • R 1 is an alkylene group or a fluoroalkylene group.
  • the alkylene group and fluoroalkylene group for R 1 may be linear or may have a branched and/or cyclic structure. From the viewpoint of ease of synthesis and the like, a linear or branched alkylene group or fluoroalkylene group is preferable, and a linear or branched alkylene group or fluoroalkylene group having a methyl group or a fluoromethyl group is more preferable.
  • the number of carbon atoms in R 1 is preferably 1-6, more preferably 1-3.
  • R 1 is bonded to R 11 when L 1 is a single bond. In this case, the carbon atom bonded to R 11 in R 1 should be bonded to at least one fluorine atom or fluoroalkyl group.
  • j represents the number of [R f1 -(OR f11 ) y1 -OR 1 ] in one molecule, and may be an integer of 1 or more, preferably 1 to 20, more preferably 1 to 10, 1 to 4 is more preferred.
  • R 11 is an alkylene group in which the atom bonded to L 1 may be an etheric oxygen atom or may have an etheric oxygen atom between carbon atoms.
  • the alkylene group for R 11 may be linear or may have a branched and/or cyclic structure.
  • a linear or branched alkylene group having a methyl group is preferable, and a linear alkylene group is more preferable, because the compound (A1) is likely to be densely arranged when forming a surface layer.
  • R 11 can be specifically represented by the following formula (g2).
  • R g2 is an alkylene group having 1 or more carbon atoms, and a plurality of R g2 may be the same or different, a1 is 0 or 1, a2 is an integer of 0 or more, * is a bond that binds to L1 , ** is a bond that binds to T11 .
  • a1 When a1 is 0, the atom having the bond * becomes a carbon atom, and when a1 is 1, the atom having the bond * becomes an oxygen atom.
  • a1 may be either 0 or 1, and may be selected as appropriate from the viewpoint of synthesis and the like.
  • a2 is the number of repetitions of R g2 O, preferably 0 to 6, more preferably 0 to 3, even more preferably 0 to 1, from the viewpoint of durability as a surface layer.
  • R 11 is more preferably a group represented by the following formula (g3) from the viewpoint that the surface layer is excellent in water and oil repellency, fingerprint stain removability, and durability such as abrasion resistance.
  • *-(O) a1 -R g3 -** (g3) however, R g3 is an alkylene group, a1, * and ** are the same as in formula (g2).
  • the alkylene group for R g3 may be linear or may have a branched and/or cyclic structure.
  • a linear alkylene group is preferable from the viewpoint that the compound (A1) is likely to be densely arranged when forming the surface layer.
  • the number of carbon atoms in R g3 may be 1 or more, preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 6.
  • T 11 is —SiR a11 z11 R a12 3-z11 , R a11 , R a12 and z11 are respectively the same as R a1 , R a2 and z1 constituting the above group (g1), and preferred embodiments are also the same. be.
  • x1 represents the number of R 11 -T 11 in one molecule, and may be an integer of 1 or more, preferably 1-32, more preferably 1-18, even more preferably 2-12.
  • the atoms bonded to R 1 and R 11 may be the same atom or different atoms.
  • L 1 is at least one branch point (hereinafter referred to as "branch point P 1 '').
  • the branch point P 1 When N is the branch point P 1 , the branch point P 1 is represented by * ⁇ N( ⁇ **) 2 or (* ⁇ ) 2 N ⁇ **, for example. However, * is a bond on the R1 side, and ** is a bond on the R11 side.
  • the branch point P 1 When C is the branch point P 1 , the branch point P 1 is, for example, * ⁇ C( ⁇ **) 3 , (* ⁇ ) 2 C( ⁇ **) 2 , (* ⁇ ) 3 C ⁇ **, *-CR 29 (-**) 2 or (*-) 2 CR 29 -**.
  • the branch point P 1 is, for example, *-Si(-**) 3 , (*-) 2 Si(-**) 2 , (*-) 3 Si-**, *-SiR 29 (-**) 2 or (*-) 2 SiR 29 -**.
  • R 29 is a monovalent group such as a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, and the like. be done.
  • a 3- to 8-membered aliphatic ring is used because it facilitates the production of a fluorine-containing ether compound and the abrasion resistance, light resistance, and chemical resistance of the surface layer are further excellent.
  • One selected from the group consisting of a ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocyclic ring, and a condensed ring consisting of two or more of these rings is preferable, and is listed in the following formula. is more preferred.
  • organopolysiloxane residue constituting the branch point P1 examples include the following groups.
  • R25 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the number of carbon atoms in the alkyl group and alkoxy group of R 25 is preferably 1 to 10, more preferably 1.
  • L 1 Divalent or higher L 1 is —C(O)N(R 26 )—, —N(R 26 )C(O)—, —C(O)O—, —OC(O)—, —C( O)-, -O-, -N(R 26 )-, -S-, -OC(O)O-, -NHC(O)O-, -OC(O)NH-, -NHC(O)N (R 26 )-, -SO 2 N(R 26 )-, -N(R 26 )SO 2 -, -Si(R 26 ) 2 -, -OSi(R 26 ) 2 -, -Si(CH 3 ) 2 -Ph-Si(CH 3 ) 2 - and at least one bond selected from the group consisting of divalent organopolysiloxane residues (hereinafter also referred to as ").
  • R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Ph is a phenylene group.
  • the number of carbon atoms in the alkyl group of R 26 is preferably 1 to 6, more preferably 1 to 3, even more preferably 1 to 2, from the viewpoint of facilitating production of the fluorine-containing ether compound.
  • Examples of the divalent organopolysiloxane residue include groups of the following formula.
  • R27 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the number of carbon atoms in the alkyl group and alkoxy group of R 27 is preferably 1 to 10, more preferably 1.
  • bond B 1 -C(O)NR 26 -, -N(R 26 )C(O)-, -C(O)-, and -NR 26 -, from the viewpoint of easy production of fluorine-containing ether compounds.
  • At least one bond selected from the group consisting of -C(O)NR 26 -, -N(R 26 )C(O)- or -C(O)- is more preferred.
  • Specific examples of divalent L 1 include a single bond, one or more bonds B 1 (eg, *-B 1 -**, *-B 1 -R 28 -B 1 -**), and the like.
  • R 28 is a single bond or a divalent organic group
  • * is a bond on the R 1 side
  • ** is a bond on the R 11 side.
  • L 1 having a valence of 3 or more include one or more branch points P 1 (eg ⁇ (*-) j P 1 (-**) x1 ⁇ , ⁇ (*-) j P 1 -R 28 - P 1 (-**) x1 ⁇ , etc.), combinations of one or more branch points P 1 and one or more bonds B 1 (eg, ⁇ *-B 1 -R 28 -P 1 (-**) x1 ⁇ , ⁇ *-B 1 -R 28 -P 1 (-R 28 -B 1 -**) x1 ⁇ , etc.).
  • R 28 is a single bond or a divalent organic group
  • * is a bond on the R 1 side
  • ** is a bond on the R 11 side.
  • the divalent organic group for R 28 includes, for example, a hydrocarbon group such as a divalent aliphatic hydrocarbon group (alkylene group, cycloalkylene group, etc.), a divalent aromatic hydrocarbon group (phenylene group, etc.) and may have a bond B 1 between the carbon-carbon atoms of the hydrocarbon group.
  • the number of carbon atoms in the divalent organic group is preferably 1-10, more preferably 1-6, even more preferably 1-4.
  • L 1 is preferably a group represented by any one of the following formulas (L1) to (L7) from the viewpoint of easy production of the fluorine-containing ether compound.
  • a 1 is a single bond, -B 3 -, -B 3 -R 30 -, or -B 3 -R 30 -B 2 -
  • R 30 is an alkylene group, or a A group having -C(O)NR e6 -, -C(O)-, -NR e6 - or -O- between carbon-carbon atoms of an alkylene group
  • B 2 is -C(O)NR e6 -, -C(O)-, -NR e6 -, or -O-
  • B 3 is -C(O)NR e6 -, -C(O)-, or -NR e6 -
  • a 2 is a single bond or -B 3
  • a group having -O-, Q 22 is a single bond, -B 3 -, -R 30 -B 3 - or -B 2 -R 30 -B 3 -;
  • Q 23 is a single bond or -R 30 -B 3 -;
  • Q 24 is Q 22 when the atom in Z 1 to which Q 24 is bonded is a carbon atom, and Q 23 when the atom in Z 1 to which Q 24 is bonded is a nitrogen atom;
  • Q 25 is a single bond or -R 30 -B 3 -;
  • Q 26 is a single bond or -R 30 -B 3 -;
  • Z 1 is a group having a (d8+d9) valent ring structure having a carbon or nitrogen atom to which A 3 is directly bonded and a carbon or nitrogen atom to which Q is directly bonded,
  • R e1 is a hydrogen atom or an alkyl group
  • R e2 is a hydrogen atom, a hydroxyl
  • the plurality of A 1 's may be the same or different.
  • d1+d3, d5, d7, d8, d10 is j
  • d2+d4 d6, 3-d7, d9, d11, 1+d12 is x1.
  • the number of carbon atoms in the alkylene group of R 30 is preferably 1 to 10, more preferably 1 to 6, from the viewpoints of easy production of the fluorine-containing ether compound and further excellent abrasion resistance, light resistance and chemical resistance of the surface layer. More preferably, 1 to 4 are even more preferable. However, the lower limit of the number of carbon atoms in the alkylene group is 2 when it has a specific bond between carbon atoms.
  • the ring structure of Z 1 includes the ring structures described above, and preferred forms are also the same.
  • 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, even more preferably 1 to 2, from the viewpoint of easy production of the fluorine-containing ether compound.
  • the number of carbon atoms in the alkyl group portion of the acyloxy group of R e2 is preferably 1 to 6, more preferably 1 to 3, even more preferably 1 to 2, from the viewpoint of facilitating production of compound 1.
  • d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoints of easy production of a fluorine-containing ether compound and further excellent abrasion resistance and fingerprint stain removability of the surface layer. .
  • L 1 include groups represented by any of the following formulas (L11) to (L17).
  • G is a group (G21) below, and two or more Gs in L 1 may be the same or different. Codes other than G are the same as the codes in formulas (L11) to (L17). -Si(R 21 ) 3-k (-Q 3 -) k (G21) However, in formula (G21), the Si side connects to Q22 , Q23 , Q24 , Q25 or Q26 , and the Q3 side connects to R11 .
  • R21 is an alkyl group.
  • Q 3 is a single bond or -R 31 -B 3 -
  • R 31 is an alkylene group, or -C(O)NR 32 - between carbon atoms of an alkylene group having 2 or more carbon atoms, a group having -C(O)-, -NR 32 - or -O-, or -(OSi(R 22 ) 2 ) p11 -O- and two or more Q 3 may be the same or different; good too.
  • k is 2 or 3;
  • R 32 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 22 is an alkyl group, a phenyl group or an alkoxy group, and two R 22s may be the same or different.
  • p11 is an integer of 0 to 5, and when p11 is 2 or more, two or more (OSi(R 22 ) 2 ) may be the same or different.
  • the number of carbon atoms in the alkylene group of Q 3 is preferably 1 to 10, and 1 to 6, from the viewpoints of easy production of the fluorine-containing ether compound and further excellent abrasion resistance, light resistance, and chemical resistance of the surface layer. More preferably, 1 to 4 are even more preferable. However, the lower limit of the number of carbon atoms in the alkylene group is 2 when it has a specific bond between carbon atoms.
  • the number of carbon atoms in the alkyl group of R 21 is preferably 1 to 6, more preferably 1 to 3, even more preferably 1 to 2, from the viewpoint of facilitating production of the fluorine-containing ether compound.
  • the number of carbon atoms in the alkyl group of R 22 is preferably 1 to 6, more preferably 1 to 3, even more preferably 1 to 2, from the viewpoint of facilitating production of the fluorine-containing ether compound.
  • the number of carbon atoms in the alkoxy group of R 22 is preferably 1 to 6, more preferably 1 to 3, even more preferably 1 to 2, from the viewpoint of excellent storage stability of the fluorine-containing ether compound.
  • p11 is preferably 0 or 1.
  • Examples of compound (A1) include the following. where R f is [R f1 -(OR f11 ) y1 -OR 1 ].
  • Compound (A2) has a structure represented by the following formula (A2). (T 31 -R 31 ) x3 -L 3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(R 21 -T 21 ) x2 (A2) However, each symbol in the formula (A2) is as described above.
  • R f12 and (OR f12 ) y2 are the same as R f11 and (OR f11 ) y1 , and preferred embodiments are also the same.
  • R 2 and R 3 are each independently the same as R 1 above, and preferred embodiments are also the same.
  • R 21 and R 31 are the same as R 11 above, and preferred embodiments are also the same.
  • “binds to L1” is read as “binds to L2 " for R21
  • “binds to T11” is read as “binds to T21 " in the case of R21
  • L2 is a single bond
  • R21 directly bonds to R2
  • L3 is a single bond
  • R31 directly bonds to R3 .
  • T 21 and T 31 are each independently —SiR a21 z21 R a22 3-z21 , and R a21 , R a22 and z21 are respectively the same as R a1 , R a2 and z1 constituting the group (g1); , and preferred embodiments are also the same.
  • x2 and x3 are each independently the same as x1, and preferred embodiments are also the same.
  • L 2 and L 3 are each independently the same as when j is 1 in L 1 above.
  • compound (A2) is represented by the following formula (A2').
  • each symbol in formula (A2') is the same as in formula (A2).
  • L 2 or L 3 is a trivalent or higher group
  • L 2 or L 3 is selected from the group consisting of C, N, Si, a ring structure and a (1+x2)-valent or (1+x3)-valent organopolysiloxane residue. has at least one type of branch point (hereinafter also referred to as “branch point P 2 ”).
  • the branch point P2 When N is the branch point P2 , the branch point P2 is represented by *-N(-**) 2 , for example. However, * is a bond on the R2 or R3 side, and ** is a bond on the R21 or R31 side.
  • the branch point P 2 When C is the branch point P 2 , the branch point P 2 is represented by *-C(-**) 3 or *-CR 29 (-**) 2 , for example.
  • * is a bond on the R 2 or R 3 side
  • ** is a bond on the R 21 or R 31 side
  • R 29 is a monovalent group such as a hydrogen atom, a hydroxyl group, an alkyl group. , an alkoxy group, and the like.
  • the branch point P 2 is represented by *-Si(-**) 3 or *-SiR 29 (-**) 2 , for example.
  • * is a bond on the R 2 or R 3 side
  • ** is a bond on the R 21 or R 31 side
  • R 29 is a monovalent group such as a hydrogen atom, a hydroxyl group, an alkyl group. , an alkoxy group, and the like.
  • each of L 2 or L 3 having a valence of 2 or more may independently have the above bond B 1 .
  • the aspect of bond B1 is as described above, and the preferred aspects are also the same.
  • Specific examples of divalent L 2 or L 3 include a single bond, one or more bonds B 1 (eg, *-B 1 -**, *-B 1 -R 28 -B 1 -**), etc. are mentioned.
  • R 28 is a single bond or a divalent organic group
  • * is a bond on the R 2 or R 3 side
  • ** is a bond on the R 21 or R 31 side.
  • L 2 or L 3 having a valence of 3 or more include one or more branch points P 2 (eg ⁇ *-P 2 (-**) x ⁇ , ⁇ *-P 1 -R 28 -P 1 - ** x1 ⁇ , etc.), combinations of one or more branch points P 2 and one or more bonds B 1 (for example, ⁇ * ⁇ B 1 ⁇ R 28 ⁇ P 1 ( ⁇ **) x ⁇ , ⁇ * -B 1 -R 28 -P 1 (-R 28 -B 1 -**) x ⁇ etc.).
  • x is x2 for L2 and x3 for L3 .
  • R 28 is a single bond or a divalent organic group
  • * is a bond on the R 2 or R 3 side
  • ** is a bond on the R 21 or R 31 side.
  • the aspect of R 28 is as described above, and the preferred aspects are also the same.
  • L 2 or L 3 is preferably a group independently represented by any one of the following formulas (L21) to (L27) from the viewpoint of easy production of the fluorine-containing ether compound.
  • the A 1 , A 2 or A 3 side is connected to formula R 2 or R 3
  • the Q 22 , Q 23 , Q 24 , Q 25 or Q 26 side is R 21 Or connect to R31 .
  • a 1 , A 2 , A 3 , Q 11 , Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , R e1 , R e2 R e3 and R e6 are the same as those described in L 1 above. and preferred embodiments are also the same.
  • Z 1 is a group having a (1+d9) valent ring structure having a carbon or nitrogen atom to which A 3 is directly bonded and a carbon or nitrogen atom to which Q is directly bonded
  • d2 is an integer from 0 to 3
  • d4 is an integer from 0 to 3
  • d2+d4 is an integer from 1 to 5
  • d6 is an integer from 1 to 3
  • d9 is an integer of 1 or more
  • d11 is an integer of 1-3
  • d12 is an integer of 1-3. Note that d2+d4, d6, d9, d11 and 1+d12 are x2 or x3.
  • d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoints of easy production of a fluorine-containing ether compound and further excellent abrasion resistance and fingerprint stain removability of the surface layer. .
  • L 2 or L 3 include groups represented by any of the following formulas (L31) to (L37).
  • the A 1 , A 2 or A 3 side is connected to R 2 or R 3 in the formula, and the Q 22 , Q 23 , Q 24 , Q 25 or Q 26 side is R 21 Or connect to R31 .
  • G is the above group (G21), and preferred embodiments are also the same. Codes other than G are the same as the codes in formulas (L21) to (L27), and preferred embodiments are also the same.
  • Examples of the compound (A2) include the following. where Q f is -R 3 -(OR f12 ) y2 -OR 2 -.
  • Compound (A3) has a structure represented by the following formula (A3).
  • Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 (A3)
  • each symbol in the formula (A3) is as described above.
  • R f13 and (OR f13 ) y3 are the same as R f11 and (OR f11 ) y1 , and preferred embodiments are also the same.
  • R 4 is the same as R 1 above, and preferred embodiments are also the same.
  • R 41 is the same as R 11 above, and preferred embodiments are also the same. However, “bind to L1 " shall be read as “bind to L4 ". In addition, “bind to T11 " shall be read as “bind to T41 ". When L4 is a single bond, R41 directly bonds to R4 .
  • T 41 is —SiR a41 z41 R a42 3-z41 , R a41 , R a42 and z41 are respectively the same as R a1 , R a2 and z1 constituting the above group (g1), and preferred embodiments are also the same. is.
  • x4 is the same as x1, and the preferred embodiment is also the same.
  • L 4 is the same as L 2 or L 3 , and preferred embodiments are also the same.
  • Q1 is an r1-valent group having a branch point, and r1 is 3 or 4;
  • the branch point P3 constituting Q1 includes N, C, Si, or a ring structure.
  • the number of branch points P3 may be one, or two or more.
  • the branch point P 1 is represented by N(-*) 3 , NR 29 (-*) 2 , for example.
  • the branch point P 3 includes, for example, C(-*) 4 , CR 29 (-*) 3 , C(R 29 ) 2 (-*) 2 and the like.
  • Si serves as the branch point P 3
  • the branch point P 3 includes, for example, Si(-*) 4 , SiR 29 (-*) 3 , Si(R 29 ) 2 (-*) 2 and the like.
  • * is a bond on the OR f13 side
  • R29 is a monovalent group. Examples of R 29 include a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, and a fluoropolyether chain having no R 41 -T 41 .
  • Examples of the ring structure constituting the branch point P 3 include those similar to those of the branch point P 1.
  • Examples of the substituents of the ring structure include the substituents described above, as well as a fluorine atom, a fluoroalkyl group, and R 41 -T It may also have a fluoropolyether chain that does not have 41 .
  • a 11 , A 12 or A 13 is connected to (OR f13 ).
  • a 11 is a single bond
  • R 40 is an alkylene group, a fluoroalkylene group, or a carbon atom of an alkylene group having 2 or more carbon atoms or a fluoroalkylene group - is a group having -C(O)NR e17 -, -C(O)-, -NR e17 - or -O- between carbon atoms
  • B 13 is -C(O)NR e6 -, -C (O)-, -NR e6 - or -O-
  • a 12 is a single bond or -R 40 -
  • a 13 is A 11 when the atom in Z 1 to which A 13 is attached is a carbon atom
  • a 12 when the atom in Z 1 to which A 13 is attached is a
  • the number of carbon atoms in the alkylene group or fluoroalkylene group of R 40 is preferably 1 to 10 from the viewpoints of easy production of the fluorine-containing ether compound and further excellent abrasion resistance, light resistance and chemical resistance of the surface layer. 1 to 6 are more preferred, and 1 to 4 are even more preferred. However, the lower limit of the number of carbon atoms in the alkylene group is 2 when it has a specific bond between carbon atoms.
  • the ring structure of Z 1 includes the ring structures described above, and preferred forms are also the same.
  • the number of carbon atoms in the alkyl group or fluoroalkylene group is preferably 1 to 6, and 1 to 3, from the viewpoint of facilitating production of the fluorine-containing ether compound. is more preferred, and 1 to 2 are even more preferred.
  • Examples of the compound (A3) include the following. However, R f3 is (OR f13 ) y3 —OR 4 .
  • the fluorine-containing ether compound contained in the present treatment agent may be one kind or two or more kinds.
  • the treatment agent comprises at least one fluorine-containing ether compound having a fluoropolyether chain containing (OCF 2 ), (OC 2 F 4 ) and (OC 3 F 6 ), and (OCF 2 ) and (OC 2 F 4 ) and may contain one or more fluorine-containing ether compounds having a fluoropolyether chain that does not contain (OC 3 F 6 ).
  • the treatment agent contains a fluorine-containing ether compound, and may further contain at least one of the following impurities and a fluorine-containing compound other than the fluorine-containing ether compound.
  • Impurities include fluorine-containing ether compounds and compounds that are unavoidable in the production of other fluorine-containing compounds.
  • this processing agent does not contain the liquid medium mentioned later.
  • fluorine-containing compounds include fluorine-containing compounds that are by-produced in the production process of fluorine-containing ether compounds (hereinafter also referred to as "by-product fluorine-containing compounds"), and known fluorine-containing compounds that are used for the same purposes as fluorine-containing ether compounds.
  • by-product fluorine-containing compounds fluorine-containing compounds that are by-produced in the production process of fluorine-containing ether compounds
  • the other fluorine-containing compound a compound that is unlikely to deteriorate the properties of the fluorine-containing ether compound is preferable.
  • the content of the other fluorine-containing compound is preferably less than 50% by mass, more preferably less than 30% by mass, and less than 10% by mass, based on the total amount of the present treatment agent, from the viewpoint of sufficiently exhibiting the properties of the fluorine-containing ether compound. is more preferred.
  • Examples of by-product fluorine-containing compounds include unreacted fluorine-containing compounds during the synthesis of fluorine-containing ether compounds.
  • the treatment agent contains a by-product fluorine-containing compound, the purification process for removing the by-product fluorine-containing compound or reducing the amount of the by-product fluorine-containing compound can be simplified.
  • fluorine-containing compounds include, for example, those described in the following documents. perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 11-029585; a silicon-containing organic fluorine-containing polymer described in Japanese Patent No. 2874715; Organosilicon compounds described in Japanese Patent Application Laid-Open No. 2000-144097, perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 2000-327772; Fluorinated siloxane described in Japanese Patent Publication No. 2002-506887, Organosilicone compounds described in Japanese Patent Publication No. 2008-534696, A fluorinated modified hydrogen-containing polymer described in Japanese Patent No.
  • fluorine-containing compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., and SURECO AF such as SURECO (registered trademark) 2101S manufactured by AGC. series, Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509 and the like manufactured by Daikin Industries.
  • the content of the fluorine-containing ether compound is 100% by mass or less, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, relative to the total mass of the present treatment agent.
  • the content of the other fluorine-containing compounds with respect to the total content of the fluorine-containing ether compound and other fluorine-containing compounds in the present processing agent is 40% by mass or less. It is preferably 30% by mass or less, more preferably 20% by mass or less.
  • the total content of the fluorine-containing ether compound and other fluorine-containing compounds in the present treatment agent is preferably 80% by mass or more, more preferably 85% by mass or more.
  • the surface layer is excellent in water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity and appearance.
  • This treatment agent is suitable as a surface treatment agent for forming a surface layer imparting water and oil repellency, abrasion resistance, and fingerprint stain removability to the substrate surface.
  • the coating liquid of the present invention (hereinafter also referred to as "the present coating liquid") contains the present processing agent and a liquid medium.
  • the present coating liquid may be in a liquid state, and may be a solution or a dispersion liquid.
  • the present coating liquid only needs to contain the present treating agent, and may contain impurities such as by-products produced in the production process of the fluorine-containing ether compound.
  • the concentration of the fluorine-containing ether compound or the treatment agent is preferably 0.001 to 40% by mass, preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass in the coating liquid.
  • the organic solvent may be a fluorinated organic solvent, may be a non-fluorinated organic solvent, or may contain both solvents.
  • Fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols and the like.
  • fluorinated alkane compounds having 4 to 8 carbon atoms are preferred.
  • Commercially available products include C 6 F 13 H (manufactured by AGC, Asahiklin (registered trademark) AC-2000), C 6 F 13 C 2 H 5 (manufactured by AGC, Asahiklin (registered trademark) AC-6000), C 2 F 5 CHFCHFCF 3 (Vertrel (registered trademark) XF manufactured by Chemours) and the like.
  • fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.
  • fluoroalkyl ether compounds having 4 to 12 carbon atoms are preferred.
  • fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine.
  • fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol and hexafluoroisopropanol.
  • non-fluorinated organic solvent compounds consisting only of hydrogen atoms and carbon atoms and compounds consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferable, and hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, Examples include ether-based organic solvents and ester-based organic solvents.
  • the present coating liquid preferably contains 60 to 99.999% by mass of the liquid medium, preferably 85 to 99.99% by mass, more preferably 90 to 99.9% by mass.
  • the present coating liquid may contain, in addition to the present processing agent and the liquid medium, other components within a range that does not impair the effects of the present invention.
  • Other components include, for example, known additives such as acid catalysts and basic catalysts that promote hydrolysis and condensation reaction of hydrolyzable silyl groups.
  • the content of other components in the present coating liquid is preferably 10% by mass or less, more preferably 1% by mass or less.
  • the total concentration of the fluorine-containing ether compound and other components or the total concentration of the present treatment agent and other components (hereinafter also referred to as "solid content concentration") of the present coating liquid is preferably 0.001 to 40% by mass. 0.01 to 20% by mass is more preferable, 0.01 to 10% by mass is even more preferable, and 0.01 to 1% by mass is particularly preferable.
  • the solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120°C.
  • the article of the present invention (hereinafter also referred to as “the article") has a substrate and a surface layer disposed on the substrate.
  • the surface layer is a layer formed from the present treatment agent or the present coating liquid, and contains the fluoropolyether chain.
  • the article satisfies Requirement 2 below.
  • generating negative secondary ions by irradiating the surface layer of the article with pulsed primary ions; separating the generated negative secondary ions based on their mass-to-charge ratio using a first time-of-flight secondary ion mass spectrometer; Selecting negative secondary ions having a mass-to-charge ratio of 348 u as precursor ions from the separated negative secondary ions using an ion selection device, introducing selected precursor ions into a collision cell for cleavage by high-energy collision-induced dissociation to produce product ions;
  • a mass spectrum showing the relationship between the mass-to-charge ratio and area intensity of product ions obtained from the generated product ions using a second mass spectrometer, The sum of the area intensities of each peak corresponding to product ions with mass-to-charge ratios of 66u, 166u, 182u and 282u with respect to the total IA of the area intensities of each peak corresponding to product ions
  • the surface layer of the article that satisfies Requirement 2 above has excellent lubricity.
  • water and oil repellency, abrasion resistance, and fingerprint stain removability are imparted to the surface layer of the article.
  • the evaluation method of Requirement 2 in the article, the range of the suitable ratio I B / IA , the method of adjusting the ratio I B / IA in the surface layer, etc. all comply with Requirement 1 above.
  • the material and shape of the base material may be selected as appropriate according to the intended use of the product.
  • Materials for the substrate include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof.
  • the glass may be chemically strengthened.
  • examples of substrates that require water and oil repellency include substrates for touch panels, substrates for displays, and substrates that constitute housings of electronic devices.
  • a touch panel substrate and a display substrate have translucency. "Having translucency" means having a vertical incident visible light transmittance of 25% or more according to JIS R3106:1998 (ISO 9050:1990). Glass or transparent resin is preferable as the material for the touch panel substrate.
  • the surface layer is formed from the present treatment agent containing a fluorine-containing ether compound having a fluoropolyether chain and a reactive group, or a coating liquid containing the present treatment agent.
  • the fluoropolyether chain contained in the surface layer is the same as the fluoropolyether chain possessed by the fluorine-containing ether compound contained in the surface treatment agent, including preferred embodiments.
  • the reactive groups of the fluorine-containing ether compound react with and bond to the reactive groups on the surface of the base material or the underlying layer, thereby obtaining a base material having excellent adhesion to the base material or the underlying layer.
  • the fluorine-containing ether compound may form a condensate or polymer with another compound.
  • the reactive group of the fluorine-containing ether compound is a reactive silyl group
  • the surface layer forms a silanol group (Si—OH) by hydrolysis of the reactive silyl group, and the silanol group undergoes an intermolecular condensation reaction.
  • the surface layer may contain a condensate of a fluorine-containing compound other than the fluorine-containing ether compound. That is, the surface layer may contain a fluorine-containing compound having a reactive group in a state in which a part or all of the reactive groups of the fluorine-containing compound are reacted.
  • the fluoropolyether chain structure of the fluorine-containing ether compound is usually maintained even after the surface layer is formed.
  • the thickness of the surface layer is preferably 1-100 nm, more preferably 1-50 nm. If the thickness of the surface layer is at least the lower limit, the effect of the surface layer can be sufficiently obtained. If the thickness of the surface layer is equal to or less than the upper limit, the utilization efficiency is high.
  • the thickness of the surface layer is the thickness obtained with an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated from the vibration period of the interference pattern obtained by obtaining an interference pattern of reflected X-rays by the X-ray reflectance method using an X-ray diffractometer for thin film analysis.
  • this item is a touch panel.
  • the surface layer is preferably formed on the surface of the member that constitutes the surface of the touch panel that is touched by a finger.
  • the method for producing the present article is a method of forming a surface layer on a substrate by a dry coating method or a wet coating method using the present treating agent or the present coating liquid.
  • This treatment agent can be used as it is in the dry coating method.
  • This treatment agent is suitable for forming a surface layer with excellent adhesion by a dry coating method.
  • the dry coating method includes methods such as vacuum deposition, CVD, and sputtering.
  • a vacuum vapor deposition method can be preferably used from the viewpoint of suppressing the decomposition of the fluorine-containing ether compound and the simplicity of the apparatus.
  • a pellet-like substance in which a fluorine-containing ether compound is supported on a metal porous body made of a metal material such as iron or steel may be used.
  • a pellet-like substance supporting a fluorine-containing ether compound can be produced by impregnating a metal porous body with a solution of the present treating agent and drying to remove the liquid medium.
  • the present coating liquid can be used as the solution of the present treatment agent.
  • This coating liquid can be suitably used for wet coating methods.
  • Wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure. A coat method and the like can be mentioned.
  • the reaction between the fluorine-containing ether compound and the substrate (or underlayer) may be promoted, if necessary.
  • the operation for promoting the reaction includes heating, humidification, light irradiation, and the like. For example, by heating a base material on which a surface layer is formed in an atmosphere containing moisture, hydrolysis reaction of hydrolyzable groups, reaction between hydroxyl groups on the surface of the base material and silanol groups, and condensation reaction of silanol groups It can promote reactions such as generation of siloxane bonds.
  • compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed if necessary. Specific examples include a method of pouring a solvent over the surface layer, a method of wiping off with a cloth impregnated with the solvent, and the like.
  • Examples 2-7 are working examples, and example 1 is a comparative example. However, the present invention is not limited to these examples.
  • the compounding amount of each component in the table to be described later indicates a mass standard.
  • the total amount of benzene injected was 0.17 g. Further, stirring was continued for 1 hour while blowing 20% fluorine gas at a constant flow rate. Nitrogen gas was then blown in for 1 hour. The contents of the autoclave were concentrated by an evaporator to obtain 11.6 g of compound b5.
  • Preparation Example 4 Preparation of Surface Treatment Agent 4
  • 1.0 g of the surface treating agent 1 and 0.8 g of the surface treating agent 3 were dissolved in 10 g of SR solvent and then mixed. After that, the SR solvent was distilled off to obtain a surface treatment agent 4 containing compound X1 and compound X3.
  • Examples 1 to 7 A base material (non-alkali glass (Eagle XG: product name, manufactured by Corning, 50 mm ⁇ 50 mm, thickness 0.5 mm)) is placed in a vacuum deposition apparatus, and the vacuum deposition apparatus is 5 ⁇ 10 -3 Pa or less. was evacuated to a pressure of At a position at a distance of 1000 mm so as to face one main surface of the substrate, a vapor deposition container containing the surface treatment agent 1 of Preparation Example 1 was heated to 300° C. by resistance heating to vapor-deposit the surface treatment agent. When the thickness of the surface treatment agent on the base material reached 10 nm, the film formation was terminated.
  • a base material non-alkali glass (Eagle XG: product name, manufactured by Corning, 50 mm ⁇ 50 mm, thickness 0.5 mm)
  • the vacuum deposition apparatus is 5 ⁇ 10 -3 Pa or less. was evacuated to a pressure of At a position at a distance of 1000 mm
  • the base material on which the surface treatment agent was deposited was heated at a temperature of 200° C. for 30 minutes (post-treatment) to obtain a base material (article) with a surface layer. Substrates with a surface layer were similarly obtained with surface treatment agents 2 to 7.
  • ⁇ Requirement 1> The surface layer of the obtained substrate with a surface layer is subjected to the primary ion source, the first mass spectrometer (time-of-flight mass spectrometer), the ion selection device, the collision cell, and the second mass according to the method described above. Analysis was performed using a tandem mass spectrometer equipped with an analyzer (time-of-flight mass spectrometer). The analysis conditions in this example are as shown below.
  • Tandem mass spectrometer “PHI nanoTOF II” manufactured by ULVAC-Phi ⁇ Primary ion: Bi 3 ++ ⁇ Primary ion acceleration voltage: 30 kV ⁇ Raster size: 500 ⁇ 500 ⁇ m 2 ⁇ Bunching: Yes ⁇ Charge neutralization: Yes ⁇ Polarity of secondary ions: Negative ⁇ Collision gas (MS/MS): Ar ⁇ Collision energy: 1.5 keV
  • the surface layer was bombarded with pulsed primary ions to generate negative secondary ions, and the generated negative secondary ions were separated based on mass-to-charge ratio using a first mass spectrometer.
  • Precursor ions having a mass-to-charge ratio of 348 u were selected from the separated negative secondary ions using an ion selector, and the selected precursor ions were introduced into a collision cell to generate product ions.
  • the produced product ions were analyzed by a second mass spectrometer to obtain a mass spectrum showing the relationship between the mass-to-charge ratio of the product ions and the area intensity.
  • the total area intensity IA corresponding to the product ion A with a mass-to-charge ratio of 116u or 232u is 100000 counts or more, or the mass-to-charge ratio is 66u, 166u, 182u or 282u. Integration was performed until the total area intensity I B corresponding to product ion B reached 1000 counts or more. Then, the ratio IB / IA of the total area intensity IB to the total area intensity IA was calculated.
  • the obtained total area intensity I A , total area intensity I B , and ratio I B / IA of each example are shown in Table 1 below.
  • the dynamic friction coefficient of the surface layer against artificial skin was measured using a variable load type friction and wear test system (manufactured by Shinto Kagaku Co., Ltd., HHS2000), contact area: 3 cm ⁇ 3 cm, load: 0.98 N was measured under the conditions of The smaller the coefficient of dynamic friction, the better the lubricity.
  • Evaluation criteria are as follows. A: The dynamic friction coefficient of the surface layer is 0.017 or less. B: The dynamic friction coefficient of the surface layer is more than 0.017 and 0.019 or less. C: The dynamic friction coefficient of the surface layer is more than 0.019 and 0.021 or less. D: The dynamic friction coefficient of the surface layer is over 0.021.
  • m1 to m3 correspond to m1 to m3 in formulas (f2) and (f4), respectively, m1 represents the average number of units of a fluoroalkylene group having 1 carbon atom in the compound, and m2 represents the average number of units of fluoroalkylene groups having 2 carbon atoms in the compound, and m3 represents the average number of units of fluoroalkylene groups having 3 carbon atoms in the compound.

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Abstract

L'invention concerne : un agent de traitement de surface pouvant former une couche de surface dotée d'un excellent pouvoir lubrifiant ; un liquide de revêtement ; un article ; et un procédé de production de l'article.　Cet agent de traitement de surface contient un composé d'éther contenant du fluor possédant une chaîne fluoropolyéther et un groupe réactif, et satisfait l'exigence 1. Exigence 1 : dans un spectre de masse d'ions produits obtenu par utilisation d'un premier spectromètre de masse à temps de vol en vue de séparer des ions secondaires négatifs obtenus par irradiation d'une couche de surface formée à l'aide de l'agent de traitement de surface avec des ions pulsés, et par sélection d'un ion secondaire négatif présentant un rapport masse sur charge de 348 u en tant qu'ion précurseur, le rapport (IB/IA), qui équivaut à l'intensité de surface totale IB de pics présentant des rapports masse sur charge de 66 u, 166 u, 182 u et 282 u par rapport à l'intensité de surface totale IA de pics présentant des rapports masse sur charge de 116 u et 232 u, est de 0,025 ou plus.
PCT/JP2023/004226 2022-02-09 2023-02-08 Agent de traitement de surface, liquide de revêtement, article et procédé de production d'un article WO2023153450A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013121984A1 (fr) * 2012-02-17 2013-08-22 旭硝子株式会社 Composé d'éther contenant du fluor, composition à base d'éther contenant du fluor, fluide de revêtement, substrat présentant une couche traitée en surface et procédé de production dudit substrat
JP2014159573A (ja) * 2007-11-29 2014-09-04 Lg Chem Ltd 耐摩耗性および指紋除去性に優れたコーティング組成物およびコーティングフィルム
JP2020502100A (ja) * 2016-12-14 2020-01-23 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． （ペル）フルオロポリエーテルポリマー
WO2020230618A1 (fr) * 2019-05-14 2020-11-19 信越化学工業株式会社 Élément hydrofuge et oléofuge, et procédé de production d'un élément hydrofuge et oléofuge
JP2021107524A (ja) * 2019-08-02 2021-07-29 ダイキン工業株式会社 表面処理剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014159573A (ja) * 2007-11-29 2014-09-04 Lg Chem Ltd 耐摩耗性および指紋除去性に優れたコーティング組成物およびコーティングフィルム
WO2013121984A1 (fr) * 2012-02-17 2013-08-22 旭硝子株式会社 Composé d'éther contenant du fluor, composition à base d'éther contenant du fluor, fluide de revêtement, substrat présentant une couche traitée en surface et procédé de production dudit substrat
JP2020502100A (ja) * 2016-12-14 2020-01-23 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． （ペル）フルオロポリエーテルポリマー
WO2020230618A1 (fr) * 2019-05-14 2020-11-19 信越化学工業株式会社 Élément hydrofuge et oléofuge, et procédé de production d'un élément hydrofuge et oléofuge
JP2021107524A (ja) * 2019-08-02 2021-07-29 ダイキン工業株式会社 表面処理剤

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