Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/12—Organic material
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/24—Vacuum evaporation

Definitions

• the present invention relates to a composition, a method for producing a composition, a coating liquid, an article, and a method for producing 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 comprising a condensate of a fluorine-containing ether compound (Patent Document 1).
• an object of the present invention is to provide a composition capable of forming a surface layer with excellent lubricity, a method for producing the composition, a coating liquid, an article, and a method for producing the article.
• the present inventors found that at least two of the fluorine-containing ether compounds contained in the composition contain structures represented by (OCF 2 ) m31 and (OCF 2 CF 2 ) m32 .
• the composition includes, for example, a first compound having a fluoropolyether chain having a structure represented by (OCF 2 ) m11 ⁇ (OCF 2 CF 2 ) m12 , and (OCF 2 ) m21 ⁇ (OCF 2 CF 2 ) It can be prepared by mixing with a second compound having a fluoropolyether chain having a structure represented by m22 .
• the fluorine-containing ether compound having the minimum M is compound B
• m31 means the number of (OCF 2 ) and is an integer of 2 or more
• m32 means the number of (OCF 2 CF 2 ) and is an integer of 2 or more.
• a method for producing a composition containing two or more fluorine-containing ether compounds having a fluoropolyether chain and a reactive silyl group Among the fluorine-containing ether compounds, the first compound has a fluoropolyether chain having a structure represented by the following formula (G1), Among the fluorine-containing ether compounds, the second compound has a fluoropolyether chain having a structure represented by the following formula (G2), m11 in the following formula (G1) and m21 in the following formula (G2) are different, and/or m12 in the following formula (G1) and m22 in the following formula (G2) are different, A method for producing a composition, comprising mixing the first compound and the second compound.
• m11 means the average number of (OCF 2 ) in the first compound and is a positive number of 2 or more.
• m12 means the average number of (OCF 2 CF 2 ) in the first compound and is a positive number of 2 or more.
• m21 means the average number of (OCF 2 ) in the second compound and is a positive number of 2 or more.
• m22 means the average number of (OCF 2 CF 2 ) in the second compound and is a positive number of 2 or more.
• the first compound contains the compound A
• the method for producing a composition according to [11] wherein the second compound contains the compound B.
• the method for producing a composition according to [12] wherein the M A /M B is 1.35 or more.
• [14] The method for producing a composition according to [12] or [13], wherein the M A /M B is 1.50 or more.
• [15] The method for producing a composition according to any one of [12] to [14], wherein M A /M B is 2.00 or more.
• [16] The method for producing a composition according to any one of [12] to [15], wherein M A /M B is 4.00 or more.
• the content of each of the first compound and the second compound is 0.1% by mass or more relative to the total mass of the composition, according to any one of [12] to [16].
• a method of making the composition is a method of making the composition.
• a coating liquid comprising the composition according to any one of [1] to [8] and a liquid medium.
• An article comprising a substrate and a surface layer formed from the composition according to any one of [1] to [8] or the coating liquid according to [19].
• a surface layer is formed on a substrate by a dry coating method or a wet coating method using the composition according to any one of [1] to [8] or the coating liquid according to [19].
• the present invention it is possible to provide a composition capable of forming a surface layer with excellent lubricity, a method for producing the composition, a coating liquid, an article, and a method for producing the article.
• 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. That is, 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. means.
• 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 is the number average molecular weight calculated by obtaining the number (average value) of oxyfluoroalkylene units based on the terminal groups by 1 H-NMR and 19 F-NMR. " ⁇ " indicating a numerical range means that the numerical values before and after it are included as lower and upper limits.
• composition of the present invention is a composition containing two or more fluorine-containing ether compounds having a fluoropolyether chain and a reactive silyl group, At least two of the fluorine-containing ether compounds have a fluoropolyether chain containing a structure represented by the following formula (G11),
• the fluorine-containing ether compound having the minimum M is compound B
• m31 means the number of (OCF 2 ) and is an integer of 2 or more
• m32 means the number of (OCF 2 CF 2 ) and is an integer of 2 or more.
• a surface layer having excellent lubricity can be formed. Although the details of this reason have not been clarified, it is presumed to be due to the following reasons.
• a surface layer was formed using the present composition containing two or more fluorine-containing ether compounds different in the average number of structures represented by (OCF 2 ) or in the average number of structures represented by (OCF 2 CF 2 ).
• the packing of the molecular chains between the fluorine-containing ether compounds having different average numbers of structures tends to be poor (that is, it becomes difficult for the molecular chains to be densely arranged on the substrate).
• the ratio of the ratio M (the M A /M This tendency appears remarkably when B ) is 1.35 or more.
• the composition is suitable as a surface treatment agent for forming a surface layer imparting water and oil repellency, abrasion resistance, and fingerprint stain removability on a substrate.
• the fluorine-containing ether compound has a fluoropolyether chain and a reactive silyl group, and two or more of them are contained in the present composition.
• at least two of the two or more fluorine-containing ether compounds have fluoropolyether chains containing the structure represented by the above formula (G11), and further contain other fluoropolyether chains.
• a fluorine-containing ether compound has a reactive silyl group. Since the reactive silyl group is strongly chemically bonded to the base material or the underlying layer, the surface layer obtained using this composition 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 f11 ) y1 (f1)
• R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and a plurality of R f11 may be the same or different.
• y1 may be an integer of 2 or more, preferably 2-200.
• (OR f11 ) y1 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
• 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 f11 ) y1 preferably has any one of the structures represented by the following formulas (f3) to (f5) because it is superior in water and oil repellency, abrasion resistance, and fingerprint stain removability. preferable.
• the symbols in formulas (f3) to (f5) are the same as in formula (f2) above.
• the bonding order of (OG f1 ) and (OG f2 ) and (OG f2 ) and (OG f4 ) is arbitrary.
• (OG f1 ) and (OG f2 ) may be alternately arranged, (OG f1 ) and (OG f2 ) may be arranged in blocks, or may be randomly arranged.
• m1 is preferably 1 to 50, more preferably 1 to 30, even more preferably 1 to 20.
• m2 is preferably 1 to 50, more preferably 1 to 30, even more preferably 1 to 20.
• m2 is preferably from 1 to 50, more preferably from 1 to 30, even more preferably from 1 to 20. Also, m4 is preferably 1 to 50, more preferably 1 to 30, even more preferably 1 to 20. In formula (f5), m3 is preferably 1 to 50, more preferably 1 to 30, even more preferably 1 to 20.
• the ratio of fluorine atoms in the fluoropolyether chain (OR f11 ) y1 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. Further, the molecular weight of the fluoropolyether chain (OR f11 ) y1 portion is preferably 2,000 to 20,000, more preferably 2,500 to 15,000, more preferably 3,000 to 10,000, from the viewpoint of abrasion resistance. 000 is more preferred.
• 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 is excellent in 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 fluoropolyether chain and the group (g1) are bonded directly or via a linking group.
• the linking group include divalent or higher organic groups.
• L 1 in formula (1-1), L 2 and L 3 in formula (1-2), and formula (1-3 ) of L4 are bonded directly or via a linking group.
• 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 groups (g1) 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, even more preferably 2 to 12, from the viewpoint of achieving both abrasion resistance and water/oil repellency.
• the plurality of fluoropolyether chains may be the same or different.
• the multiple groups (g1) may be the same or different.
• Examples of the fluorine-containing ether compound include compounds represented by the following formula (1), the following formula (2), or the following formula (3).
• Q 1 [-(OR f11 ) y1 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 (3) however, (OR f11 ) y1 is as described above;
• T is the above -SiR a1 z1 R a2 3-z1 ,
• Other symbols are the same as those in equations (1-1), (1-2), and (1-3) described later.
• the content of the fluorine-containing ether compound is preferably 0.01 to 100% by mass, more preferably 0.10 to 99.99% by mass, and 1.00 to 99.00% by mass, relative to the total mass of the present composition. % is more preferred.
• the surface layer is more excellent in water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity and appearance.
• the present composition contains two or more compounds selected from the fluorine-containing ether compounds described above. Further, in the present composition, among the plurality of fluorine-containing ether compounds, at least two have fluoropolyether chains containing structures represented by the following formula (G11).
• m31 means the number of (OCF 2 ) and is an integer of 2 or more
• m32 means the number of (OCF 2 CF 2 ) and is an integer of 2 or more.
• a fluorine-containing ether compound having a fluoropolyether chain containing the structure represented by formula (G11) is sometimes referred to as "compound (G11)."
• Formula (G11) above represents a fluoropolyether chain containing a perfluoroalkylene group having 1 to 2 carbon atoms.
• the fluoropolyether chain of the formula (G11) contains a fluoroalkylene group having 1 to 2 carbon atoms, so that it has excellent flexibility, friction resistance, and lubricity.
• the fluoropolyether chain of (G11) contains a perfluoroalkylene group, it is excellent in water/oil repellency and fingerprint stain removability.
• the present composition has a structure represented by (G11) and contains two or more fluorine-containing ether compounds having different ratios of (OCF 2 CF 2 ) and (OCF 2 ).
• Fluorine-containing ether compounds having different ratios of (OCF 2 CF 2 ) and (OCF 2 ) are less likely to cause stacking due to a shift in the position of the ether bond. Thereby, the flexibility of the fluoropolyether chain is maintained even in the surface layer, and the lubricity is further improved.
• the bonding order of (OCF 2 ) and (OCF 2 CF 2 ) is arbitrary.
• (OCF 2 ) and (OCF 2 CF 2 ) may be alternately arranged, (OCF 2 ) and (OCF 2 CF 2 ) may be arranged in blocks, or randomly may be
• m31 is an integer of 2 or more, preferably an integer of 2 to 100, more preferably an integer of 3 to 80, and even more preferably an integer of 4 to 60.
• m32 is an integer of 2 or more, preferably an integer of 2 to 100, more preferably an integer of 3 to 80, and even more preferably an integer of 4 to 60.
• the value M of m31/m32 is preferably 0.3 to 10.0, more preferably 0.4 to 8.0, even more preferably 0.5 to 6.0.
• m31 represents the total number of (OCF 2 ) in the molecule
• m32 represents the total number of (OCF 2 ) in the molecule. Let it represent the total number of (OCF 2 CF 2 ).
• the fluoropolyether chain in compound (G11) may contain an oxyfluoroalkylene unit other than (OCF 2 ) and (OCF 2 CF 2 ) (hereinafter also referred to as “another oxyfluoroalkylene unit”).
• other oxyfluoroalkylene units include (OG f1 ) m1 (provided that G f1 is —CF 2 — excluded), (OG f2 ) m2 (provided that G Except when f2 is -CF 2 CF 2 -), (OG f3 ) m3 , (OG f4 ) m4 , (OG f5 ) m5 and (OG f6 ) m6 .
• the definitions of G f1 to G f6 and m1 to m6 are as described above.
• Compound (G11) may be any compound as long as it satisfies the above configuration. From the viewpoint of ease of synthesis, ease of compound handling, among others, compounds represented by the following formula (1-1), (1-2) or (1-3) are preferred. preferable. [R f1 ⁇ (OCF 2 ) m31 ⁇ (OCF 2 CF 2 ) m32 ⁇ OR 1 ] j ⁇ L 1 ⁇ (R 11 ⁇ T 11 ) x1 (1-1) (T 31 ⁇ R 31 ) x3 ⁇ L 3 ⁇ R 3 ⁇ (OCF 2 ) m31 ⁇ (OCF 2 CF 2 ) m32 ⁇ OR 2 ⁇ L 2 ⁇ (R 21 ⁇ T 21 ) x2 (1 -2) Q 1 [-(OCF 2 ) m31 (OCF 2 CF 2 ) m32 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 (1-3) however, R f1 is
• Compound (1-1) has a structure represented by the following formula (1-1). [R f1 ⁇ (OCF 2 ) m31 ⁇ (OCF 2 CF 2 ) m32 ⁇ OR 1 ] j ⁇ L 1 ⁇ (R 11 ⁇ T 11 ) x1 (1-1) However, each symbol in the formula (1-1) 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 1 is an alkylene group or a fluoroalkylene group. However, when R 1 is a fluoroalkylene group, R 1 is a fluoroalkylene group other than -CF 2 - and -CF 2 CF 2 -.
• 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.
• 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 -(OCF 2 ) m31 ⁇ (OCF 2 CF 2 ) m32 -OR 1 ] in one molecule, and may be an integer of 1 or more, preferably 1 to 20, 1 ⁇ 10 is more preferred, and 1-4 is even 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, from the viewpoint that they are easily arranged densely when the present composition forms 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 straight-chain alkylene group is preferable because the compound (1-1) 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 groups in one molecule, and may be an integer of 1 or more, preferably 1 to 32, more preferably 1 to 18, even more preferably 2 to 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 ring is preferred because the compound (1-1) can be easily produced and the surface layer has further excellent abrasion resistance, light resistance and chemical resistance.
• One selected from the group consisting of an aliphatic 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 the following formula A ring structure exemplified in is more preferable.
• 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 compound (1-1).
• 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 At least one bond selected from the group consisting of 26 - is preferable, and -C(O)NR 26 -, -N(R 26 )C(O) from the viewpoint of further improving the light resistance and chemical resistance of the surface layer. - 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 compound (1-1).
• a 1 is a single bond, -B 3 -, -B 3 -R 30 -, -B 3 -R 30 -B 2 -, -R 33 -, or -R 33 -B 2 -
• R 30 is an alkylene group, or a group having —C(O)NR e6 —, —C(O)—, —NR e6 — or —O— between carbon atoms of an alkylene group having 2 or more carbon atoms;
• B 2 is -C(O)NR e6 -, -C(O)-, -NR e6 - or -O-
• B 3 is -C(O)NR e6 -, -C(O)-, -C(O)-
• 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 24 is directly bonded,
• R e1 is a hydrogen atom or an alkyl group
• R e2 is a hydrogen atom, a hydroxy
• 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 and the number of carbon atoms in the oxyalkylene group of R 33 make it easier to produce the compound (1-1), and the abrasion resistance, light resistance and chemical resistance of the surface layer are further excellent. 1 to 10 are preferred, 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 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 facilitating production of compound (1-1).
• 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 easy production of compound (1-1).
• d9 is preferably 2 to 6, more preferably 2 to 4, and 2 or 3 from the viewpoints of easy production of compound (1-1) and further excellent abrasion resistance and fingerprint stain removability of the surface layer. More preferred.
• L 1 include groups represented by any of the following formulas (L11) to (L17).
• the A 1 , A 2 or A 3 side is connected to R 1 of formula (1-1), and the Q 22 , Q 23 , Q 24 , Q 25 or Q 26 side is Connect to R11 .
• 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 (L1) to (L7). -Si(R 21 ) 3-k (-Q 3 -) k (G21) However, in the formula (G21), the Si side is connected to Q22 , Q23 , Q24 , Q25 or Q26 , and the Q3 side is connected to R11 .
• R21 is an alkyl group.
• Q 3 is a single bond or -R 31 -B 3 -, and 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 from 1 to 10, and from 1 to 6 is 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 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 compound (1-1).
• 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 compound (1-1).
• 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 compound (1-1).
• p11 is preferably 0 or 1.
• Examples of compound (1-1) include the following. where R f is [R f1 ⁇ (OCF 2 ) m31 ⁇ (OCF 2 CF 2 ) m32 ⁇ OR 1 ].
• Compound (1-2) has a structure represented by the following formula (1-2). (T 31 ⁇ R 31 ) x3 ⁇ L 3 ⁇ R 3 ⁇ (OCF 2 ) m31 ⁇ (OCF 2 CF 2 ) m32 ⁇ OR 2 ⁇ L 2 ⁇ (R 21 ⁇ T 21 ) x2 (1 -2) However, each code in the formula (1-2) is as described above.
• 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 (1-2) is represented by the following formula (1-2′).
• each symbol in formula (1-2') is the same as in formula (1-2).
• 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 facilitating the production of compound (1-2).
• 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 L1 above. It is the same, 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.
• d2+d4, d6, d9, d11 and 1+d12 are x2 or x3.
• d9 is preferably 2 to 6, more preferably 2 to 4, and 2 or 3 from the viewpoints of easy production of the compound (1-2) and further excellent abrasion resistance and fingerprint stain removability of the surface layer. More preferred.
• 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 compound (1-2) include the following. where Q f is -R 3 -(OCF 2 ) m31 ⁇ (OCF 2 CF 2 ) m32 -OR 2 -.
• Compound (1-3) has a structure represented by the following formula (1-3).
• Q 1 [-(OCF 2 ) m31 (OCF 2 CF 2 ) m32 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 (1-3)
• each code in the formula (1-3) is as described above.
• 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 (OCF 2 ) m31 ⁇ (OCF 2 CF 2 ) m32 side
• R 29 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 without 41 .
• a 11 , A 12 or A 13 is connected to (OCF 2 ) m31 ⁇ (OCF 2 CF 2 ) m32 .
• 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, and
• the number of carbon atoms in the alkylene group or fluoroalkylene group of R 40 is 1 to 10 because the compound (1-3) can be easily produced and the surface layer has further excellent abrasion resistance, light resistance and chemical resistance.
• 1 to 6 are more preferable, and 1 to 4 are even more preferable.
• 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 from the viewpoint of facilitating production of compound (1-3). ⁇ 3 is more preferred, and 1-2 is even more preferred.
• R f3 is (OCF 2 ) m31 ⁇ (OCF 2 CF 2 ) m32 --OR 4 .
• the total content of the compound (G11) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the present composition, from the viewpoint of better lubricity of the surface layer. , more preferably 1.0% by mass or more.
• the content of compound (G11) is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, relative to the total mass of the present composition.
• M A /M B is preferably 1.50 or more, more preferably 2.00 or more, and still more preferably 4.00 or more.
• M A /M B is usually 30 or less, preferably 20 or less, and more preferably 10 or less.
• the value of MA is not particularly limited, it is preferably 1.00 or more, more preferably 1.10 or more, and still more preferably 1.15 or more from the viewpoint of lubricity. Moreover, from the point that the abrasion resistance of a surface layer is more excellent, 20 or less are preferable, 15 or less are more preferable, and 10 or less are still more preferable.
• the value of M B is not particularly limited, it is preferably less than 1.00, more preferably 0.98 or less, and still more preferably 0.95 or less from the viewpoint of lubricity. Among them, it is preferable that MA is 1.00 or more and MB is less than 1.00.
• the fluoropolyether chain of compound A has a high ratio of (OCF 2 ), and the fluoropolyether chain of compound B has a high ratio of (OCF 2 CF 2 ), so that the position of the ether bond is likely to shift, Stacking is less likely to occur and lubricity is further improved.
• the absolute value of the difference between M A and M B is preferably from 1 to 8, more preferably from 1.5 to 7, even more preferably from 2 to 6, from the viewpoint of better lubricity of the surface layer.
• the content of compound A and compound B in the present composition is each independently preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the composition. 0% or more is more preferable. By containing 0.1% by mass or more of each of the compound A and the compound B, the lubricity is further improved.
• the upper limit of the content of compound A and compound B is not particularly limited, but each independently is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, relative to the total mass of the composition. However, the total content of compound A and compound B is 100% by mass or less with respect to the total amount of the composition.
• the ratio of compound A to compound B is preferably 0.01 to 100, and 5 to 80 is preferable. More preferably, 10 to 70 is even more preferable.
• the mass ratio is at least the lower limit, the friction resistance is more excellent, and when the mass ratio is at most the upper limit, the lubricity is more excellent.
• Structures other than structure (G11) of compound A and compound B are not particularly limited, except that they have a fluoropolyether chain and a reactive silyl group.
• Examples of the combination of compound A and compound B include a combination of compounds each independently having the branch point P1 and having N, C or Si as the branch point P1 .
• compound A and compound B are each independently preferably a compound having a structure of formula (1-1), and among them, L 1 is formula (L2), formula (L3) or formula (L5) is more preferred, and compounds in which A 1 and A 2 are a single bond, —B 3 —R 30 —, or —R 33 — are more preferred.
• L 1 is formula (L2), formula (L3) or formula (L5) is more preferred, and compounds in which A 1 and A 2 are a single bond, —B 3 —R 30 —, or —R 33 — are more preferred.
• Combinations of compounds in which both compound A and compound B are represented by formula (1-1) include combinations of compounds with different structures of structures 1 to 4 below, and combinations of different fluoropolyether chains in the same structure Combinations of compounds are included.
• Structure 1 In formula (1-1), L 1 is formula (L2), d6 is 3, A 1 is —B 3 —R 30 —, and B 3 is —C(O)NR e6 — and wherein R 30 is an alkylene group
• Structure 2 a compound of formula (1-1) wherein L 1 is formula (L3) and A 2 is -C(O)-;
• Structure 3 a compound of formula (1-1) in which L 1 is formula (L5), d11 is 2, R e3 is a hydroxyl group, and A 2 is a single bond or —R 33 —;
• Structure 4 A compound of formula (1-1) in which L 1 is formula (L5), d11 is 3, and A 2 is a single bond or -R 33 -.
• Structure 1 includes the following compounds.
• Structure 2 includes the following compounds.
• Structure 3 includes the following structure.
• Structure 4 includes the following structures.
• Combinations of structure 1 and structure 2 include a combination of structure 1 and structure 3, a combination of structure 1 and structure 4, a combination of structure 2 and structure 3, a combination of structure 2 and structure 4, and a combination of structure 3 and structure 4. mentioned.
• Compound A and compound B preferably have similar chemical structures, except for the number of repeating units in the fluoropolyether chain, because at least one of the surface layer's abrasion resistance and water/oil repellency is superior.
• both compound A and compound B are a combination of compounds represented by formula (1-1) in a first embodiment, and both are a combination of compounds represented by formula (1-2).
• Two aspects and the third aspect, which is a combination of compounds represented by formula (1-3), are preferred.
• the first mode is preferred because at least one of the abrasion resistance and water/oil repellency of the surface layer is more excellent, and a combination of compounds in which L1 of compound A and compound B is the same is more preferred.
• the present composition may contain a fluorine-containing compound other than the fluorine-containing ether compound and at least one of the following impurities.
• Impurities include compounds that are unavoidable in the production of the fluorine-containing ether compounds and other fluorine-containing compounds.
• this composition does not contain the liquid medium mentioned later.
• fluorine-containing compounds include fluorine-containing compounds by-produced in the production process of the above-mentioned fluorine-containing ether compounds (hereinafter also referred to as "by-product fluorine-containing compounds"), which are used for the same purposes as the above-mentioned fluorine-containing ether compounds.
• by-product fluorine-containing compounds fluorine-containing compounds by-produced in the production process of the above-mentioned fluorine-containing ether compounds
• a well-known fluorine-containing compound etc. are mentioned.
• compounds that are unlikely to deteriorate the properties of the fluorine-containing ether compound are preferred.
• Examples of by-product fluorine-containing compounds include unreacted fluorine-containing compounds during the synthesis of the fluorine-containing ether compound.
• the purification step 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, compounds 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 other fluorine-containing compound with respect to the total mass of the present composition is such that the properties of the fluorine-containing ether compound can be sufficiently exhibited. Less than 50% by mass is preferable, less than 30% by mass is more preferable, and less than 10% by mass is even more preferable.
• the method for producing the present composition is a method for producing a composition containing two or more fluorine-containing ether compounds having a fluoropolyether chain and a reactive silyl group, Among the fluorine-containing ether compounds, the first compound has a fluoropolyether chain having a structure represented by the following formula (G1), Among the fluorine-containing ether compounds, the second compound has a fluoropolyether chain having a structure represented by the following formula (G2), m11 in the following formula (G1) and m21 in the following formula (G2) are different, and/or m12 in the following formula (G1) and m22 in the following formula (G2) are different, A method for producing a composition, comprising mixing the first compound and the second compound.
• m11 means the average number of (OCF 2 ) in the first compound and is a positive number of 2 or more.
• m12 means the average number of (OCF 2 CF 2 ) in the first compound and is a positive number of 2 or more.
• m21 means the average number of (OCF 2 ) in the second compound and is a positive number of 2 or more.
• m22 means the average number of (OCF 2 CF 2 ) in the second compound and is a positive number of 2 or more.
• the present composition can be suitably produced by a simple method.
• the present composition is obtained by mixing the first compound, the second compound, and optionally other fluorine-containing compounds.
• the first compound is one of the above fluorine-containing ether compounds, which are raw materials of the present composition, and has the above reactive silyl group and a fluoropolyether chain having the following structure (G1).
• (OCF 2 ) m11 (OCF 2 CF 2 ) m12 (G1) however, m11 means the average number of (OCF 2 ) in the first compound and is a positive number of 2 or more, m12 means the average number of (OCF 2 CF 2 ) in the first compound and is a positive number of 2 or more.
• the first compound is a raw material compound of the present composition, and may be a single compound or a composition containing two or more fluorine-containing ether compounds.
• the bonding order of (OCF 2 ) and (OCF 2 CF 2 ) is arbitrary.
• (OCF 2 ) and (OCF 2 CF 2 ) may be alternately arranged, (OCF 2 ) and (OCF 2 CF 2 ) may be arranged in blocks, or randomly may be
• m11 is a positive number of 2 or more, preferably a positive number of 2 to 100, more preferably a positive number of 3 to 80, and even more preferably a positive number of 4 to 60.
• m12 is a positive number of 2 or more, preferably a positive number of 2 to 100, more preferably a positive number of 3 to 80, and even more preferably a positive number of 4 to 60.
• the value of m11/m12 is preferably 1.0 to 10.0, more preferably 1.5 to 8.0, even more preferably 2.0 to 6.0.
• the average number of (OCF 2 ) and the average number of (OCF 2 CF 2 ) in the first compound are measured by 19 F-NMR.
• the fluoropolyether chain in the first compound may contain oxyfluoroalkylene units other than (OCF 2 ) and (OCF 2 CF 2 ) (hereinafter also referred to as “other oxyfluoroalkylene units”).
• other oxyfluoroalkylene units include (OG f1 ) m1 (provided that G f1 is —CF 2 — excluded), (OG f2 ) m2 (provided that G Except when f2 is -CF 2 CF 2 -), (OG f3 ) m3 , (OG f4 ) m4 , (OG f5 ) m5 and (OG f6 ) m6 .
• the definitions of G f1 to G f6 and m1 to m6 are as described above.
• the first compound may be anything as long as it satisfies the above configuration. From the viewpoint of ease of synthesis, ease of compound handling, among others, compounds represented by the following formula (1-1), (1-2) or (1-3) are preferred. preferable. [R f1 ⁇ (OCF 2 ) m11 ⁇ (OCF 2 CF 2 ) m12 ⁇ OR 1 ] j ⁇ L 1 ⁇ (R 11 ⁇ T 11 ) x1 (1-1) (T 31 ⁇ R 31 ) x3 ⁇ L 3 ⁇ R 3 ⁇ (OCF 2 ) m11 ⁇ (OCF 2 CF 2 ) m12 ⁇ OR 2 ⁇ L 2 ⁇ (R 21 ⁇ T 21 ) x2 (1 -2) Q 1 [-(OCF 2 ) m11 (OCF 2 CF 2 ) m12 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 (1-3) however, (OCF 2 ) m11
• the content of the first compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the present composition, from the viewpoint of better lubricity of the surface layer. 0% by mass or more is more preferable.
• the content of the first compound is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, relative to the total mass of the present composition.
• the second compound is one of the fluorine-containing ether compounds described above, and has the reactive silyl group described above and a fluoropolyether chain having the following structure (G2).
• the second compound is a raw material compound of the present composition, and may be a single compound or a composition containing two or more fluorine-containing ether compounds.
• m11 in formula (G1) and m21 in formula (G2) are different, and/or m12 in formula (G1) and m22 in formula (G2) are different.
• m11 and m21 are different, m12 and m22 may be the same or different, and when m12 and m22 are different, m11 and m21 may be the same or different.
• the bonding order of (OCF 2 ) and (OCF 2 CF 2 ) is arbitrary.
• (OCF 2 ) and (OCF 2 CF 2 ) may be alternately arranged, (OCF 2 ) and (OCF 2 CF 2 ) may be arranged in blocks, or randomly may be
• m21 is a positive number of 2 or more, preferably a positive number of 2 to 100, more preferably a positive number of 3 to 80, and even more preferably a positive number of 4 to 60.
• m22 is a positive number of 2 or more, preferably a positive number of 2 to 100, more preferably a positive number of 3 to 80, and even more preferably a positive number of 4 to 60.
• the value of m21/m22 is preferably 1.0 to 10.0, more preferably 1.5 to 8.0, even more preferably 2.0 to 6.0.
• the average number of (OCF 2 ) and the average number of (OCF 2 CF 2 ) in the second compound are measured by the same method as for the first compound.
• the fluoropolyether chain in the second compound may contain the above-mentioned other oxyfluoroalkylene units.
• At least the first compound and the second compound have different values of m11/m12 in formula (G1) and m21/m22 in formula (G2). preferable.
• the absolute value of the difference between m11/m12 and m21/m22 is preferably from 1 to 8, more preferably from 1.5 to 7, and even more preferably from 2 to 6, in terms of better lubricity of the surface layer.
• the second compound may be any compound as long as it satisfies the above configuration. From the point of view of ease of synthesis, ease of handling of compounds, among others, compounds represented by the following formula (2-1), (2-2) or (2-3) are preferred. preferable. [R f2 ⁇ (OCF 2 ) m21 ⁇ (OCF 2 CF 2 ) m22 ⁇ OR 5 ] j1 ⁇ L 5 ⁇ (R 12 ⁇ T 12 ) x11 (2-1) (T 32 -R 32 ) x13 -L 7 -R 7 -(OCF 2 ) m21 .(OCF 2 CF 2 ) m22 -OR 6 -L 6 -(R 22 -T 22 ) x12 (2 -2) Q 2 [-(OCF 2 ) m21 (OCF 2 CF 2 ) m22 -OR 8 -L 8 -(R 42 -T 42 ) x14 ] r2 (2-3) however, (OCF 2
• the content of the second compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the present composition, from the viewpoint of better lubricity of the surface layer. 0% by mass or more is more preferable.
• the content of the second compound is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, relative to the total mass of the present composition.
• the mass ratio of the content of the first compound to the content of the second compound is preferably 0.01 to 100, more preferably 5 to 80, and even more preferably 10 to 70.
• the mass ratio is at least the lower limit, the friction resistance is more excellent, and when the mass ratio is at most the upper limit, the lubricity is more excellent.
• the first compound contains the compound A and the second compound contains the compound B in order to prepare the composition that facilitates the formation of a surface layer with excellent lubricity.
• the ratio of the M A to the M B is preferably 1.35 or more, more preferably 1.50 or more. 00 or more is more preferable, and 4.00 or more is particularly preferable.
• the coating liquid of the present invention (hereinafter also referred to as "the present coating liquid") contains the present composition 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 composition, and may contain impurities such as by-products produced in the production process of the fluorine-containing ether compound.
• the content of the composition is preferably 0.001 to 40% by mass, preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, relative to the total mass of 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, and fluoroalcohols.
• fluorinated alkanes 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 (Bertrell (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, compounds consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferable, and hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ethers and ester-based organic solvents.
• the 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 other components in addition to the present composition and the liquid medium 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 present composition and other components is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and 0.01 to 10% by mass is more preferred, and 0.01 to 1% by mass is particularly preferred.
• 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 “this article") has a base material, a surface layer disposed on the base material, and has an underlying layer between the base material and the surface layer. is preferred.
• the surface layer is a layer formed from the present composition or the present coating liquid, and contains the condensate of the fluorine-containing ether compound.
• 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 base material may be one that has undergone surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc. on the surface on which the base layer is to be provided.
• a surface that has undergone a surface treatment has even better adhesion between the base material and the underlying layer, and as a result, the abrasion resistance of the surface layer is further improved.
• the surface treatment corona discharge treatment or plasma treatment is preferable because the abrasion resistance of the surface layer is further excellent.
• the underlying layer is preferably a layer containing an oxide containing silicon (preferably silicon oxide), and may further contain other elements.
• the underlayer contains silicon oxide, the reactive silyl groups of the fluorine-containing ether compound undergo dehydration condensation, forming Si—O—Si bonds with the underlayer, forming a surface layer with excellent abrasion resistance. be done.
• the content of silicon oxide in the underlayer is preferably 65% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, and particularly preferably 90% by mass or more. If the content of silicon oxide is at least the lower limit, sufficient Si--O--Si bonds are formed in the underlayer, and sufficient mechanical properties of the underlayer are ensured.
• the content of silicon oxide is the remainder obtained by subtracting the total content of other elements (the amount converted to oxide in the case of oxide) from the mass of the underlayer.
• the oxides in the underlayer further include alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, and molybdenum. , and tungsten.
• alkali metal elements alkaline earth metal elements
• platinum group elements platinum group elements
• boron aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, and molybdenum.
• tungsten By including these elements, the bond between the underlayer and the fluorine-containing ether compound is strengthened, and the abrasion resistance is improved.
• the thickness of the underlayer is preferably 1 to 200 nm, more preferably 2 to 20 nm.
• the thickness of the underlayer is equal to or greater than the lower limit, the effect of improving the adhesion due to the underlayer tends to be sufficiently obtained.
• the thickness of the underlying layer is equal to or less than the upper limit, the abrasion resistance of the underlying layer itself increases.
• Methods for measuring the thickness of the underlayer include a method of cross-sectional observation of the underlayer with an electron microscope (SEM, TEM, etc.), and a method of using an optical interference film thickness meter, a spectroscopic ellipsometer, a profilometer, and the like.
• Examples of the method of forming the underlying layer include a method of vapor-depositing a vapor deposition material having a desired composition of the underlying layer on the surface of the base material.
• An example of the vapor deposition method is a vacuum vapor deposition method.
• the vacuum deposition method is a method of evaporating a deposition material in a vacuum chamber and attaching it to the surface of a substrate.
• the temperature during vapor deposition (for example, the temperature of the boat in which the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 100 to 3000.degree. C., more preferably 250 to 3000.degree.
• the pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the absolute pressure in the tank in which the vapor deposition material is placed) is preferably 1 Pa or less, more preferably 0.1 Pa or less.
• one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used. Evaporation materials can be melted and vaporized on a resistance heating boat made of high-melting-point metal. and the electron gun method of evaporating.
• the evaporation method of the vapor deposition material it is possible to evaporate high-melting-point substances because it can be locally heated, and since the temperature is low where the electron beam is not applied, there is no risk of reaction with the container or contamination with impurities. gun law is preferred.
• the vapor deposition material used in the electron gun method a molten granular material or a sintered material is preferable because it is difficult to scatter even when an air current is generated.
• the surface layer contains the condensate of the fluorine-containing ether compound.
• the hydrolyzable silyl group in the fluorine-containing ether compound undergoes a hydrolysis reaction to form a silanol group (Si-OH), and the silanol group undergoes an intermolecular condensation reaction to form Si- A structure in which an O—Si bond is formed, and a silanol group in the fluorine-containing ether compound is condensed with a silanol group or a Si—OM group (where M is an alkali metal element) on the surface of the base material or underlayer. It includes structures that have reacted to form Si--O--Si bonds.
• the surface layer may contain a condensate of a fluorine-containing compound other than the fluorine-containing ether compound. That is, the surface layer contains a fluorine-containing compound having a reactive silyl group in a state in which a part or all of the reactive silyl groups of the fluorine-containing compound undergo a condensation reaction.
• 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 composition or the present coating liquid.
• the composition can be used as such in a dry coating method.
• the composition 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 the present composition is supported on a metal porous body made of a metal material such as iron or steel may be used.
• a pellet-like material supporting the present composition can be produced by impregnating a porous metal body with a solution of the present composition and drying to remove the liquid medium.
• the present coating liquid can be used as the solution of the present composition.
• 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.
• an operation for promoting the reaction between the fluorine-containing ether compound and the base material (or underlayer) may be performed.
• the operation includes heating, humidification, light irradiation, and the like.
• 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 formation 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 methods include a method of pouring a solvent over the surface layer, a method of wiping off with a cloth impregnated with a solvent, and the like.
• Examples 1-9 and 15-17 are working examples, and examples 10-14 are comparative examples. 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.
• (OCF 2 CF 2 ) 14 OCF 2 CH 2 —OCH 2 CH 2 CH 2 —Si[CH 2 CH 2 CH 2 —Si(OCH 3 ) 3 ] 3 ( X3) CF 3 —(OCF 2 ) 24.
• (OCF 2 CF 2 ) 11 OF 2 CH 2 —OCH 2 CH 2 CH 2 —Si[CH 2 CH 2 CH 2 —Si(OCH 3 ) 3 ] 3 ( X4) CF 3 —(OCF 2 ) 30.
• (OCF 2 CF 2 ) 7 OCF 2 CH 2 —OCH 2 CH 2 CH 2 —Si[CH 2 CH 2 CH 2 —Si(OCH 3 ) 3 ] 3 ( X5) CF 3 —(OCF 2 ) 14.
• (OCF 2 CF 2 ) 17 OF 2 CH 2 —OCH 2 CH 2 CH 2 —Si[CH 2 CH 2 CH 2 —Si(OCH 3 ) 3 ] 3 ( X6)
• the numerical values in parentheses of (OCF 2 ) and (OCF 2 CF 2 ) represent the average numbers of (OCF 2 ) and (OCF 2 CF 2 ) in compounds X2 to X6, respectively. means.
• mA means the average number of ( OCF2 ) in each compound
• mB means the average number of ( OCF2CF2 ) in each compound.
• compositions 1 to 11 were obtained by mixing fluorine-containing ether compounds so as to obtain the compositions shown in Table 2.
• Examples 1 to 8 and Examples 15 to 17 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 each composition described in Table 3 is heated to 300 ° C. by resistance heating, and the composition is vacuum-deposited, Film formation was completed when the thickness of the composition on the substrate reached 10 nm. Thereafter, the substrate on which the composition was deposited was heated at a temperature of 200° C. for 30 minutes (post-treatment) to obtain a substrate (article) with a surface layer.
• a base material non-alkali glass (Eagle XG: product name, manufactured by Corning, 50 mm ⁇ 50 mm, thickness 0.5 mm)
• Example 9 The composition shown in Table 1 was mixed with C 4 F 9 OC 2 H 5 (Novec-7200: product name, manufactured by 3M) as a liquid medium, and the content of the composition in the coating agent was 0. A coating solution was prepared which was .1% by weight. Alkali-free glass (Eagle XG: product name, manufactured by Corning, 50 mm ⁇ 50 mm, thickness 0.5 mm) was prepared as a substrate. After spray-coating the coating agent on one main surface of the substrate at a coating amount of 6.0 g/sec using a Nordson spray, the coating agent formed on the substrate is heated at 120 ° C. for 10 It was dried for a minute to obtain a base material (article) with a surface layer. The thickness of the surface layer was 10 nm.
• Example 10-12 Substrates (articles) with a surface layer were obtained in the same manner as in Examples 1 to 8, except that the compounds listed in Table 1 were used instead of the compositions.
• Example 13-14 A base material (article) with a surface layer was obtained in the same manner as in Example 9, except that the compounds listed in Table 1 were used instead of the composition.
• ⁇ Initial water contact angle> The contact angle of approximately 2 ⁇ L of distilled water placed on the surface of the surface layer was measured using a contact angle measurement device (manufactured by Kyowa Interface Science Co., Ltd., DM-500). Measurements were taken at five different points on the surface of the surface layer, and the average value was calculated as the initial contact angle. The 2 ⁇ method was used to calculate the contact angle. Based on the obtained initial contact angle, the water repellency was evaluated according to the following criteria. A (excellent): 115 degrees or more. B (good): 110 degrees or more and less than 115 degrees. C (acceptable): 100 degrees or more and less than 110 degrees. D (impossible): Less than 100 degrees.
• M A /M B ) is 1.35 or more, it was confirmed that the dynamic friction coefficient is low and a surface layer with excellent lubricity can be formed (Examples 1 to 9 and 15 to 17).

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