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WO2025070069A1 - Agent de traitement de surface - Google Patents

Agent de traitement de surface Download PDF

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Publication number
WO2025070069A1
WO2025070069A1 PCT/JP2024/032570 JP2024032570W WO2025070069A1 WO 2025070069 A1 WO2025070069 A1 WO 2025070069A1 JP 2024032570 W JP2024032570 W JP 2024032570W WO 2025070069 A1 WO2025070069 A1 WO 2025070069A1
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group
independently
integer
formula
atom
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Japanese (ja)
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由夏 川上
裕介 渡邊
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Daikin Industries Ltd
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Daikin Industries Ltd
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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
    • 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
    • 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
    • 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
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • This disclosure relates to a surface treatment agent.
  • a layer obtained from a surface treatment agent containing a fluoropolyether group-containing silane compound (hereinafter also referred to as a "surface treatment layer”) is applied as a so-called functional thin film to a wide variety of substrates, such as glass, plastics, textiles, sanitary products, and building materials (Patent Document 1).
  • the fluoropolyether group-containing silane compound described in Patent Document 1 can provide a surface treatment layer with excellent functionality, but there is a demand for a surface treatment layer with even greater durability.
  • the purpose of this disclosure is to provide a surface treatment agent that can produce a film with good abrasion resistance.
  • the compound (B) is represented by the following formula (3), (4) or (5):
  • Each A is independently a C atom or a Si atom;
  • Each R F1 is independently Rf 1 -R F -O q -;
  • R F2 is -Rf 2 p -R F -O q -;
  • Each Rf 1 is independently a
  • Each ⁇ is independently an integer from 1 to 3.
  • a composition comprising at least one compound represented by the formula (A) (wherein compound (A) and compound (B) are different).
  • the silane compound (A) having a fluoropolyether group is represented by the formula (1) or (2): [Wherein: Each R F1 is independently Rf 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; Each Rf 1 is independently a C 1-16 alkyl group optionally substituted by one or more fluorine atoms; Rf 2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms; Each R F is independently a divalent fluoropolyether group; p is 0 or 1; Each q is independently 0 or 1; R Si is each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which
  • composition according to [1] comprising at least one compound represented by the formula: [3]
  • composition according to [1] or [2] wherein the proportion of R B1 contained in the composition with respect to the total of R Si and R B1 contained in the composition is 25 mol % or less.
  • the silane compound (A) is represented by the formula (1a): R F1 -X A -R Si (1a) [Wherein: Each R F1 is independently Rf 1 -R F -O q -; Each Rf 1 is independently a C 1-16 alkyl group optionally substituted by one or more fluorine atoms; Each R F is independently a divalent fluoropolyether group; Each q is independently 0 or 1; R Si is each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group is bonded; In formula (1), at least one R Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto; In formula (1), R Si does not contain an allyl ether group; Each XA is independently a single bond or a divalent to decavalent organic group.
  • X A is a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 - [Wherein: R 51 represents a single bond, —(CH 2 ) s5 —, or an o-, m- or p-phenylene group, preferably —(CH 2 ) s5 —; s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, even more preferably 1 or 2; X 51 represents -(X 52 ) l5 -; X 52 each independently represents a group selected from the group consisting of -O-, -S-, o-, m- or p-phenylene group, -C(O)O-, -Si(R 53 ) 2 -, -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -, -CONR 54 -, -O-
  • R Si is represented by the following formula (S3): -SiR a1 k1 R b1 l1 R c1 m1 (S3) [Wherein, Each R a1 independently represents -Z 1 -SiR 22 q1 R 23 r1 ; Z 1 's each independently represent an oxygen atom or a divalent organic group, and in the structure hereinafter described as Z 1 , the right side is bonded to (SiR 22 q1 R 23 r1 ); R 22 each independently represents a hydroxyl group or a hydrolyzable group; Each R 23 independently represents a hydrogen atom or a monovalent organic group; q1 is independently an integer of 1 to 3 for each (SiR 22 q1 R 23 r1 ) unit; Each R b1 independently represents a hydroxyl group or a hydrolyzable group; Each R c1 independently represents a hydrogen atom or a monovalent organic group; each k1 is independently an integer of 0 to 3,
  • composition according to any one of [1] to [3], comprising a compound represented by the following formula: [5] A surface treatment agent comprising the composition according to any one of [1] to [4]. [6] The surface treatment agent according to [5], further comprising one or more components selected from fluorine-containing oils and silicone oils. [7] The surface treatment agent according to [5] or [6], which is used as an antifouling coating agent or a waterproof coating agent. [8] An article comprising a substrate and a layer formed on a surface of the substrate from the composition according to any one of items [1] to [4]. [9] An article comprising a substrate and a layer formed on the surface of the substrate from the surface treatment agent according to any one of [5] to [7].
  • the present invention provides a surface treatment agent that can produce a film with good abrasion resistance.
  • composition of the present disclosure contains a silane compound (A) having a fluoropolyether group and a compound (B) having a fluoropolyether group and an allyl ether group. Since the composition of the present disclosure contains the above-mentioned compound (A) and compound (B), a film with good abrasion resistance can be realized. However, compound (A) and compound (B) are different.
  • silane compound (A) can provide a film with good abrasion resistance, particularly abrasion resistance against steel wool.
  • compound (B) in addition to compound (A), a film can be obtained that is not only abrasion resistant against steel wool, but also has good abrasion resistance against softer materials, for example, resin-based materials such as erasers.
  • compound (B) has a vinyl ether group at the end, and it is believed that such a group can act to suppress damage to the film when friction occurs with a soft material.
  • the silane compound (A) having a fluoropolyether group may be a compound having a fluoropolyether group and a hydrolyzable silyl group, and preferably does not contain an allyl ether group.
  • the compound (A) is represented by the following formula (1) or (2): [Wherein: Each R F1 is independently Rf 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; Each Rf 1 is independently a C 1-16 alkyl group optionally substituted by one or more fluorine atoms; Rf2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms; Each R F is independently a divalent fluoropolyether group; p is 0 or 1; Each q is independently 0 or 1; R Si is each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group is bonded; In each of formula (1) and formula (2), at least one R Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group
  • each R F1 is independently Rf 1 -R F -O q -.
  • R F2 is —Rf 2 p —R F —O q —.
  • each Rf 1 is independently a C 1-16 alkyl group optionally substituted with one or more fluorine atoms.
  • the "C 1-16 alkyl group" in the above-mentioned C 1-16 alkyl group optionally substituted by one or more fluorine atoms may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-6 alkyl group, particularly a straight chain or branched chain C 1-3 alkyl group, more preferably a straight chain C 1-6 alkyl group, particularly a straight chain C 1-3 alkyl group.
  • Rf 1 is preferably a C 1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 perfluoroalkylene group, and even more preferably a C 1-16 perfluoroalkyl group.
  • the above C 1-16 perfluoroalkyl group may be linear or branched, and is preferably a linear or branched C 1-6 perfluoroalkyl group, in particular a C 1-3 perfluoroalkyl group, and more preferably a linear C 1-6 perfluoroalkyl group, in particular a C 1-3 perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , or -CF 2 CF 2 CF 3 .
  • Rf2 is a C 1-6 alkylene group optionally substituted with one or more fluorine atoms.
  • C 1-6 alkylene group in the above-mentioned C 1-6 alkylene group optionally substituted by one or more fluorine atoms may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 alkylene group, and more preferably a straight chain C 1-3 alkylene group.
  • Rf 2 is preferably a C 1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C 1-6 perfluoroalkylene group, and even more preferably a C 1-3 perfluoroalkylene group.
  • the C 1-6 perfluoroalkylene group may be linear or branched, and is preferably a linear or branched C 1-3 perfluoroalkylene group, more preferably a linear C 1-3 perfluoroalkylene group, specifically, -CF 2 -, -CF 2 CF 2 -, or -CF 2 CF 2 CF 2 -.
  • p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.
  • each q is independently 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.
  • each R 1 F is independently a divalent fluoropolyether group.
  • RF is preferably of the formula: -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 R Fa 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f - [Wherein: Each R Fa is independently a hydrogen atom, a fluorine atom, or a chlorine atom; a, b, c, d, e, and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more.
  • each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula. However, when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e, and f is 1 or more.] (hereinafter, also referred to as a group represented by "PFPE").
  • R Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom, provided that when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.
  • A, b, c, d, e and f may each preferably be independently an integer from 0 to 100.
  • the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
  • the sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, and even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.
  • repeating units may be linear or branched, and may contain a ring structure.
  • -(OC 6 F 12 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF 2 CF (CF 3 )CF 2 )-, etc.
  • -(OC 6 F 12 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )-, etc.
  • -(OC 5 F 10 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF(CF 3 ))-, etc. may be used.
  • -( OC4F8 )- may be any of -( OCF2CF2CF2CF2 ) -, -(OCF( CF3 ) CF2CF2 )-, -( OCF2CF ( CF3 ) CF2 )-, -( OCF2CF2CF ( CF3 ))-, -(OC( CF3 ) 2CF2 )-, -(OCF2C( CF3 ) 2 )-, -( OCF ( CF3 )CF( CF3 ) )-, -(OCF( C2F5 ) CF2 ) - and - ( OCF2CF ( C2F5 ))-.
  • -(OC 3 F 6 )- (i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )-, and -(OCF 2 CF(CF 3 ))-.
  • -(OC 2 F 4 )- may be any of -(OCF 2 CF 2 )- and -(OCF(CF 3 ))-.
  • the ring structure may be a three-, four-, five-, or six-membered ring as described below. [In the formula, * indicates the bond position.]
  • the ring structure may preferably be a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.
  • the repeating unit having a ring structure may preferably be the following unit. [In the formula, * indicates the bond position.]
  • the repeating unit is linear. By making the repeating unit linear, the surface slip properties, abrasion resistance, etc. of the film (surface treatment layer) can be improved.
  • the repeating unit is a branched chain.
  • the dynamic friction coefficient of the film (surface treatment layer) can be increased.
  • each R F is independently a group represented by any one of the following formulas (f1) to (f6). -(OC 3 F 6 ) d - (OC 2 F 4 ) e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1.] -(OC 4 F 8 ) c - (OC 3 R Fa 6 ) d - (OC 2 F 4 ) e - (OCF 2 ) f - (f2) [In the formula, each R Fa independently represents a hydrogen atom, a fluorine atom, or a chlorine atom, and is preferably a fluorine atom; each c and d independently represent an integer of 0 to 30; each e and f independently represent an integer of 1 to 200; the sum of c, d, e, and f is 2 or more; The order of occurrence of each repeat unit enclosed in parentheses with the subscript c, d, e, or f is .
  • R6 is OCF2 or OC2F4
  • R7 is a group selected from OC2F4 , OC3F6 , OC4F8 , OC5F10 and OC6F12 , or a combination of two or three groups independently selected from these groups
  • g is an integer from 2 to 100
  • R6 ' is OCF2 or OC2F4
  • R 7′ is a group selected from OC 2 F 4 , OC 3 F 6
  • d is preferably an integer of 5 to 200, more preferably 10 to 100, further preferably 15 to 50, for example, 25 to 35.
  • OC 3 F 6 is preferably (OCF 2 CF 2 CF 2 ), (OCF(CF 3 )CF 2 ) or (OCF 2 CF(CF 3 )), more preferably (OCF 2 CF 2 CF 2 ).
  • (OC 2 F 4 ) is preferably (OCF 2 CF 2 ) or (OCF(CF 3 )), more preferably (OCF 2 CF 2 ).
  • e is 0. In another embodiment, e is 1.
  • e and f are each independently an integer of preferably 5 to 200, more preferably 10 to 200.
  • the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
  • the above formula (f2) is preferably a group represented by -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -, more preferably a group represented by -(OCF 2 CF 2 CF 2 CF 2 ) c -(OCF 2 CF 2 CF 2 ) d -(OCF 2 CF 2 ) e -(OCF 2 ) f -.
  • formula (f2) may be a group represented by -(OC 2 F 4 ) e -(OCF 2 ) f -.
  • formula (f2) may be -(OC 4 F 8 ) c -(OCF 2 CF 2 (CR Fa ) 2 ) d10 -(OCF 2 CF(CF 3 )) d11 -(OCF 2 CF 2 ) e -(OCF 2 ) f -.
  • d10 and d11 are each independently an integer of 0 to 200, preferably an integer of 5 to 200, more preferably an integer of 10 to 200. However, the sum of d10 and d11 is 0 to 200, preferably 5 to 200, more preferably 10 to 200.
  • R6 is preferably OC2F4
  • R 7 is preferably a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or a combination of two or three groups independently selected from these groups, and more preferably a group selected from OC 3 F 6 and OC 4 F 8 .
  • the combination of two or three groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited, and examples thereof include -OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 4 F 8 -, -OC 3 F 6 OC 2 F 4 -, -OC 3 F 6 OC 3 F 6 -, -OC 3 F 6 OC 4 F 8 -, -OC 4 F 8 OC 4 F 8 -, -OC 4 F 8 OC 3 F 6 -, -OC 4 F 8 OC 2 F 4 -, -OC 2 F 4 OC 2 F 4 OC 3 F 6 - , -OC 2 F 4 OC 2 F 4 OC 3 F 6 - , -OC 2 F 4 OC 2 F 4 OC 4 F 8 -, -OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 4 F 8 -, -OC 2 F 4 OC 3 F 6 -
  • g is preferably an integer of 3 or more, more preferably 5 or more.
  • the above g is preferably an integer of 50 or less.
  • OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, and are preferably linear.
  • the above formula (f3) is preferably -(OC 2 F 4 -OC 3 F 6 ) g - or -(OC 2 F 4 -OC 4 F 8 ) g -.
  • R 6 , R 7 and g have the same meanings as those described in the above formula (f3) and have the same embodiments.
  • R 6 ' , R 7 ' and g ' have the same meanings as those described in the above formula (f3) and have the same embodiments.
  • R r is preferably [In the formula, * indicates the bond position.] and more preferably [In the formula, * indicates the bond position.] It is.
  • e is preferably an integer of 1 or more and 100 or less, more preferably an integer of 5 or more and 100 or less.
  • the sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.
  • f is preferably an integer of 1 or more and 100 or less, more preferably an integer of 5 or more and 100 or less.
  • the sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.
  • the R F is a group represented by the formula (f1).
  • the RF is a group represented by the formula (f2).
  • the R F is a group represented by the formula (f3).
  • the R F is a group represented by the formula (f4).
  • the R F is a group represented by the formula (f5).
  • the ratio of e to f (hereinafter referred to as "e/f ratio”) is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85.
  • e/f ratio 10 or less the slipperiness, wear resistance, and chemical resistance of the film (surface treatment layer) obtained from this compound are further improved.
  • the smaller the e/f ratio the more the slipperiness and wear resistance of the film are improved.
  • the e/f ratio 0.1 or more the stability of the compound can be further improved. The larger the e/f ratio, the more the stability of the compound is improved.
  • the number average molecular weight of the RF1 and RF2 portions is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000.
  • the number average molecular weights of RF1 and RF2 are values measured by 19F -NMR.
  • the number average molecular weight of the RF1 and RF2 portions may be from 500 to 30,000, preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, even more preferably from 2,000 to 10,000, for example, from 3,000 to 6,000.
  • the number average molecular weight of the RF1 and RF2 portions can be from 4,000 to 30,000, preferably from 5,000 to 10,000, and more preferably from 6,000 to 10,000.
  • R 3 Si is each independently a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group is bonded, and at least one R 3 Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.
  • R 3 Si contributes to adhesion to a substrate and may chemically react with the material of the substrate.
  • R 1 Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto.
  • R Si is represented by the following formula (S3) or (S4): It is a group represented by the following formula:
  • each R a1 is independently —Z 1 —SiR 22 q1 R 23 r1 .
  • Z1 's are each independently an oxygen atom or a divalent organic group.
  • the right side is bonded to ( SiR22q1R23r1 ) .
  • Z1 is a divalent organic group.
  • Z 1 does not include any that forms a siloxane bond with the Si atom to which Z 1 is bonded.
  • (Si-Z 1 -Si) does not include a siloxane bond.
  • the above Z 1 is preferably a C 1-6 alkylene group, -(CH 2 ) z1 -O-(CH 2 ) z2 - (wherein z1 is an integer of 0 to 6, for example an integer of 1 to 6, and z2 is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 - (wherein z3 is an integer of 0 to 6, for example an integer of 1 to 6, and z4 is an integer of 0 to 6, for example an integer of 1 to 6 ).
  • Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
  • These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but are preferably unsubstituted.
  • Z 1 is a C 1-6 alkylene group or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 -, preferably -phenylene-(CH 2 ) z4 -.
  • Z 1 is such a group, light resistance, particularly ultraviolet resistance, may be improved.
  • Z 1 is a C 1-3 alkylene group. In one embodiment, Z 1 can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 1 can be -CH 2 CH 2 -.
  • R 22s each independently represent a hydroxyl group or a hydrolyzable group.
  • each R 22 is independently a hydrolyzable group.
  • R j includes unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred.
  • R j is a methyl group, and in another embodiment, R j is an ethyl group.
  • Each R23 is independently a hydrogen atom or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • Each q1 is independently an integer of 0 to 3, and each r1 is independently an integer of 0 to 3.
  • the sum of q1 and r1 is 3 in the (SiR 22 q1 R 23 r1 ) unit.
  • q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR 22 q1 R 23 r1 ) unit.
  • q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3, for each (SiR 22 q1 R 23 r1 ) unit.
  • each R b1 is independently a hydroxyl group or a hydrolyzable group.
  • each of the R b1 's is independently a hydrolyzable group.
  • R j include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred.
  • R j is a methyl group, and in another embodiment, R j is an ethyl group.
  • each R c1 is independently a hydrogen atom or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • Each k1 is independently an integer of 0 to 3
  • each l1 is independently an integer of 0 to 3
  • each m1 is independently an integer of 0 to 3.
  • the sum of k1, l1 and m1 is 3 in the (SiR a1 k1 R b1 l1 R c1 m1 ) unit.
  • k1 is independently for each (SiR a1 k1 R b1 l1 R c1 m1 ) unit an integer from 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.
  • R Si is a group represented by formula (S3), preferably, at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal portion of formula (1) and formula (2).
  • k1 is 2 or 3, preferably 3, and q1 is 2 or 3, preferably 3.
  • R e1 are each independently —Z 3 —SiR 34 n2 R 35 3-n2 .
  • Z3 's are each independently a single bond, an oxygen atom or a divalent organic group.
  • the right side is bonded to (SiR 34 n2 R 35 3-n2 ).
  • Z3 is an oxygen atom.
  • Z3 is a divalent organic group.
  • These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but are preferably unsubstituted.
  • Z 3 is a C 1-6 alkylene group or --(CH 2 ) z7" -phenylene-(CH 2 ) z8" --, preferably -phenylene-(CH 2 ) z8" --.
  • Z 3 is such a group, light resistance, particularly ultraviolet resistance, may be improved.
  • Z 3 is a C 1-3 alkylene group. In one embodiment, Z 3 can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 3 can be -CH 2 CH 2 -.
  • R 34 s each independently represent a hydroxyl group or a hydrolyzable group.
  • each R 34 is independently a hydrolyzable group.
  • R j includes unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred.
  • R j is a methyl group, and in another embodiment, R j is an ethyl group.
  • Each R 35 is independently a hydrogen atom or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • n2 is independently an integer from 0 to 3 for each (SiR n2 R 35 3-n2 ) unit.
  • R Si is a group represented by formula (S4)
  • at least one (SiR n2 R 35 3-n2 ) unit in which n2 is 1 to 3 is present in the terminal portion of formula (1) and formula (2). That is, in such terminal portion, all n2's do not become 0 at the same time.
  • at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present in the terminal portion of formula (1) and formula (2).
  • n2 is preferably an integer of 1 to 3, more preferably 2 or 3, and further preferably 3, independently for each (SiR 34 n2 R 35 3-n2 ) unit.
  • Each R f1 is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
  • R f1 is a hydroxyl group.
  • R f1 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • R Si is a group represented by formula (S4)
  • the (SiR n2 R 35 3 -n2 ) units where n2 is 1 to 3, preferably 2 or 3, and more preferably 3, are present in each terminal portion of formula (1) and formula (2) at 2 or more, for example 2 to 27, preferably 2 to 9, more preferably 2 to 6, even more preferably 2 to 3, and particularly preferably 3.
  • n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, in at least one, preferably all, R e1 .
  • l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.
  • the divalent to decavalent organic group in XA is preferably a divalent to octavalent organic group.
  • the divalent to decavalent organic group is preferably a divalent to tetravalent organic group, more preferably a divalent organic group.
  • the divalent to decavalent organic group is preferably a trivalent to octavalent organic group, more preferably a trivalent to hexavalent organic group.
  • X 1 A is a single bond or a divalent organic group, ⁇ is 1 and ⁇ is 1.
  • X 1 A is a single bond or a divalent organic group and ⁇ is 1.
  • XA is a trivalent to hexavalent organic group and ⁇ is 2 to 5.
  • XA is a trivalent organic group and ⁇ is 2.
  • formulas (1) and (2) are represented by the following formulas (1a) and (2a).
  • R 1 Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto.
  • R 1 Si does not contain an allyl ether group.
  • XA is a divalent organic group.
  • X A (typically a hydrogen atom of X A ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group. In a preferred embodiment, X A is not substituted with these groups.
  • each of the XA 's is independently -( R51 ) p5- ( X51 ) q5 - R52- .
  • R52 represents a single bond, -( CH2 ) t5- or an o-, m- or p-phenylene group, and is preferably -( CH2 ) t5- .
  • t5 is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3.
  • R52 (typically the hydrogen atom of R52 ) may be substituted with one or more substituents selected from a fluorine atom, a C1-3 alkyl group, and a C1-3 fluoroalkyl group.
  • R56 is not substituted with these groups.
  • each XA is independently Single bond, a C 1-20 alkylene group, -R 51 -X 53 -R 52 -, or -X 54 -R 52 - [In the formula, R 51 and R 52 are as defined above, X53 is -O-, -S-, -C(O)O-, -CONR 54- , -O-CONR 54 -, -Si(R 53 ) 2 -, -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -, -O-(CH 2 ) u5 -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -, -O-( CH2 ) u5 -Si( R53 ) 2 -O-Si( R53 ) 2- CH2CH2 - Si ( R53 ) 2 -O-Si( R53 ) 2- , -O-(CHCH2
  • each XA is independently Single bond, a C 1-20 alkylene group, -(CH 2 ) s5 -X 53 -, -(CH 2 ) s5 -X 53 -(CH 2 ) t5 - -X54- or -X54- ( CH2 ) t5- [In the formula, X 53 , X 54 , s5 and t5 are as defined above.] It is.
  • each XA is independently a single bond C 1-20 alkylene group, -(CH 2 ) s5 -X 53 - or -(CH 2 ) s5 -X 53 -(CH 2 ) t5 - [Wherein, X 53 is —O—, —CONR 54 —, or —O—CONR 54 —; R 54 each independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group; s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It could be.
  • each XA is independently -(CH 2 ) s5 -O-(CH 2 ) t5 - -CONR 54 -(CH 2 ) t5 - [Wherein, R 54 each independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group; s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It could be.
  • each XA is independently Single bond, a C 1-20 alkylene group, -(CH 2 ) s5 -O-(CH 2 ) t5 -, -(CH 2 ) s5 -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -(CH 2 ) t5 -, -(CH 2 ) s5 -O-(CH 2 ) u5 -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -(CH 2 ) t5 -, or -(CH 2 ) s5 -O-(CH 2 ) t5 -Si(R 53 ) 2 -(CH 2 ) u5 -Si( R53 ) 2- ( Cv5H2v5 )- [In the formula, R 53 , m5, s5, t5 and u5 are defined as above, and v5 is an
  • --(C v H 2v )-- may be a straight chain or a branched chain, for example, --CH 2 CH 2 --, --CH 2 CH 2 CH 2 --, --CH(CH 3 )--, or --CH(CH 3 )CH 2 --.
  • Each of the X 1 A may be independently substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group). In one embodiment, X 1 A is unsubstituted.
  • each formula of XA above is bonded to R F1 or R F2
  • the right side is bonded to R Si .
  • each X 1 A may independently be other than an —O—C 1-6 alkylene group.
  • XA includes, for example, the following groups: [In the formula, each R 41 independently represents a hydrogen atom, a phenyl group, a C 1-6 alkyl group, or a C 1-6 alkoxy group, preferably a methyl group; D is -CH 2 O(CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 -, -CF 2 O(CH 2 ) 3 -, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -( CH2 ) 4- , -CONH-(CH 2 ) 3 -, -CON( CH3 )-( CH2 ) 3- , -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl), and (In the formula, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more
  • XA Specific examples include: Single bond, -CH 2 OCH 2 -, -CH 2 O(CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 -, -CH 2 O(CH 2 ) 4 -, -CH 2 O(CH 2 ) 5 -, -CH 2 O(CH 2 ) 6 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (
  • XA is each independently a group represented by the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH 2 ) z1 -, where x1, y1 and z1 are each independently an integer of 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of occurrence of each repeat unit enclosed in parentheses in the formula is arbitrary.
  • the "lower alkyl group” is, for example, a C 1-6 alkyl group, such as methyl, ethyl, or n-propyl, which may be substituted with one or more fluorine atoms.
  • R 17 is each independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom.
  • the "lower fluoroalkyl group” is, for example, a C 1-6 , preferably a C 1-3 fluoroalkyl group, preferably a C 1-3 perfluoroalkyl group, more preferably a trifluoromethyl group or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • examples of XA include the following groups: [Wherein, R 41 is each independently a hydrogen atom, a phenyl group, a C 1-6 alkyl group, or a C 1-6 alkoxy group, preferably a methyl group; In each XA group, any one of T's may be the following group bonded to RF1 or RF2 of the molecular backbone: -CH 2 O(CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 -, -CF 2 O(CH 2 ) 3 -, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -( CH2 ) 4- , -CONH-(CH 2 ) 3 -, -CON( CH3 )-( CH2 ) 3- , -CON(Ph)-(CH 2 ) 3 -, where Ph is phenyl, or [In the formula, each R 42 independently represents a hydrogen atom, a C 1-6
  • the radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation, but examples include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, or triazines.
  • the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, but examples include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.
  • preferred radical scavenging groups or UV absorbing groups include groups represented by the following formula:
  • each X 1 A may independently be a trivalent to decavalent organic group.
  • examples of XA include the following groups: [In the formula, R 25 , R 26 and R 27 each independently represent a divalent to hexavalent organic group, R 25 is bonded to at least one R F1 , and R 26 and R 27 are each bonded to at least one R Si .
  • R 25 is a single bond, a C 1-20 alkylene group, a C 3-20 cycloalkylene group, a C 5-20 arylene group, -R 57 -X 58 -R 59 -, -X 58 -R 59 -, or -R 57 -X 58 -.
  • R 57 and R 59 are each independently a single bond, a C 1-20 alkylene group, a C 3-20 cycloalkylene group, or a C 5-20 arylene group.
  • X 58 is -O-, -S-, -CO-, -O-CO-, or -COO-.
  • R 26 and R 27 are each independently a hydrocarbon or a group having at least one atom selected from N, O and S at the end or in the main chain of the hydrocarbon, preferably a C 1-6 alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2 -, etc.
  • R 36 is each independently a single bond or a C 1-6 alkyl group, preferably a C 1-6 alkyl group.
  • R 37 is N, O or S, preferably N or O.
  • R 38 is -R 45 -R 46 -R 45 -, -R 46 -R 45 - or -R 45 -R 46 -.
  • R 45 is each independently a C 1-6 alkyl group.
  • R 46 is N, O or S, preferably O.
  • the compound may have an average molecular weight of 5 x 10 2 to 1 x 10 5 , but is not particularly limited thereto. Among these, from the viewpoint of UV resistance and friction durability, it is preferable that the compound has an average molecular weight of preferably 2,000 to 30,000, more preferably 2,500 to 12,000.
  • the "average molecular weight” refers to a number average molecular weight, and the “average molecular weight” is a value measured by 19 F-NMR.
  • compound (A) may be preferably a compound represented by formula (1), more preferably a compound represented by formula (1a), and even more preferably a compound represented by formula (1b), and in another embodiment, compound (A) may be preferably a compound represented by formula (2), more preferably a compound represented by formula (2a), and even more preferably a compound represented by formula (2b).
  • the fluoropolyether group-containing silane compound represented by the above formula (1) or formula (2) may have an average molecular weight of 5 x 10 2 to 1 x 10 5 , but is not particularly limited thereto. Within this range, it is preferable from the viewpoint of wear resistance that the average molecular weight is 2,000 to 32,000, more preferably 2,500 to 12,000. Note that the "average molecular weight” refers to a number average molecular weight, and the "average molecular weight” is a value measured by 19 F-NMR.
  • the total content of the compounds represented by formula (1) or (2) in compound (A) may be preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less.
  • the compound (B) having a fluoropolyether group and an allyl ether group has a fluoropolyether group and an allyl ether group, and in a preferred embodiment, is represented by the following formula (3), (4) or (5):
  • RF1 , RF2 , RSi , XA , ⁇ , ⁇ and ⁇ are as defined above.
  • A is, independently of one another, a C atom or a Si atom. In one embodiment, A is a C atom. In another embodiment, A is a Si atom. A is preferably a Si atom.
  • Each R B1 is independently —R B3 —O—CH ⁇ CH— CH3 .
  • Each R B2 is independently one or more selected from -R B3 -O-CH 2 CH 2 CH 2 -SiR B4 ⁇ R B5 3- ⁇ and a hydrogen atom.
  • R B2 can be -R B3 -O-CH 2 CH 2 CH 2 -SiR B4 ⁇ R B5 3- ⁇ .
  • R B2 can be a hydrogen atom.
  • R B3 are each independently a single bond or a C 1-20 alkylene group.
  • R B3 may preferably be a single bond.
  • R B3 may preferably be a C 1-20 alkylene group, more preferably a C 1-6 alkylene group.
  • Each R B4 is independently a hydroxyl group or a hydrolyzable group.
  • each R B4 is independently a hydrolyzable group.
  • R j includes unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred.
  • R j is a methyl group, and in another embodiment, R j is an ethyl group.
  • Each R B5 is independently a hydrogen atom or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • ⁇ is independently an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3 for each (SiR B4 ⁇ R B5 3- ⁇ ) unit.
  • ⁇ is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (AR B1 ⁇ R B2 3- ⁇ ) unit.
  • the compound (B) represented by the above formula (3), formula (4) or formula (5) may have an average molecular weight of, but is not particularly limited to, 5 x 10 2 to 1 x 10 5. Within this range, it is preferable from the viewpoint of wear resistance that the compound (B) has an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000.
  • the ratio of R B1 contained in the above composition to the total of R Si and R B1 contained in the above composition is preferably 25 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and may be, for example, 0.1 mol% or more, even 1 mol% or more. By being in this range, it can be easy to provide a film with better abrasion resistance, especially abrasion resistance against soft materials (for example, resin-based materials such as erasers).
  • the content of compound (B) represented by formula (3), formula (4) or formula (5) above may be preferably 0.1% by mass or more and 25% by mass or less, more preferably 1% by mass or more and 20% by mass or less, based on 100% by mass of the total of compound (A) and compound (B) above.
  • the content may be easier to provide a film with better abrasion resistance, particularly abrasion resistance against soft materials (e.g., resin-based materials such as erasers).
  • the total content of the compound (A) and the compound (B) may be preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less.
  • the surface treatment agent of the present disclosure includes the above composition.
  • the total content of the above compound (A) and the above compound (B) may be preferably 0.02 to 40.0 mass%, more preferably 0.02 to 30.0 mass%, even more preferably 0.04 to 25.0 mass%, and particularly preferably 0.05 to 20.0 mass% in 100 mass% of the surface treatment agent.
  • the non-volatile content may be the portion excluding the solvent from the total amount of the composition.
  • the surface treatment agent of the present disclosure may further contain a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter collectively referred to as "fluorine-containing oil”), a (non-reactive) silicone compound that can be understood as a silicone oil (hereinafter referred to as "silicone oil”), alcohols, catalysts, surfactants, polymerization inhibitors, sensitizers, etc.
  • the other components are components different from the above-mentioned compound (A) and compound (B).
  • the surface treatment agent of the present disclosure further contains one or more components selected from fluorine-containing oils and silicone oils.
  • Rf 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms
  • Rf 6 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom
  • Rf 5 and Rf 6 are more preferably each independently a C 1-3 perfluoroalkyl group.
  • a", b", c" and d respectively represent the number of four types of repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer and are each independently an integer of 0 to 300, and the sum of a", b", c" and d" is greater than 30, preferably 40 to 300, and more preferably 50 to 300.
  • the order of occurrence of each repeating unit enclosed in parentheses with the subscript a", b", c" or d" is arbitrary in the formula.
  • Examples of the perfluoro(poly)ether compound represented by the above general formula (6) include compounds represented by the following general formulas (6a) and (6b) (which may be one type or a mixture of two or more types): Rf 5 - (OCF 2 CF 2 CF 2 ) b" - Rf 6 ... (6a) Rf 5 - (OCF 2 CF 2 CF 2 ) a" - (OCF 2 CF 2 CF 2 ) b" - (OCF 2 CF 2 ) c" - (OCF 2 ) d" - Rf 6 ...
  • the fluorine-containing oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass, relative to the surface treatment agent.
  • the surface treatment agent of the present disclosure is substantially free of fluorine-containing oil. "Substantially free of fluorine-containing oil” means that the surface treatment agent does not contain any fluorine-containing oil, or may contain a very small amount of fluorine-containing oil.
  • the silicone oil for example, a linear or cyclic silicone oil having 2,000 or less siloxane bonds can be used.
  • the linear silicone oil may be so-called straight silicone oil or modified silicone oil.
  • straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil.
  • modified silicone oil include straight silicone oil modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc.
  • Examples of cyclic silicone oil include cyclic dimethylsiloxane oil, etc.
  • such silicone oil can be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, per 100 parts by mass of the total of the fluorine-containing silane compounds of the present disclosure (if there are two or more types, the total of these, the same applies below).
  • Silicone oil can help improve the surface slipperiness of the surface treatment layer.
  • the alcohols include alcohols having 1 to 6 carbon atoms which may be substituted with one or more fluorine atoms, such as methanol, ethanol, isopropanol, tert-butanol, CF 3 CH 2 OH, CF 3 CF 2 CH 2 OH, and (CF 3 ) 2 CHOH. Addition of these alcohols to the surface treatment agent improves the stability of the surface treatment agent and also improves the compatibility of the fluorine-containing silane compound with the solvent.
  • fluorine atoms such as methanol, ethanol, isopropanol, tert-butanol, CF 3 CH 2 OH, CF 3 CF 2 CH 2 OH, and (CF 3 ) 2 CHOH.
  • the catalyst promotes the hydrolysis and dehydration condensation of the fluorine-containing silane compound of the present disclosure, and promotes the formation of the layer formed by the surface treatment agent of the present disclosure.
  • the surface treatment agent disclosed herein may contain trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates.
  • impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates.
  • the article of the present disclosure includes a substrate and a layer (surface treatment layer) formed on the surface of the substrate from the composition and/or surface treatment agent of the present disclosure.
  • the article of the present disclosure includes a substrate and a layer formed on the surface of the substrate from the composition of the present disclosure.
  • the article of the present disclosure includes a substrate and a layer formed on the surface of the substrate from the surface treatment agent of the present disclosure.
  • Substrates that can be used in the present disclosure may be composed of any suitable material, such as glass, resin (which may be a natural or synthetic resin, such as a common plastic material), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, sanitary products, etc.
  • resin which may be a natural or synthetic resin, such as a common plastic material
  • metal ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, sanitary products, etc.
  • the material constituting the surface of the substrate may be a material for optical members, such as glass or transparent plastic.
  • some layer (or film), such as a hard coat layer or an anti-reflection layer may be formed on the surface (outermost layer) of the substrate.
  • the anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer.
  • Examples of inorganic substances that can be used for the anti-reflection layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , Ta 3 O 5 , Nb 2 O 5 , HfO 2 , Si 3 N 4 , CeO 2 , MgO, Y 2 O 3 , SnO 2 , MgF 2 , WO 3 and the like. These inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture). When a multi-layer antireflection layer is used, it is preferable to use SiO 2 and/or SiO 2 for the outermost layer.
  • a transparent electrode for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a part of the surface of the substrate (glass).
  • the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, depending on the specific specifications.
  • the shape of the substrate is not particularly limited and may be, for example, a plate, a film, or other shape.
  • the surface region of the substrate on which the surface treatment layer is to be formed may be at least a part of the substrate surface, and may be appropriately determined depending on the application and specific specifications of the product to be manufactured.
  • At least the surface portion of the substrate may be made of a material that originally has hydroxyl groups.
  • materials include glass, metals (particularly base metals), ceramics, semiconductors, etc., on whose surfaces natural oxide films or thermal oxide films are formed.
  • the substrate may be subjected to some pretreatment to introduce or increase the number of hydroxyl groups on the substrate surface. Examples of such pretreatment include plasma treatment (e.g., corona discharge) and ion beam irradiation.
  • Plasma treatment can introduce or increase hydroxyl groups on the substrate surface, and can also be suitably used to clean the substrate surface (remove foreign matter, etc.).
  • Another example of such pretreatment is a method in which an interfacial adsorbent having carbon-carbon unsaturated bond groups is formed in advance in the form of a monomolecular film on the substrate surface by the LB method (Langmuir-Blodgett method) or chemical adsorption method, and then the unsaturated bonds are cleaved in an atmosphere containing oxygen, nitrogen, etc.
  • At least the surface portion of such a substrate may be made of a material containing another reactive group, such as a silicone compound having one or more Si-H groups, or an alkoxysilane.
  • the substrate is glass.
  • glass examples include sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass, and particularly preferred are chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass.
  • the article of the present disclosure can be produced by forming a layer of the surface treatment agent of the present disclosure on the surface of the substrate, and then post-treating this layer as necessary, thereby forming a layer from the surface treatment agent of the present disclosure.
  • the formation of a layer of the surface treatment agent of the present disclosure can be carried out by applying the surface treatment agent to the surface of the substrate so as to coat the surface.
  • the coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.
  • wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and similar methods.
  • dry coating methods include deposition (usually vacuum deposition), sputtering, CVD, and similar methods.
  • deposition methods usually vacuum deposition
  • deposition methods include resistance heating, electron beam, high frequency heating such as using microwaves, ion beam, and similar methods.
  • CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.
  • the surface treatment agent of the present disclosure may be diluted with a solvent and then applied to the substrate surface.
  • the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C 6 F 13 CH 2 CH 3 (e.g., Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorora (registered trademark) H manufactured by Zeon Corporation); hydrofluoro
  • alkyl perfluoroalkyl ethers perfluoroalkyl groups and alkyl groups may be linear or branched), or CF 3 CH 2 OCF 2 CHF 2 (e.g., Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.).
  • solvents can be used alone or as a mixture of two or more kinds.
  • hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) and/or perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) are particularly preferred.
  • the surface treatment agent of the present disclosure may be subjected to the dry coating method as is, or may be diluted with the above-mentioned solvent and then subjected to the dry coating method.
  • the layer of the surface treatment agent is preferably formed so that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation.
  • the surface treatment agent of the present disclosure may be diluted with a solvent, and then a catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure immediately before application to the substrate surface.
  • the surface treatment agent of the present disclosure to which a catalyst has been added may be directly subjected to deposition (usually vacuum deposition) treatment, or a pellet-shaped material in which the surface treatment agent of the present disclosure to which a catalyst has been added is impregnated onto a metal porous body such as iron or copper may be used to perform deposition (usually vacuum deposition) treatment.
  • Any suitable acid or base can be used as the catalyst.
  • acid catalysts that can be used include acetic acid, formic acid, and trifluoroacetic acid.
  • base catalysts that can be used include ammonia and organic amines.
  • the surface treatment layer included in the article of the present disclosure has both high abrasion resistance and low wear resistance.
  • the surface treatment layer may also have water repellency, oil repellency, stain resistance (preventing adhesion of stains such as fingerprints), waterproofing (preventing water from penetrating into electronic components, etc.), surface slipperiness (or lubricity, e.g. ease of wiping off stains such as fingerprints and excellent tactile feel against the fingers), chemical resistance, etc., and may be suitably used as a functional thin film.
  • the present disclosure also relates to an optical material having the above-mentioned surface treatment layer as the outermost layer.
  • optical materials in addition to optical materials related to displays such as those exemplified below, a wide variety of optical materials are preferably used: for example, displays such as cathode ray tubes (CRTs; e.g., personal computer monitors), liquid crystal displays, plasma displays, organic electroluminescent displays, inorganic thin-film electroluminescent dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs; Field Emission Displays), or protective plates for such displays, or displays with anti-reflection coating applied to their surfaces.
  • CTRs cathode ray tubes
  • LCDs organic electroluminescent displays
  • inorganic thin-film electroluminescent dot matrix displays rear projection displays
  • fluorescent display tubes (VFDs) fluorescent display tubes
  • FEDs Field Emission Displays
  • protective plates for such displays, or displays with anti-reflection coating applied to their surfaces.
  • the article of the present disclosure may be, but is not limited to, an optical component.
  • optical components include the following: lenses for glasses and the like; front protection plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; the display surfaces of watches, etc.
  • the article of the present disclosure may also be a medical device or medical material.
  • the thickness of the layer is not particularly limited. In the case of optical components, the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and preferably 1 to 15 nm, from the viewpoints of optical performance, abrasion resistance, and antifouling properties.
  • perfluoropolyether group-containing silane compound (A4) having trimethylsilyl groups at the terminal.
  • Perfluoropolyether group-containing silane compound (A4) CF 3 CF 2 CF 2 O(CF 2 CF 2 CF 2 O) 20 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 Si[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 3
  • Examples 1 to 6 are examples of the present disclosure, and it was confirmed that the films obtained from these compositions had good abrasion resistance.
  • Comparative Example 1 is an example that does not contain the compound (B). Although the initial water contact angle was good, the abrasion resistance was inferior to those of Examples 1-6.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Silicon Polymers (AREA)

Abstract

Le but de la présente divulgation est de fournir un agent de traitement de surface capable de produire un film ayant une bonne résistance à l'abrasion.　Une composition selon la présente divulgation comprend : un composé silane (A) comportant un groupe fluoropolyéther ; et un composé (B) comportant un groupe fluoropolyéther et un groupe éther allylique, le composé (B) comprenant au moins un composé représenté par la formule (3), (4) ou (5) (à condition que le composé (A) soit différent du composé (B)). RF1 α-XA-[ARB1 δRB2 3-δ]β (3), [RB1 δRB2 3-δA]γ-XA-RF2-XA-[ARB1 δRB2 3-δ]γ (4), RSi γ-XA-RF2-XA-[ARB1 δRB2 3-δ]γ (5) [dans la formule, les A représentent chacun indépendamment un atome de C ou un atome de Si ; les R F1 représentent chacun indépendamment Rf1-RF-Oq- ; RF2 représente -Rf2 p-RF-Oq- ; les Rf1 représentent chacun indépendamment un groupe alkyle en C1-16 qui peut être substitué par au moins un atome de fluor ; Rf 2 est un groupe alkylène en C1-6 qui peut être substitué par au moins un atome de fluor ; les RF représentent chacun indépendamment un groupe fluoropolyéther divalent ; p est 0 ou 1 ; les q représentent chacun indépendamment 0 ou 1; RB1 est -RB3-O-CH= CH-CH3 ; les RB2 représentent chacun indépendamment au moins un élément choisi parmi -R B3-O-CH2CH2CH2-SiRB4 εRB5 3-ε et un atome d'hydrogène ; les RB3 représentent chacun indépendamment une liaison simple ou un groupe alkylène en C1-20 ; les RB4 représentent chacun indépendamment un groupe hydroxyle ou un groupe hydrolysable ; les RB5 représentent chacun indépendamment un atome d'hydrogène ou un groupe organique monovalent ; et les RSi représentent chacun indépendamment un groupe monovalent contenant un atome de Si ayant un groupe hydroxyle, un groupe hydrolysable, un atome d'hydrogène ou un groupe organique monovalent lié à celui-ci ; au moins un RSi dans la formule (5) est un groupe monovalent contenant un atome de Si ayant un groupe hydroxyle ou un groupe hydrolysable lié à celui-c i; les Xa représentent chacun indépendamment une liaison simple ou un groupe organique divalent à décavalent ; α est un nombre entier de 1 à 9 ; β est un nombre entier de 1 à 9 ; les γ représentent chacun indépendamment un nombre entier de 1 à 9 ; et les δ représentent chacun indépendamment un nombre entier de 1 à 3. Les ε représentent chacun indépendamment un nombre entier de 1 à 3.]
PCT/JP2024/032570 2023-09-27 2024-09-11 Agent de traitement de surface Pending WO2025070069A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54117414A (en) * 1978-03-02 1979-09-12 Central Glass Co Ltd New vinyl ethers containing fluorine and their synthesis
WO2009008380A1 (fr) * 2007-07-06 2009-01-15 Asahi Glass Company, Limited Agent de traitement de surface, article et nouveau composé éther contenant du fluor
WO2013042732A1 (fr) * 2011-09-21 2013-03-28 旭硝子株式会社 Composé d'éther contenant du fluor, fluide de revêtement, et procédé pour fabriquer un substrat ayant une couche traitée en surface
JP2022155508A (ja) * 2021-03-30 2022-10-13 ダイキン工業株式会社 フルオロポリエーテル基含有シラン化合物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54117414A (en) * 1978-03-02 1979-09-12 Central Glass Co Ltd New vinyl ethers containing fluorine and their synthesis
WO2009008380A1 (fr) * 2007-07-06 2009-01-15 Asahi Glass Company, Limited Agent de traitement de surface, article et nouveau composé éther contenant du fluor
WO2013042732A1 (fr) * 2011-09-21 2013-03-28 旭硝子株式会社 Composé d'éther contenant du fluor, fluide de revêtement, et procédé pour fabriquer un substrat ayant une couche traitée en surface
JP2022155508A (ja) * 2021-03-30 2022-10-13 ダイキン工業株式会社 フルオロポリエーテル基含有シラン化合物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SANGERMANO MARCO, BONGIOVANNI ROBERTA, MALUCELLI GIULIO, PRIOLA ALDO, THOMAS RICHARD R, KAUSCH CHARLES M, KIM YONGSIN: "Synthesis and cationic photopolymerization of new fluorinated, polyfunctional propenyl ether oligomers", JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY, JOHN WILEY & SONS, INC., US, vol. 44, no. 24, 1 December 2006 (2006-12-01), US , pages 6943 - 6951, XP093298268, ISSN: 0887-624X, DOI: 10.1002/pola.21807 *

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