WO2018123978A1 - Surface treatment agent - Google Patents

Surface treatment agent Download PDF

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Publication number
WO2018123978A1
WO2018123978A1 PCT/JP2017/046444 JP2017046444W WO2018123978A1 WO 2018123978 A1 WO2018123978 A1 WO 2018123978A1 JP 2017046444 W JP2017046444 W JP 2017046444W WO 2018123978 A1 WO2018123978 A1 WO 2018123978A1
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WIPO (PCT)
Prior art keywords
unit
carbon atoms
group
copolymer
formula
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PCT/JP2017/046444
Other languages
French (fr)
Japanese (ja)
Inventor
龍二郎 山崎
歩 鈴木
知弘 高橋
好彦 坂根
Original Assignee
旭硝子株式会社
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Publication of WO2018123978A1 publication Critical patent/WO2018123978A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • 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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to a surface treatment agent.
  • water repellency is imparted to the surfaces of various equipment and instruments.
  • a method for imparting water repellency generally, a method of decreasing the surface energy of the surface of an article to be imparted with water repellency and increasing the water contact angle is applied.
  • a method for reducing the surface energy of the surface of an article for example, a method of forming a film on the surface using a water repellent such as a fluorine-containing compound or a silicone compound is known.
  • Patent Document 1 a polymer having a polyfluoroalkyl group and an organopolysiloxane chain is known (Patent Document 1).
  • Patent Document 1 when the polymer described in Patent Document 1 was confirmed for mud drop-off property and ice / frost adhesion prevention property, it was inadequate.
  • An object of the present invention is to provide a material capable of forming a film excellent in mud removal and ice / frost adhesion prevention.
  • the present invention provides a surface treating agent and an article having the following configurations [1] to [13].
  • the following unit (a), the following unit (c), and optionally the following unit (b) are included, and the ratio of the unit (a) to the total of the unit (a) and the unit (b) is 30 to 100 mass.
  • the total proportion of units (a) and units (b) with respect to all units in the copolymer is 60 to 90% by mass, and all units in the copolymer
  • a surface treatment agent comprising a copolymer having a ratio of the unit (c) to 10 to 40% by mass.
  • Unit (a) a unit derived from a monomer represented by the following formula (a).
  • C (X 1 ) 2 CX 1 —COO—R 1 —R F1 (a)
  • three X 1 s are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom
  • R 1 is an alkylene group having 1 to 6 carbon atoms
  • F1 is a perfluoroalkyl group having 1 to 3 carbon atoms.
  • C (X 2 ) 2 CX 2 —COO—R 2 —R F2 (b)
  • three X 2 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom
  • R 2 is an alkylene group having 1 to 6 carbon atoms
  • F2 is a C 4-6 perfluoroalkyl group.
  • C (X 3 ) 2 CX 3 —COO—R 3 (c)
  • three X 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 3 is a group having an organopolysiloxane chain.
  • the copolymer further includes at least one monomer unit other than the unit (a), the unit (b), and the unit (c), and the total proportion of the monomer units is a copolymer.
  • the surface treating agent according to [6], wherein at least a part of the monomer units other than the unit (a), the unit (b) and the unit (c) is the following unit (d).
  • three X 4 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom
  • three X 5 are each independently a hydrogen atom, having 1 to 3 carbon atoms.
  • 3 is an alkyl group, a chlorine atom or a fluorine atom
  • R 9 is an alkylene group having 1 to 6 carbon atoms.
  • Unit (e) A unit derived from a monomer represented by the following formula (e).
  • C (X 6 ) 2 CX 6 -R 10 -COOH (e)
  • three X 6 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 10 is a single bond or an alkyl group having 1 to 10 carbon atoms. is there.
  • D) [In the formula (d), three X 4 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and three X 5 are each independently a hydrogen atom, having 1 to 3 carbon atoms.
  • Unit (e) A unit derived from a monomer represented by the following formula (e).
  • C (X 6 ) 2 CX 6 -R 10 -COOH (e)
  • three X 6 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom
  • R 10 is a single bond or an alkyl group having 1 to 10 carbon atoms. is there.
  • the surface treatment agent according to any one of [1] to [9], further comprising a solvent.
  • the surface treatment agent forms a film of the copolymer on the surface to be treated of the base material, thereby suppressing the adhesion of the aqueous substance to the surface of the base material as compared with the untreated surface.
  • An article comprising a copolymer film formed from the surface treating agent according to any one of [1] to [11] on a substrate surface.
  • the film has a characteristic that ice and frost do not easily adhere to the surface of the film, a characteristic that aqueous mud adhering to the surface of the film easily falls off, or both of the two characteristics.
  • the surface treatment agent of the present invention it is possible to form a film having excellent surface characteristics such as mud dropping and ice / frost adhesion prevention.
  • the monomer represented by the formula (a) is also referred to as “monomer (a)”.
  • a unit derived from a monomer is also referred to as a “monomer unit”.
  • a unit derived from the monomer (a) is also referred to as a unit (a).
  • the “aqueous substance” refers to water (aqueous mud or the like) in which insoluble matter such as soil or dust is suspended, or liquid or solid water (water droplets, ice, frost or the like).
  • the “drop-off property” of the attached aqueous substance means a property that the aqueous substance attached to the surface is easily separated from the surface, and the smaller the water falling angle described later, the higher the drop-off property.
  • the surface treatment agent of the present invention forms a copolymer film on the treated surface by treating the substrate surface, and imparts a film surface property different from the original substrate surface property to the substrate surface.
  • the treatment with the surface treatment agent of the present invention imparts the property that the aqueous substance is difficult to adhere to the surface of the substrate to be treated (water repellency) and the property that the attached aqueous substance tends to fall off (sliding property). .
  • the property that the attached mud easily falls off (hereinafter also referred to as “mud removal”), the property that ice and frost do not easily adhere (hereinafter also referred to as “ice / frost adhesion prevention”), and these A property having both characteristics is imparted to the surface to be processed.
  • the “surface characteristics” of the surface to be treated refers to the properties of the surface of the copolymer film that are different from the original substrate surface imparted by the treatment with the surface treatment agent.
  • the surface treatment agent of the present invention includes the following unit (a), the following unit (c), and optionally the following unit (b).
  • this agent includes the following unit (a), the following unit (c), and optionally the following unit (b).
  • a copolymer having a ratio of unit (c) to 10 to 40% by mass with respect to all units in the copolymer examples include a copolymer (hereinafter referred to as “copolymer (1)”) in which the ratio of the unit (a) to the total of the units (a) and (b) is 30 to 70% by mass. Are preferred).
  • copolymer (2) A copolymer containing no unit (b) (hereinafter also referred to as “copolymer (2)”) is preferred.
  • copolymer (1) and the copolymer (2) may be collectively referred to as “the present copolymer”.
  • the copolymer may further contain units (d) and units (e) described later.
  • the polymerization form of the copolymer is not particularly limited, and each unit may be random, block, or alternating, but is preferably random.
  • the production method of the copolymer is not particularly limited, and various known methods can be applied.
  • the number average molecular weight (Mn) of the copolymer is preferably 1 ⁇ 10 3 to 1 ⁇ 10 7 , and particularly preferably 1 ⁇ 10 4 to 1 ⁇ 10 6 . It is excellent in film forming property as it is more than the lower limit of the said range, and has mud fall-off property and ice / frost adhesion prevention property. It is preferable that it is not more than the upper limit of the above range in that the copolymer is excellent in solubility in a solvent and the agent can be easily applied to a substrate.
  • This agent may contain a solvent as necessary. The solvent is removed during the surface treatment to form a film of the copolymer.
  • This agent may further contain components other than those described above as needed, as long as the stability of the composition, the surface characteristics of the formed film, the appearance, and the like are not impaired.
  • the unit (a) is a unit derived from a monomer represented by the following formula (a).
  • C (X 1 ) 2 CX 1 —COO—R 1 —R F1 (a)
  • three X 1 s are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom
  • R 1 is an alkylene group having 1 to 6 carbon atoms
  • F1 is a perfluoroalkyl group having 1 to 3 carbon atoms.
  • X 1 is preferably a hydrogen atom or a methyl group from the viewpoint that a monomer is easily available.
  • R 1 has 2 or more carbon atoms, the alkylene group may have a linear structure or a branched structure, but a linear structure is preferred from the viewpoint of excellent surface characteristics of the copolymer.
  • the number of carbon atoms of R 1 is preferably 1 to 3 and particularly preferably 1 to 2 in view of easy availability of the monomer.
  • the perfluoroalkyl group may have a linear structure or a branched structure, but a linear structure is preferred from the viewpoint of excellent surface characteristics of the copolymer.
  • the number of carbon atoms in R F1 is particularly preferably 1 because the falling angle can be further reduced.
  • the monomer (a) are the following compounds. CH 2 ⁇ CH—COO—CH 2 —CF 3 CH 2 ⁇ C (CH 3 ) —COO—CH 2 —CF 3 CH 2 ⁇ CH—COO—CH 2 —CF 2 CF 3 CH 2 ⁇ C (CH 3 ) —COO—CH 2 —CF 2 CF 3
  • the unit (b) is a unit derived from a monomer represented by the following formula (b).
  • C (X 2 ) 2 CX 2 —COO—R 2 —R F2 (b)
  • three X 2 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom
  • R 2 is an alkylene group having 1 to 6 carbon atoms
  • F2 is a C 4-6 perfluoroalkyl group.
  • the surface of the film of the copolymer is excellent in water repellency.
  • X 2 has the same examples and preferred ranges as X 1
  • C (X 2 ) 2 ⁇ CX 2 — represents CH 2 ⁇ CH— or CH 2 ⁇ C (CH 3 ) —. It is particularly preferred.
  • R 2 is the same as R 1 in both illustration and preferred range.
  • the perfluoroalkyl group of R F2 may have a linear structure or a branched structure, but a linear structure is preferable from the viewpoint that the copolymer (1) is excellent in water repellency.
  • the number of carbon atoms of R F2 is particularly preferably 6 because the copolymer (1) is more excellent in water repellency.
  • CH 2 CH-COO- (CH 2 ) 2- (CF 2 ) 3 CF 3 CH 2 ⁇ C (CH 3 ) —COO— (CH 2 ) 2 — (CF 2 ) 3 CF 3 CH 2 ⁇ CH—COO— (CH 2 ) 2 — (CF 2 ) 5 CF 3 CH 2 ⁇ C (CH 3 ) —COO— (CH 2 ) 2 — (CF 2 ) 5 CF 3
  • the unit (c) is a unit derived from a monomer represented by the following formula (c).
  • C (X 3 ) 2 CX 3 —COO—R 3 (c)
  • three X 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 3 is a group having an organopolysiloxane chain.
  • X 3 has the same examples and preferred ranges as X 1 and C (X 3 ) 2 ⁇ CX 3 — represents CH 2 ⁇ CH— or CH 2 ⁇ C (CH 3 ) —. It is particularly preferred.
  • the organopolysiloxane chain is a group having a plurality of repeating units represented by — (Si (R) 2 O) — (R is an alkyl group. Two Rs may be the same), and — (Si (CH 3 ) A polydimethylsiloxane chain having a plurality of repeating units represented by 2 O)-is preferred.
  • the bond at the oxygen atom side end of R 3 is a bond of a carbon atom and has a linking group with the silicon atom at the end of the organopolysiloxane chain.
  • the bond at the silicon atom side terminal of this linking group is also a bond of a carbon atom. Therefore, this linking group consists of a divalent organic group whose both bond ends are carbon atoms.
  • R 3 has a monovalent organic group bonded to the silicon atom at the end of the organopolysiloxane chain on the free end side, and the bond at the silicon atom side end of this monovalent organic group is also bonded to a carbon atom. It is a hand. Therefore, this monovalent organic group is a monovalent organic group whose bond end is a carbon atom.
  • Examples of the divalent organic group and monovalent organic group in R 3 include hydrocarbon groups such as an alkylene group and an alkyl group. It may be a cyclic hydrocarbon group such as a cycloalkylene group, an arylene group, a cycloalkyl group, a cyclic hydrocarbon group such as an aryl group, or a cyclic hydrocarbon group between carbon atoms of an alkylene group or an alkyl group or at the end of an alkyl group. It may be a hydrocarbon group having The above divalent organic group and monovalent organic group may have a functional group. Examples of the functional group include a hydroxyl group, an epoxy group, a carboxy group, an amino group, and an amide group.
  • a group having a polymerizable carbon-carbon double bond is not preferred as the functional group.
  • a functional group having an oxygen atom or a nitrogen atom is preferable, and a functional group having an oxygen atom such as a hydroxyl group, an epoxy group, or a carboxy group is preferable.
  • Said divalent organic group and monovalent organic group may have a hetero atom in parts other than a functional group.
  • the hetero atom include a fluorine atom, a chlorine atom, an oxygen atom, and a nitrogen atom.
  • the heteroatom may be a heteroatom constituting a heterocyclic ring.
  • the hetero atom is preferably an oxygen atom
  • examples of the organic group having an oxygen atom include organic groups having an alkoxy group, an acyloxy group, an acyl group, and the like. Further, it may be an organic group having an etheric oxygen atom such as a polyoxyalkylene chain in the main chain.
  • the monomer (c) is more preferably a monomer represented by the following formula (c1).
  • C (X 3 ) 2 CX 3 —COO—R 4 — (Si (R 5 ) 2 O) m —Si (R 6 ) 2 —R 7 (c1)
  • X 3 is as described above, R 4 is an alkylene group having 1 to 6 carbon atoms, and two R 5 are each independently an alkyl group having 1 to 3 carbon atoms, Each R 6 is independently an alkyl group having 1 to 3 carbon atoms, R 7 is a monovalent organic group which may have a functional group, and m is an integer of 10 to 800.
  • m is an integer of 10 to 800.
  • the alkylene group when R 4 has 2 or more carbon atoms, the alkylene group may have a linear structure or a branched structure, but a linear structure is preferred.
  • the number of carbon atoms of R 4 is particularly preferably 1 to 3 from the viewpoint of easy availability of monomers.
  • R 5 and R 6 have 3 carbon atoms, the alkyl group may have a linear structure or a branched structure, but a linear structure is preferred.
  • R 5 and R 6 are particularly preferably both methyl groups from the viewpoint of easy availability.
  • m is more preferably an integer of 50 to 600, particularly preferably an integer of 100 to 400.
  • R 7 is preferably a hydrocarbon group or a hydrocarbon group having an etheric oxygen atom, an acyloxy group, an acyl group or the like between carbon atoms.
  • the functional group that R 7 may have include a hydroxyl group, a carboxy group, an epoxy group, a primary amino group, a secondary amino group, and the like. From the viewpoint of easy production and reactivity, an epoxy group. A group having a (for example, glycidyloxy group) is preferred.
  • R 7 is preferably an aliphatic hydrocarbon group having a functional group and optionally having an etheric oxygen atom or an acyloxy group between carbon atoms, particularly having an epoxy group and an etheric carbon atom. An aliphatic hydrocarbon group which may be contained is preferable.
  • the unit (d) is a monomer-derived unit represented by the following formula (d).
  • three X 4 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and each X 5 is independently a hydrogen atom, having 1 to 3 carbon atoms.
  • An alkyl group, a chlorine atom or a fluorine atom, and R 9 is an alkylene group having 1 to 6 carbon atoms; ]
  • X 4 has the same examples and preferred ranges as X 1
  • C (X 4 ) 2 ⁇ CX 4 — represents CH 2 ⁇ CH— or CH 2 ⁇ C (CH 3 ) —. It is particularly preferred.
  • X 5 has the same exemplified and preferred range as X 1, and it is particularly preferable that —CX 5 ⁇ C (X 5 ) 2 is —CH ⁇ CH 2 or —C (CH 3 ) ⁇ CH 2 .
  • R 9 has 2 or more carbon atoms
  • the alkylene group may have a linear structure or a branched structure, but a linear structure is preferred.
  • the number of carbon atoms of R 9 is particularly preferably 1 to 3 from the viewpoint of easy availability of monomers.
  • the unit (e) is a unit derived from a monomer represented by the following formula (e).
  • C (X 6 ) 2 CX 6 -R 10 -COOH (e)
  • three X 6 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 10 is a single bond or an alkylene group having 1 to 10 carbon atoms. is there. ]
  • the present copolymer has excellent adhesion of the copolymer film to the substrate.
  • X 6 has the same examples and preferred ranges as X 1
  • C (X 6 ) 2 ⁇ CX 6 — represents CH 2 ⁇ CH— or CH 2 ⁇ C (CH 3 ) —. It is particularly preferred.
  • R 10 has 2 or more carbon atoms, the alkylene group may have a linear structure or a branched structure, but a linear structure is preferred.
  • R 10 is particularly preferably a single bond from the viewpoint that a monomer is easily available.
  • the total ratio of the unit (a) and the unit (b) to the whole unit is 60 to 90% by mass, preferably 65 to 85% by mass, particularly preferably 70 to 80% by mass.
  • the ratio of the unit (a) to the total of the units (a) and (b) is 30 to 70% by mass, preferably 40 to 60% by mass, and 45 to 55% by mass. Particularly preferred.
  • the content of the unit (a) with respect to all units is from 60 to 90% by mass, preferably from 65 to 85% by mass, particularly preferably from 70 to 80% by mass.
  • the ratio of the unit (c) to the total units is 10 to 40% by mass, and 10 to 30% by mass is particularly preferable.
  • the total ratio of the unit (d) and the unit (e) to the whole unit is preferably from 0.1 to 5% by mass, particularly preferably from 0.1 to 3% by mass.
  • the ratio of the unit (d) to all units is preferably from 0.1 to 5% by mass, particularly preferably from 0.1 to 3% by mass.
  • the ratio of the unit (e) to the whole unit is preferably from 0.1 to 5% by mass, particularly preferably from 0.1 to 3% by mass.
  • a preferred embodiment of the present copolymer (1) is that the total ratio of the unit (a) and the unit (b) to the whole unit is 60 to 90% by mass, and the unit is based on the total of the unit (a) and the unit (b).
  • the ratio of (a) is 40 to 60% by mass
  • the ratio of unit (c) to all units is 10 to 40% by mass
  • the total ratio of units (d) and units (e) to all units is 0.1 5% by mass
  • the ratio of the unit (d) to the whole unit is 0.1 to 5% by mass
  • the ratio of the unit (e) to the whole unit is 0.1 to 5% by mass.
  • the ratio of the total of the unit (a) and the unit (b) to 70 to 80% by mass, the ratio of the unit (a) to the total of the unit (a) and the unit (b) is 45 to 55% by mass, the total unit
  • the ratio of unit (c) to 10 to 30% by mass of the total of unit (d) and unit (e) with respect to all units If the 0.1 to 3 wt%, the proportion of 0.1 to 3% by weight of units (d) to all the units, the proportion of the unit (e) to all the units is 0.1 to 3 wt%.
  • a preferred embodiment of the present copolymer (2) is that the ratio of the unit (a) to the total unit is 60 to 90% by mass, the ratio of the unit (c) to the total unit is 10 to 40% by mass, the unit (d ) And unit (e) are 0.1 to 5% by mass, the unit (d) is 0.1 to 5% by mass with respect to all units, and the unit (e) is 0% with respect to all units. 1 to 5% by mass, and the most preferable embodiment is that the ratio of the unit (a) to the total unit is 70 to 80% by mass, the ratio of the unit (c) to the total unit is 10 to 30% by mass, and the unit to the total unit.
  • the total ratio of (d) and unit (e) is 0.1 to 3% by mass, the ratio of unit (d) to all units is 0.1 to 3% by mass, and the ratio of unit (e) to all units Is 0.1 to 3% by mass.
  • the concentration of the copolymer in the agent is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, and particularly preferably 1 to 5% by mass.
  • the agent contains a solvent and an optional component other than the solvent
  • the solid content concentration of the agent is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass.
  • the copolymer concentration or solid content concentration is in the range of 0.1 to 20% by mass, the film is sufficiently thick and has excellent film forming properties. It is easy to form a film with excellent film slidability.
  • the agent contains a solvent
  • the content of the solvent in the agent is preferably 80 to 99.9% by mass, more preferably 90 to 99% by mass, and particularly preferably 95 to 98% by mass.
  • the solvent is not particularly limited as long as the copolymer can be dissolved, and can be appropriately selected from various known solvents.
  • a fluorine-containing solvent having a fluorine atom content of less than 60% by mass is preferable, and a fluorine-containing solvent having a content of less than 55% by mass is particularly preferable.
  • examples thereof include m-xylene hexafluoride (hereinafter also referred to as “m-XHF”), p-xylene hexafluoride, and the like.
  • the fluorine atom content (hereinafter also referred to as “F content”) is determined by the following formula (I).
  • (F content) ((number of fluorine atoms in the molecule) ⁇ 19) / (molecular weight) ⁇ 100 (I)
  • the article of the present invention has a film formed from this agent on the surface of the substrate.
  • the thickness of the film is preferably from 100 to 1,000 nm, particularly preferably from 120 to 400 nm. If the thickness of the film is within the above range, sufficient water repellency and water slidability are likely to be exhibited, and if it is 120 nm or more, good mud removal and ice / frost adhesion prevention properties are likely to be exhibited.
  • the thickness of the membrane is It is calculated
  • the base material in the present invention is not particularly limited as long as it is required to impart water repellency and water slidability, and in particular, provision of mud detachability and ice / frost adhesion prevention.
  • Examples of the base material include metals, resins, glass, sapphire, ceramics, stones, wood, fibers, and composite materials of two or more of these.
  • the article of the present invention can be produced, for example, by a method in which the present agent containing a solvent is applied to the surface of a substrate and dried to form a film.
  • a coating method of this agent a known wet coating method can be used, for example, dip coating method, spin coating method, wipe coating method, spray coating method, squeegee coating method, die coating method, inkjet method, flow coating method, roll coating. Method, casting method, Langmuir-Blodgett method, gravure coating method and the like.
  • a drying method a method of heating at a temperature equal to or higher than the boiling point of the solvent is preferable. However, when heat drying is difficult due to the material of the substrate, etc., heating should be avoided to dry. What is necessary is just to select a heating condition according to a composition, the application area, etc. of this agent.
  • membrane which the article of this invention has on the surface of a base material is a film
  • the number average molecular weight of a polymer is a polymethyl methacrylate (PMMA) conversion molecular weight by a gel permeation chromatography (GPC) method.
  • the composition to be described later is applied on a copper substrate by spin coating (1,000 rpm, 30 seconds) and dried in an oven adjusted to a temperature of 100 ° C. for 10 minutes to form a film having a thickness of 150 ⁇ m. A copper substrate with a film was obtained. Subsequently, JIS test powders 1-8 (powdered Kanto loam powder) and water were mixed at a mass ratio of 1: 0.66 to prepare saturated mud water. The copper substrate with a film was placed horizontally (0 degree) on a table whose angle can be adjusted, and 100 ⁇ L of saturated mud was dropped using a micropipette.
  • the angle of the platform was increased by 5 degrees until the saturated mud on the copper substrate with film started to flow.
  • the tilt angle of the film-coated copper substrate with respect to the horizontal plane when the saturated mud water droplets started to roll was measured using a contact angle meter (DM-500, manufactured by Kyowa Interface Science Co., Ltd.), and the muddy water fall angle was obtained. The smaller this value, the higher the mud shedding.
  • the number of seconds from when the saturated mud droplets start flowing to when they fall from the substrate is measured with a stopwatch. ) was also calculated. The results are shown in Table 1.
  • X 3 is all hydrogen atoms
  • R 4 is a trimethylene group
  • R 5 , R 6 Are all methyl groups
  • R 7 is an organic group having an epoxy group
  • the average value of m is 156)
  • Example 1 Each monomer was charged in a 1 L polymerization tank so that the ratio (mass%) in Table 1 was 100 g in total. Next, 1 g of an initiator (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) and 399 g of m-XHF used as a polymerization solvent were charged. Reaction was performed at 70 ° C. for 24 hours to obtain a solution containing the copolymer (A). In addition, content (mass%) of each unit in a copolymer (A) is the value considered that all the monomers used for superposition
  • the content (mass%) of each unit of the copolymer (A) is the same as the content of each monomer described in Table 1.
  • the obtained solution was further diluted with m-XHF to obtain a composition (A) having a copolymer (A) concentration of 2% by mass.
  • the composition (A) is applied onto a glass substrate by spin coating (1,000 revolutions per minute, 30 seconds) and dried in an oven adjusted to a temperature of 100 ° C. for 10 minutes to form a film having a thickness of 150 nm.
  • Table 1 shows the results of the water contact angle and water falling angle, mud drop-off property evaluation test and ice / frost adhesion prevention test result of the copolymer (A).
  • Example 2 A copolymer, a composition and a glass substrate with a film were obtained in the same manner as in Example 1, and each evaluation was performed. The results are shown in Table 1.
  • Example 1 corresponding to the copolymer (1) of the present invention and the copolymer of Example 2 corresponding to the copolymer (2) of the present invention were found to have a water contact angle. It was also found that the water falling angle is low, the mud dropping property is excellent, and the ice / frost adhesion preventing property is also excellent.
  • the water falling angle of Example 1 is considerably lower than that of Example 2. This is because the perfluoroalkyl group having 6 carbon atoms in the unit (b-1) has higher crystallinity than the perfluoroalkyl group having 1 carbon atom in the unit (a-1), and the mobility becomes low. This is thought to be due to the difficulty in moving the water droplets.
  • Examples 1, 3 and 5 were compared in which the same proportion of the total of units (a-1) and units (b-1) with respect to all units was 78% by mass. Only in Example 1 where the ratio of the unit (a-1) to the total of the unit (a-1) and the unit (b-1) is 30 to 70% by mass, the water contact angle and the water falling angle are low, and the mud shedding property It was confirmed that it was excellent in ice and frost adhesion prevention. This is because the perfluoroalkyl group having 1 carbon atom in the unit (a-1) arranged between the perfluoroalkyl groups having 6 carbon atoms in the unit (b-1) serves as a spacer.
  • the crystallinity of the perfluoroalkyl group is reduced, and as a result, the mobility of the C 6 perfluoroalkyl group on the surface of the film is increased (A. Hozumi, C. Urata, Synthesis 2014, 7 190-198).
  • the surface treating agent of the present invention can be used for various applications where mud dropping properties and ice / frost adhesion preventing properties are required or required. Focusing on mud shedding, it can be used as a surface treatment agent that imparts mud shedding to automobiles, bicycles, motorcycles, carpets, leather shoes, and exterior materials. Focusing on the prevention of ice and frost adhesion, fins and filters of air conditioners such as air conditioners, freezers and refrigerators, general equipment used outdoors, outdoor units and greenhouses to prevent icing and snow accretion It can be used as a surface treatment agent.
  • air conditioners such as air conditioners, freezers and refrigerators, general equipment used outdoors, outdoor units and greenhouses to prevent icing and snow accretion

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Abstract

Provided is a material capable of forming a film having excellent dirt pickup resistance and ice/frost adhesion prevention properties. This surface treatment agent is characterized by containing a copolymer which includes: a unit (a) having a C1-3 perfluoroalkyl group; a unit (c) having a group having an organopolysiloxane chain; and optionally, a unit (b) having a C4-6 perfluoroalkyl group, wherein the proportion of the unit (a) with respect to the total mass of the unit (a) and the unit (b) is 30-100 mass%, the combined proportion of the unit (a) and the unit (b) with respect to all of the units in the copolymer is 60-90 mass%, and the proportion of the unit (c) with respect to all of the units in the copolymer is 10-40 mass%.

Description

表面処理剤Surface treatment agent
　本発明は、表面処理剤に関する。 The present invention relates to a surface treatment agent.
　従来、種々の設備や器具の表面に撥水性を付与することが行われている。撥水性の付与方法としては一般的に、撥水性を付与しようとする物品の表面の表面エネルギーを下げ、水接触角を大きくする方法が適用されている。物品の表面の表面エネルギーを下げる方法としては、たとえば含フッ素化合物、シリコーン化合物等の撥水剤を用いて表面に膜を形成する方法が知られている。 Conventionally, water repellency is imparted to the surfaces of various equipment and instruments. As a method for imparting water repellency, generally, a method of decreasing the surface energy of the surface of an article to be imparted with water repellency and increasing the water contact angle is applied. As a method for reducing the surface energy of the surface of an article, for example, a method of forming a film on the surface using a water repellent such as a fluorine-containing compound or a silicone compound is known.
　近年、自動車関連備品や台所設備等にあっては撥水性に加えて泥脱落性（水性の泥が脱落しやすい性質）や氷・霜付着防止性（氷および霜が付着し難い性質）も求められるようになってきている。これは、表面に泥や氷・霜が留まり続けると汚れやカビの原因となるためである。
　単純に表面エネルギーを下げて水接触角を大きくするだけでは充分な泥脱落性や氷・霜付着防止性は付与できず、逆に泥脱落性や氷・霜付着防止性が低下することがある。
　滑水性に優れた膜を形成可能な材料としては、ポリフルオロアルキル基とオルガノポリシロキサン鎖とを有する重合体が知られている（特許文献１）。 In recent years, in addition to water repellency, automobile-related equipment and kitchen equipment also require mud shedding (water mud is easily removed) and ice / frost adhesion prevention (property for ice and frost to adhere). It is getting to be. This is because if mud, ice, or frost stays on the surface, it causes dirt and mold.
Simply lowering the surface energy and increasing the water contact angle cannot provide sufficient mud shedding and ice / frost adhesion prevention, but conversely, mud shedding and ice / frost adhesion prevention may be reduced. .
As a material capable of forming a film having excellent water slidability, a polymer having a polyfluoroalkyl group and an organopolysiloxane chain is known (Patent Document 1).
特開２０１３－１８５０７２号公報JP 2013-185072 A
　しかしながら、本発明者によれば、特許文献１に記載の重合体について、泥脱落性や氷・霜付着防止性を確認したところ、不充分な傾向にあった。 However, according to the present inventor, when the polymer described in Patent Document 1 was confirmed for mud drop-off property and ice / frost adhesion prevention property, it was inadequate.
　本発明の目的は、泥脱落性や氷・霜付着防止性に優れた膜を形成できる材料を提供することにある。 An object of the present invention is to provide a material capable of forming a film excellent in mud removal and ice / frost adhesion prevention.
　本発明は、以下の［１］～［１３］の構成を有する、表面処理剤および物品を提供する。
［１］　下記単位（ａ）と下記単位（ｃ）と任意に下記単位（ｂ）とを含み、単位（ａ）と単位（ｂ）との合計に対する単位（ａ）の割合が３０～１００質量％である共重合体であって、共重合体中の全単位に対する単位（ａ）と単位（ｂ）との合計の割合が６０～９０質量％であり、かつ、共重合体中の全単位に対する単位（ｃ）の割合が１０～４０質量％である共重合体を含むことを特徴とする表面処理剤。
　単位（ａ）：下記式（ａ）で表される単量体に由来する単位。
　Ｃ（Ｘ１）２＝ＣＸ１－ＣＯＯ－Ｒ１－ＲＦ１・・・（ａ）
〔式（ａ）中、３つのＸ１はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ１は炭素数１～６のアルキレン基であり、ＲＦ１は炭素数１～３のペルフルオロアルキル基である。〕
　単位（ｂ）：下記式（ｂ）で表される単量体に由来する単位。
　Ｃ（Ｘ２）２＝ＣＸ２－ＣＯＯ－Ｒ２－ＲＦ２・・・（ｂ）
〔式（ｂ）中、３つのＸ２はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ２は炭素数１～６のアルキレン基であり、ＲＦ２は炭素数４～６のペルフルオロアルキル基である。〕
　単位（ｃ）：下記式（ｃ）で表される単量体に由来する単位。
　Ｃ（Ｘ３）２＝ＣＸ３－ＣＯＯ－Ｒ３・・・（ｃ）
〔式（ｃ）中、３つのＸ３はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ３はオルガノポリシロキサン鎖を有する基である。〕
［２］　前記単位（ａ）と単位（ｂ）との合計に対する単位（ａ）の割合が３０～７０質量％である、［１］の表面処理剤。
［３］　前記共重合体が単位（ｂ）を含まない共重合体である、［１］の表面処理剤。
［４］　前記単位（ｃ）が下記式（ｃ１）で表される単量体に由来する単位である、［１］～［３］のいずれかの表面処理剤。
　Ｃ（Ｘ３）２＝ＣＸ３－ＣＯＯ－Ｒ４－（Ｓｉ（Ｒ５）２Ｏ）ｍ－Ｓｉ（Ｒ６）２－Ｒ７・・・（ｃ１）
〔式（ｃ１）中、３つのＸ３はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ４は炭素数１～６のアルキレン基であり、２つのＲ５はそれぞれ独立に炭素数１～３のアルキル基であり、２つのＲ６はそれぞれ独立に炭素数１～３のアルキル基であり、Ｒ７は官能性基を有していてもよい１価の有機基であり、ｍは１０～８００の整数である。〕
［５］　前記Ｒ７がエポキシ基を有する有機基である、［４］の表面処理剤。
［６］　前記共重合体がさらに単位（ａ）、単位（ｂ）および単位（ｃ）以外の単量体単位の少なくとも１種を含み、該単量体単位の合計の割合が、共重合体中の全単位に対して０．１～５質量％である、［１］～［５］のいずれかの表面処理剤。
［７］　前記単位（ａ）、単位（ｂ）および単位（ｃ）以外の単量体単位の少なくとも一部が、下記単位（ｄ）である、［６］の表面処理剤。
　単位（ｄ）：下記式（ｄ）で表される単量体に由来する単位。
　Ｃ（Ｘ４）２＝ＣＸ４－ＣＯＯ－Ｒ９－ＯＣＯ－ＣＸ５＝Ｃ（Ｘ５）２・・・（ｄ）
〔式（ｄ）中、３つのＸ４はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、３つのＸ５はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ９は炭素数１～６のアルキレン基である。〕
［８］　前記単位（ａ）、単位（ｂ）および単位（ｃ）以外の単量体単位の少なくとも一部が、下記単位（ｅ）である、［６］の表面処理剤。
　単位（ｅ）：下記式（ｅ）で表される単量体に由来する単位。
　Ｃ（Ｘ６）２＝ＣＸ６－Ｒ１０－ＣＯＯＨ・・・（ｅ）
〔式（ｅ）中、３つのＸ６はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ１０は単結合または炭素数１～１０のアルキル基である。〕
［９］　前記単位（ａ）、単位（ｂ）および単位（ｃ）以外の単量体単位として下記単位（ｄ）と下記単位（ｅ）とを含む、［６］の表面処理剤。
　単位（ｄ）：下記式（ｄ）で表される単量体に由来する単位。
　Ｃ（Ｘ４）２＝ＣＸ４－ＣＯＯ－Ｒ９－ＯＣＯ－ＣＸ５＝Ｃ（Ｘ５）２・・・（ｄ）
〔式（ｄ）中、３つのＸ４はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、３つのＸ５はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ９は炭素数１～６のアルキレン基である。〕
　単位（ｅ）：下記式（ｅ）で表される単量体に由来する単位。
　Ｃ（Ｘ６）２＝ＣＸ６－Ｒ１０－ＣＯＯＨ・・・（ｅ）
〔式（ｅ）中、３つのＸ６はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ１０は単結合または炭素数１～１０のアルキル基である。〕
［１０］　さらに溶媒を含む、［１］～［９］のいずれかの表面処理剤。
［１１］　前記表面処理剤が基材の被処理面に前記共重合体の膜を形成することにより、基材表面に、未処理面と比較して、水性物質の付着性を抑制しかつ付着した水性物質の脱落性を向上させる特性を付与する、表面処理剤である、［１］～［１０］のいずれかの表面処理剤。
［１２］　前記［１］～［１１］のいずれかの表面処理剤から形成された共重合体の膜を基材表面に有することを特徴とする物品。
［１３］　前記膜が、該膜の表面に氷および霜が付着し難い特性、該膜の表面に付着した水性の泥が脱落しやすい特性、または前記２つの特性の両方を有する、［１２］の物品。 The present invention provides a surface treating agent and an article having the following configurations [1] to [13].
[1] The following unit (a), the following unit (c), and optionally the following unit (b) are included, and the ratio of the unit (a) to the total of the unit (a) and the unit (b) is 30 to 100 mass. The total proportion of units (a) and units (b) with respect to all units in the copolymer is 60 to 90% by mass, and all units in the copolymer A surface treatment agent comprising a copolymer having a ratio of the unit (c) to 10 to 40% by mass.
Unit (a): a unit derived from a monomer represented by the following formula (a).
C (X 1 ) 2 = CX 1 —COO—R 1 —R F1 (a)
[In the formula (a), three X 1 s are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom; R 1 is an alkylene group having 1 to 6 carbon atoms; F1 is a perfluoroalkyl group having 1 to 3 carbon atoms. ]
Unit (b): a unit derived from a monomer represented by the following formula (b).
C (X 2 ) 2 = CX 2 —COO—R 2 —R F2 (b)
[In the formula (b), three X 2 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom; R 2 is an alkylene group having 1 to 6 carbon atoms; F2 is a C 4-6 perfluoroalkyl group. ]
Unit (c): a unit derived from a monomer represented by the following formula (c).
C (X 3 ) 2 = CX 3 —COO—R 3 (c)
[In the formula (c), three X 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 3 is a group having an organopolysiloxane chain. ]
[2] The surface treatment agent according to [1], wherein the ratio of the unit (a) to the total of the unit (a) and the unit (b) is 30 to 70% by mass.
[3] The surface treating agent according to [1], wherein the copolymer is a copolymer containing no unit (b).
[4] The surface treatment agent according to any one of [1] to [3], wherein the unit (c) is a unit derived from a monomer represented by the following formula (c1).
C (X 3 ) 2 = CX 3 —COO—R 4 — (Si (R 5 ) 2 O) m —Si (R 6 ) 2 —R 7 (c1)
[In the formula (c1), three X 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, R 4 is an alkylene group having 1 to 6 carbon atoms, Each R 5 is independently an alkyl group having 1 to 3 carbon atoms, two R 6 are each independently an alkyl group having 1 to 3 carbon atoms, and R 7 may have a functional group It is a monovalent organic group, and m is an integer of 10 to 800. ]
[5] The surface treating agent according to [4], wherein R 7 is an organic group having an epoxy group.
[6] The copolymer further includes at least one monomer unit other than the unit (a), the unit (b), and the unit (c), and the total proportion of the monomer units is a copolymer. The surface treating agent according to any one of [1] to [5], which is 0.1 to 5% by mass with respect to all units therein.
[7] The surface treating agent according to [6], wherein at least a part of the monomer units other than the unit (a), the unit (b) and the unit (c) is the following unit (d).
Unit (d): a unit derived from a monomer represented by the following formula (d).
C (X 4 ) 2 = CX 4 —COO—R 9 —OCO—CX 5 = C (X 5 ) 2 ... (D)
[In the formula (d), three X 4 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and three X 5 are each independently a hydrogen atom, having 1 to 3 carbon atoms. 3 is an alkyl group, a chlorine atom or a fluorine atom, and R 9 is an alkylene group having 1 to 6 carbon atoms. ]
[8] The surface treating agent according to [6], wherein at least a part of the monomer units other than the unit (a), the unit (b), and the unit (c) is the following unit (e).
Unit (e): A unit derived from a monomer represented by the following formula (e).
C (X 6 ) 2 = CX 6 -R 10 -COOH (e)
[In the formula (e), three X 6 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 10 is a single bond or an alkyl group having 1 to 10 carbon atoms. is there. ]
[9] The surface treatment agent according to [6], comprising the following unit (d) and the following unit (e) as monomer units other than the unit (a), the unit (b) and the unit (c).
Unit (d): a unit derived from a monomer represented by the following formula (d).
C (X 4 ) 2 = CX 4 —COO—R 9 —OCO—CX 5 = C (X 5 ) 2 ... (D)
[In the formula (d), three X 4 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and three X 5 are each independently a hydrogen atom, having 1 to 3 carbon atoms. 3 is an alkyl group, a chlorine atom or a fluorine atom, and R 9 is an alkylene group having 1 to 6 carbon atoms. ]
Unit (e): A unit derived from a monomer represented by the following formula (e).
C (X 6 ) 2 = CX 6 -R 10 -COOH (e)
[In the formula (e), three X 6 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 10 is a single bond or an alkyl group having 1 to 10 carbon atoms. is there. ]
[10] The surface treatment agent according to any one of [1] to [9], further comprising a solvent.
[11] The surface treatment agent forms a film of the copolymer on the surface to be treated of the base material, thereby suppressing the adhesion of the aqueous substance to the surface of the base material as compared with the untreated surface. The surface treatment agent according to any one of [1] to [10], which is a surface treatment agent that imparts a property of improving the detachability of the aqueous substance.
[12] An article comprising a copolymer film formed from the surface treating agent according to any one of [1] to [11] on a substrate surface.
[13] The film has a characteristic that ice and frost do not easily adhere to the surface of the film, a characteristic that aqueous mud adhering to the surface of the film easily falls off, or both of the two characteristics. [12] Goods.
　本発明の表面処理剤によれば、泥脱落性、氷・霜付着防止性等の表面特性に優れた膜を形成できる。 According to the surface treatment agent of the present invention, it is possible to form a film having excellent surface characteristics such as mud dropping and ice / frost adhesion prevention.
　本明細書においては、式（ａ）で表される単量体を「単量体（ａ）」とも記す。他の式で表される単量体についても同様に記す。
　本明細書においては、単量体由来の単位を「単量体単位」とも記す。また、単量体（ａ）由来の単位を単位（ａ）とも記す。
　本明細書において「水性物質」とは、土、ほこり等の不溶物が懸濁した水（水性の泥等）または液体状もしくは固体状の水（水滴、氷、霜等）等をいう。
　本明細書において付着した水性物質の「脱落性」とは、表面に付着した水性物質が表面から離れやすい性質を意味し、後述の水転落角が小さいほど脱落性が高い。 In this specification, the monomer represented by the formula (a) is also referred to as “monomer (a)”. The same applies to monomers represented by other formulas.
In the present specification, a unit derived from a monomer is also referred to as a “monomer unit”. A unit derived from the monomer (a) is also referred to as a unit (a).
In the present specification, the “aqueous substance” refers to water (aqueous mud or the like) in which insoluble matter such as soil or dust is suspended, or liquid or solid water (water droplets, ice, frost or the like).
In this specification, the “drop-off property” of the attached aqueous substance means a property that the aqueous substance attached to the surface is easily separated from the surface, and the smaller the water falling angle described later, the higher the drop-off property.
　本発明の表面処理剤は、基材表面を処理して被処理面に共重合体の膜を形成し、本来の基材表面の性質とは異なる膜表面の性質を基材表面に付与するために使用されるものである。具体的には、本発明の表面処理剤の処理により、基材の被処理面に水性物質が付着し難い性質（撥水性）や付着した水性物質が脱落しやすい性質（滑水性）を付与する。特に、付着した泥が脱落しやすい性質（以下、「泥脱落性」ともいう。）、氷や霜が付しにくい性質（以下、「氷・霜付着防止性」ともいう。）、またこれらの特性の両方を兼ね備える性質を被処理面に付与する。なお、以下、被処理面の「表面特性」とは、表面処理剤による処理により付与された、本来の基材表面とは異なる、共重合体の膜の表面の性質をいう。 The surface treatment agent of the present invention forms a copolymer film on the treated surface by treating the substrate surface, and imparts a film surface property different from the original substrate surface property to the substrate surface. Is used. Specifically, the treatment with the surface treatment agent of the present invention imparts the property that the aqueous substance is difficult to adhere to the surface of the substrate to be treated (water repellency) and the property that the attached aqueous substance tends to fall off (sliding property). . In particular, the property that the attached mud easily falls off (hereinafter also referred to as “mud removal”), the property that ice and frost do not easily adhere (hereinafter also referred to as “ice / frost adhesion prevention”), and these A property having both characteristics is imparted to the surface to be processed. Hereinafter, the “surface characteristics” of the surface to be treated refers to the properties of the surface of the copolymer film that are different from the original substrate surface imparted by the treatment with the surface treatment agent.
　本発明の表面処理剤（以下、「本剤」とも記す。）は、下記単位（ａ）と下記単位（ｃ）と任意に下記単位（ｂ）とを含み、単位（ａ）と単位（ｂ）との合計に対する単位（ａ）の割合が３０～１００質量％である共重合体であって、共重合体中の全単位に対する単位（ａ）と単位（ｂ）との合計の割合が６０～９０質量％であり、かつ、共重合体中の全単位に対する単位（ｃ）の割合が１０～４０質量％である共重合体を含む。
　該共重合体としては、前記単位（ａ）と単位（ｂ）との合計に対する単位（ａ）の割合が３０～７０質量％である共重合体（以下、「共重合体（１）」とも記す。）が好ましい。また、単位（ｂ）を含まない共重合体（以下、「共重合体（２）」とも記す。）が好ましい。
　以下、共重合体（１）と共重合体（２）とをまとめて「本共重合体」と記すことがある。 The surface treatment agent of the present invention (hereinafter also referred to as “this agent”) includes the following unit (a), the following unit (c), and optionally the following unit (b). ) With a ratio of the unit (a) to the total of 30 to 100% by mass, and the total ratio of the unit (a) and the unit (b) to the total unit in the copolymer is 60 And a copolymer having a ratio of unit (c) to 10 to 40% by mass with respect to all units in the copolymer.
Examples of the copolymer include a copolymer (hereinafter referred to as “copolymer (1)”) in which the ratio of the unit (a) to the total of the units (a) and (b) is 30 to 70% by mass. Are preferred). A copolymer containing no unit (b) (hereinafter also referred to as “copolymer (2)”) is preferred.
Hereinafter, the copolymer (1) and the copolymer (2) may be collectively referred to as “the present copolymer”.
　本共重合体は、さらに後述する単位（ｄ）、単位（ｅ）を含んでいてもよい。
　本共重合体の重合形態は特に限定されず、各単位がランダム、ブロック、交互のいずれでもよいが、ランダムであることが好ましい。
　本共重合体の製造方法は特に限定されず、各種の公知の方法を適用し得る。 The copolymer may further contain units (d) and units (e) described later.
The polymerization form of the copolymer is not particularly limited, and each unit may be random, block, or alternating, but is preferably random.
The production method of the copolymer is not particularly limited, and various known methods can be applied.
　本共重合体の数平均分子量（Ｍｎ）は１×１０３～１×１０７であることが好ましく、１×１０４～１×１０６であることが特に好ましい。前記範囲の下限値以上であると、造膜性に優れ、泥脱落性、氷・霜付着防止性を有する。前記範囲の上限値以下であると、本共重合体の溶媒への溶解性に優れ、本剤を基材に塗布しやすい点で好ましい。 The number average molecular weight (Mn) of the copolymer is preferably 1 × 10 3 to 1 × 10 7 , and particularly preferably 1 × 10 4 to 1 × 10 6 . It is excellent in film forming property as it is more than the lower limit of the said range, and has mud fall-off property and ice / frost adhesion prevention property. It is preferable that it is not more than the upper limit of the above range in that the copolymer is excellent in solubility in a solvent and the agent can be easily applied to a substrate.
　本剤は、必要に応じて溶媒を含んでいてもよい。溶媒は表面処理の際に除去されて本共重合体の膜が形成される。
　本剤は、必要に応じて、本組成物の安定性、形成される膜の表面特性、外観等を損なわない範囲で、上記以外の成分をさらに含んでいてもよい。 This agent may contain a solvent as necessary. The solvent is removed during the surface treatment to form a film of the copolymer.
This agent may further contain components other than those described above as needed, as long as the stability of the composition, the surface characteristics of the formed film, the appearance, and the like are not impaired.
（単位（ａ））
　単位（ａ）は、下式（ａ）で表される単量体由来の単位である。
　Ｃ（Ｘ１）２＝ＣＸ１－ＣＯＯ－Ｒ１－ＲＦ１・・・（ａ）
〔式（ａ）中、３つのＸ１はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ１は炭素数１～６のアルキレン基であり、ＲＦ１は炭素数１～３のペルフルオロアルキル基である。〕 (Unit (a))
The unit (a) is a unit derived from a monomer represented by the following formula (a).
C (X 1 ) 2 = CX 1 —COO—R 1 —R F1 (a)
[In the formula (a), three X 1 s are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom; R 1 is an alkylene group having 1 to 6 carbon atoms; F1 is a perfluoroalkyl group having 1 to 3 carbon atoms. ]
　本共重合体は、単位（ａ）を有することで、本共重合体の膜の表面の水転落角を低くすることができる。
　式（ａ）中、Ｘ１は、単量体が入手容易な点から、水素原子またはメチル基が好ましい。３つのＸ１は同じであっても異なっていてもよい。単量体が入手容易な点から、Ｃ（Ｘ１）２＝ＣＸ１－は、ＣＨ２＝ＣＨ－またはＣＨ２＝Ｃ（ＣＨ３）－であることが特に好ましい。
　Ｒ１の炭素数が２以上の場合、アルキレン基は直鎖構造でも分岐構造でもよいが、本共重合体が表面特性に優れる点から、直鎖構造が好ましい。Ｒ１の炭素数は、単量体が入手容易な点から１～３が好ましく、１～２が特に好ましい。
　ＲＦ１の炭素数が３の場合、ペルフルオロアルキル基は直鎖構造でも分岐構造でもよいが、本共重合体が表面特性に優れる点から、直鎖構造が好ましい。ＲＦ１の炭素数は、転落角をより低くできる点から、１が特に好ましい。 By having the unit (a) in the copolymer, the water falling angle on the surface of the film of the copolymer can be lowered.
In formula (a), X 1 is preferably a hydrogen atom or a methyl group from the viewpoint that a monomer is easily available. The three X 1 may be the same or different. From a monomer points readily available, C (X 1) 2 = CX 1 - is, CH 2 = CH- or CH 2 = C (CH 3) - and particularly preferably.
When R 1 has 2 or more carbon atoms, the alkylene group may have a linear structure or a branched structure, but a linear structure is preferred from the viewpoint of excellent surface characteristics of the copolymer. The number of carbon atoms of R 1 is preferably 1 to 3 and particularly preferably 1 to 2 in view of easy availability of the monomer.
When R F1 has 3 carbon atoms, the perfluoroalkyl group may have a linear structure or a branched structure, but a linear structure is preferred from the viewpoint of excellent surface characteristics of the copolymer. The number of carbon atoms in R F1 is particularly preferably 1 because the falling angle can be further reduced.
　単量体（ａ）として最も好ましいのは、以下の化合物である。
　ＣＨ２＝ＣＨ－ＣＯＯ－ＣＨ２－ＣＦ３
　ＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯ－ＣＨ２－ＣＦ３
　ＣＨ２＝ＣＨ－ＣＯＯ－ＣＨ２－ＣＦ２ＣＦ３
　ＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯ－ＣＨ２－ＣＦ２ＣＦ３ Most preferred as the monomer (a) are the following compounds.
CH 2 ═CH—COO—CH 2 —CF 3
CH 2 ═C (CH 3 ) —COO—CH 2 —CF 3
CH 2 ═CH—COO—CH 2 —CF 2 CF 3
CH 2 ═C (CH 3 ) —COO—CH 2 —CF 2 CF 3
（単位（ｂ））
　単位（ｂ）は、下式（ｂ）で表される単量体由来の単位である。
　Ｃ（Ｘ２）２＝ＣＸ２－ＣＯＯ－Ｒ２－ＲＦ２・・・（ｂ）
〔式（ｂ）中、３つのＸ２はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ２は炭素数１～６のアルキレン基であり、ＲＦ２は炭素数４～６のペルフルオロアルキル基である。〕 (Unit (b))
The unit (b) is a unit derived from a monomer represented by the following formula (b).
C (X 2 ) 2 = CX 2 —COO—R 2 —R F2 (b)
[In the formula (b), three X 2 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom; R 2 is an alkylene group having 1 to 6 carbon atoms; F2 is a C 4-6 perfluoroalkyl group. ]
　共重合体（１）は、単位（ｂ）を有することで、本共重合体の膜の表面が撥水性に優れる。
　式（ｂ）中、Ｘ２は、例示も好ましい範囲もＸ１と同様であり、Ｃ（Ｘ２）２＝ＣＸ２－は、ＣＨ２＝ＣＨ－またはＣＨ２＝Ｃ（ＣＨ３）－であることが特に好ましい。
　Ｒ２は、例示も好ましい範囲もＲ１と同様である。
　ＲＦ２のペルフルオロアルキル基は直鎖構造でも分岐構造でもよいが、共重合体（１）が撥水性により優れる点から、直鎖構造が好ましい。ＲＦ２の炭素数は、共重合体（１）が撥水性により優れる点から、６が特に好ましい。 When the copolymer (1) has the unit (b), the surface of the film of the copolymer is excellent in water repellency.
In formula (b), X 2 has the same examples and preferred ranges as X 1 , and C (X 2 ) 2 ═CX 2 — represents CH 2 ═CH— or CH 2 ═C (CH 3 ) —. It is particularly preferred.
R 2 is the same as R 1 in both illustration and preferred range.
The perfluoroalkyl group of R F2 may have a linear structure or a branched structure, but a linear structure is preferable from the viewpoint that the copolymer (1) is excellent in water repellency. The number of carbon atoms of R F2 is particularly preferably 6 because the copolymer (1) is more excellent in water repellency.
　単量体（ｂ）として最も好ましいのは、以下の化合物である。
　ＣＨ２＝ＣＨ－ＣＯＯ－（ＣＨ２）２－（ＣＦ２）３ＣＦ３
　ＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯ－（ＣＨ２）２－（ＣＦ２）３ＣＦ３
　ＣＨ２＝ＣＨ－ＣＯＯ－（ＣＨ２）２－（ＣＦ２）５ＣＦ３
　ＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯ－（ＣＨ２）２－（ＣＦ２）５ＣＦ３ Most preferred as the monomer (b) are the following compounds.
CH 2 = CH-COO- (CH 2 ) 2- (CF 2 ) 3 CF 3
CH 2 ═C (CH 3 ) —COO— (CH 2 ) 2 — (CF 2 ) 3 CF 3
CH 2 ═CH—COO— (CH 2 ) 2 — (CF 2 ) 5 CF 3
CH 2 ═C (CH 3 ) —COO— (CH 2 ) 2 — (CF 2 ) 5 CF 3
（単位（ｃ））
　単位（ｃ）は、下式（ｃ）で表される単量体由来の単位である。
　Ｃ（Ｘ３）２＝ＣＸ３－ＣＯＯ－Ｒ３・・・（ｃ）
〔式（ｃ）中、３つのＸ３はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ３はオルガノポリシロキサン鎖を有する基である。〕 (Unit (c))
The unit (c) is a unit derived from a monomer represented by the following formula (c).
C (X 3 ) 2 = CX 3 —COO—R 3 (c)
[In the formula (c), three X 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 3 is a group having an organopolysiloxane chain. ]
　本共重合体は、単位（ｃ）を有することで、本共重合体の膜の表面が滑水性に優れる。
　式（ｃ）中、Ｘ３は、例示も好ましい範囲もＸ１と同様であり、Ｃ（Ｘ３）２＝ＣＸ３－は、ＣＨ２＝ＣＨ－またはＣＨ２＝Ｃ（ＣＨ３）－であることが特に好ましい。
　オルガノポリシロキサン鎖は、－（Ｓｉ（Ｒ）２Ｏ）－で表される繰り返し単位を複数個有する基であり（Ｒはアルキル基。２つのＲは同じでもよい。）、－（Ｓｉ（ＣＨ３）２Ｏ）－で表される繰り返し単位を複数個有する、ポリジメチルシロキサン鎖が好ましい。
　Ｒ３の酸素原子側末端の結合手は炭素原子の結合手であり、オルガノポリシロキサン鎖末端のケイ素原子との間に連結基を有する。この連結基のケイ素原子側末端の結合手もまた炭素原子の結合手である。したがって、この連結基は、両結合末端が炭素原子である２価の有機基からなる。
　また、Ｒ３の自由末端側にはオルガノポリシロキサン鎖末端のケイ素原子に結合する１価の有機基を有し、この１価の有機基のケイ素原子側末端の結合手もまた炭素原子の結合手である。したがって、この１価の有機基は、結合末端が炭素原子である１価の有機基である。 Since the present copolymer has the unit (c), the surface of the copolymer film is excellent in water slidability.
In formula (c), X 3 has the same examples and preferred ranges as X 1 and C (X 3 ) 2 ═CX 3 — represents CH 2 ═CH— or CH 2 ═C (CH 3 ) —. It is particularly preferred.
The organopolysiloxane chain is a group having a plurality of repeating units represented by — (Si (R) 2 O) — (R is an alkyl group. Two Rs may be the same), and — (Si (CH 3 ) A polydimethylsiloxane chain having a plurality of repeating units represented by 2 O)-is preferred.
The bond at the oxygen atom side end of R 3 is a bond of a carbon atom and has a linking group with the silicon atom at the end of the organopolysiloxane chain. The bond at the silicon atom side terminal of this linking group is also a bond of a carbon atom. Therefore, this linking group consists of a divalent organic group whose both bond ends are carbon atoms.
Further, R 3 has a monovalent organic group bonded to the silicon atom at the end of the organopolysiloxane chain on the free end side, and the bond at the silicon atom side end of this monovalent organic group is also bonded to a carbon atom. It is a hand. Therefore, this monovalent organic group is a monovalent organic group whose bond end is a carbon atom.
　Ｒ３中の前記の２価の有機基および１価の有機基としては、アルキレン基やアルキル基等の炭化水素基が挙げられる。シクロアルキレン基、アリーレン基、シクロアルキル基、アリール基等の環状炭化水素基等の環状炭化水素基であってもよく、アルキレン基やアルキル基の炭素原子間やアルキル基の末端に環状炭化水素基を有する炭化水素基であってもよい。
　上記の２価の有機基および１価の有機基は官能性基を有していてもよい。官能性基としては、水酸基、エポキシ基、カルボキシ基、アミノ基、アミド基等が挙げられる。ただし、官能性基として、重合性の炭素－炭素二重結合を有する基は好ましくない。官能性基としては、酸素原子または窒素原子を有する官能性基が好ましく、水酸基、エポキシ基、カルボキシ基等の酸素原子を有する官能性基が好ましい。
　上記の２価の有機基および１価の有機基は、官能性基以外の部分に、ヘテロ原子を有していてもよい。ヘテロ原子としては、フッ素原子、塩素原子、酸素原子、窒素原子等が挙げられる。ヘテロ原子は複素環を構成するヘテロ原子であってもよい。ヘテロ原子としては酸素原子が好ましく、酸素原子を有する有機基としては、アルコキシ基、アシルオキシ基、アシル基等を有する有機基が挙げられる。また、ポリオキシアルキレン鎖等のエーテル性酸素原子を主鎖に有する有機基であってもよい。 Examples of the divalent organic group and monovalent organic group in R 3 include hydrocarbon groups such as an alkylene group and an alkyl group. It may be a cyclic hydrocarbon group such as a cycloalkylene group, an arylene group, a cycloalkyl group, a cyclic hydrocarbon group such as an aryl group, or a cyclic hydrocarbon group between carbon atoms of an alkylene group or an alkyl group or at the end of an alkyl group. It may be a hydrocarbon group having
The above divalent organic group and monovalent organic group may have a functional group. Examples of the functional group include a hydroxyl group, an epoxy group, a carboxy group, an amino group, and an amide group. However, a group having a polymerizable carbon-carbon double bond is not preferred as the functional group. As the functional group, a functional group having an oxygen atom or a nitrogen atom is preferable, and a functional group having an oxygen atom such as a hydroxyl group, an epoxy group, or a carboxy group is preferable.
Said divalent organic group and monovalent organic group may have a hetero atom in parts other than a functional group. Examples of the hetero atom include a fluorine atom, a chlorine atom, an oxygen atom, and a nitrogen atom. The heteroatom may be a heteroatom constituting a heterocyclic ring. The hetero atom is preferably an oxygen atom, and examples of the organic group having an oxygen atom include organic groups having an alkoxy group, an acyloxy group, an acyl group, and the like. Further, it may be an organic group having an etheric oxygen atom such as a polyoxyalkylene chain in the main chain.
　単量体（ｃ）としては下式（ｃ１）で表される単量体がより好ましい。
　Ｃ（Ｘ３）２＝ＣＸ３－ＣＯＯ－Ｒ４－（Ｓｉ（Ｒ５）２Ｏ）ｍ－Ｓｉ（Ｒ６）２－Ｒ７・・・（ｃ１）
〔式（ｃ１）中、Ｘ３は上述の通りであり、Ｒ４は炭素数１～６のアルキレン基であり、２つのＲ５はそれぞれ独立に炭素数１～３のアルキル基であり、２つのＲ６はそれぞれ独立に炭素数１～３のアルキル基であり、Ｒ７は官能性基を有していてもよい１価の有機基であり、ｍは１０～８００の整数である。〕 The monomer (c) is more preferably a monomer represented by the following formula (c1).
C (X 3 ) 2 = CX 3 —COO—R 4 — (Si (R 5 ) 2 O) m —Si (R 6 ) 2 —R 7 (c1)
[In the formula (c1), X 3 is as described above, R 4 is an alkylene group having 1 to 6 carbon atoms, and two R 5 are each independently an alkyl group having 1 to 3 carbon atoms, Each R 6 is independently an alkyl group having 1 to 3 carbon atoms, R 7 is a monovalent organic group which may have a functional group, and m is an integer of 10 to 800. ]
　式（ｃ１）中、Ｒ４の炭素数が２以上の場合、アルキレン基は直鎖構造でも分岐構造でもよいが、直鎖構造が好ましい。Ｒ４の炭素数は、単量体が入手容易な点から１～３が特に好ましい。
　Ｒ５およびＲ６の炭素数が３の場合、アルキル基は直鎖構造でも分岐構造でもよいが、直鎖構造が好ましい。Ｒ５およびＲ６は入手容易な点からいずれもメチル基であることが特に好ましい。
　ｍは５０～６００の整数がより好ましく、１００～４００の整数が特に好ましい。
　Ｒ７は炭化水素基であるか炭素原子間にエーテル性酸素原子、アシルオキシ基、アシル基等を有する炭化水素基であることが好ましい。
　Ｒ７が有していてもよい官能基としては、水酸基、カルボキシ基、エポキシ基、１級アミノ基、２級アミノ基等が挙げられ、製造が容易な点、反応性等の点からエポキシ基を有する基（たとえば、グリシジルオキシ基）が好ましい。
　Ｒ７としては、官能基を有しかつ炭素原子間にエーテル性酸素原子またはアシルオキシ基を有していてもよい、脂肪族炭化水素基が好ましく、特にエポキシ基を有しかつエーテル性炭素原子を有していてもよい脂肪族炭化水素基が好ましい。 In the formula (c1), when R 4 has 2 or more carbon atoms, the alkylene group may have a linear structure or a branched structure, but a linear structure is preferred. The number of carbon atoms of R 4 is particularly preferably 1 to 3 from the viewpoint of easy availability of monomers.
When R 5 and R 6 have 3 carbon atoms, the alkyl group may have a linear structure or a branched structure, but a linear structure is preferred. R 5 and R 6 are particularly preferably both methyl groups from the viewpoint of easy availability.
m is more preferably an integer of 50 to 600, particularly preferably an integer of 100 to 400.
R 7 is preferably a hydrocarbon group or a hydrocarbon group having an etheric oxygen atom, an acyloxy group, an acyl group or the like between carbon atoms.
Examples of the functional group that R 7 may have include a hydroxyl group, a carboxy group, an epoxy group, a primary amino group, a secondary amino group, and the like. From the viewpoint of easy production and reactivity, an epoxy group. A group having a (for example, glycidyloxy group) is preferred.
R 7 is preferably an aliphatic hydrocarbon group having a functional group and optionally having an etheric oxygen atom or an acyloxy group between carbon atoms, particularly having an epoxy group and an etheric carbon atom. An aliphatic hydrocarbon group which may be contained is preferable.
（単位（ｄ））
　単位（ｄ）は、下式（ｄ）で表される単量体由来の単位である。
　Ｃ（Ｘ４）２＝ＣＸ４－ＣＯＯ－Ｒ９－ＯＣＯ－ＣＸ５＝Ｃ（Ｘ５）２・・・（ｄ）
　〔式（ｄ）中、３つのＸ４はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｘ５はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ９は炭素数１～６のアルキレン基である。〕 (Unit (d))
The unit (d) is a monomer-derived unit represented by the following formula (d).
C (X 4 ) 2 = CX 4 —COO—R 9 —OCO—CX 5 = C (X 5 ) 2 ... (D)
[In the formula (d), three X 4 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and each X 5 is independently a hydrogen atom, having 1 to 3 carbon atoms. An alkyl group, a chlorine atom or a fluorine atom, and R 9 is an alkylene group having 1 to 6 carbon atoms; ]
　本共重合体は、単位（ｄ）を有することで、本共重合体の膜の硬さが優れる。
　式（ｄ）中、Ｘ４は、例示も好ましい範囲もＸ１と同様であり、Ｃ（Ｘ４）２＝ＣＸ４－は、ＣＨ２＝ＣＨ－またはＣＨ２＝Ｃ（ＣＨ３）－であることが特に好ましい。Ｘ５は、例示も好ましい範囲もＸ１と同様であり、－ＣＸ５＝Ｃ（Ｘ５）２は、－ＣＨ＝ＣＨ２または－Ｃ（ＣＨ３）＝ＣＨ２であることが特に好ましい。
　Ｒ９の炭素数が２以上の場合、アルキレン基は直鎖構造でも分岐構造でもよいが、直鎖構造が好ましい。Ｒ９の炭素数は、単量体が入手容易な点から１～３が特に好ましい。 Since the present copolymer has the unit (d), the hardness of the film of the present copolymer is excellent.
In formula (d), X 4 has the same examples and preferred ranges as X 1 , and C (X 4 ) 2 ═CX 4 — represents CH 2 ═CH— or CH 2 ═C (CH 3 ) —. It is particularly preferred. X 5 has the same exemplified and preferred range as X 1, and it is particularly preferable that —CX 5 ═C (X 5 ) 2 is —CH═CH 2 or —C (CH 3 ) ═CH 2 .
When R 9 has 2 or more carbon atoms, the alkylene group may have a linear structure or a branched structure, but a linear structure is preferred. The number of carbon atoms of R 9 is particularly preferably 1 to 3 from the viewpoint of easy availability of monomers.
　単量体（ｄ）として最も好ましいのは、以下の化合物である。
　ＣＨ２＝ＣＨ－ＣＯＯ－ＣＨ２－ＯＣＯ－ＣＨ＝ＣＨ２
　ＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯ－ＣＨ２－ＯＣＯ－Ｃ（ＣＨ３）＝ＣＨ２ Most preferred as the monomer (d) are the following compounds.
CH 2 ═CH—COO—CH 2 —OCO—CH═CH 2
CH 2 ═C (CH 3 ) —COO—CH 2 —OCO—C (CH 3 ) ═CH 2
（単位（ｅ））
　単位（ｅ）は、下式（ｅ）で表される単量体由来の単位である。
　Ｃ（Ｘ６）２＝ＣＸ６－Ｒ１０－ＣＯＯＨ・・・（ｅ）
〔式（ｅ）中、３つのＸ６はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ１０は単結合か炭素数１～１０のアルキレン基である。〕 (Unit (e))
The unit (e) is a unit derived from a monomer represented by the following formula (e).
C (X 6 ) 2 = CX 6 -R 10 -COOH (e)
[In the formula (e), three X 6 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 10 is a single bond or an alkylene group having 1 to 10 carbon atoms. is there. ]
　本共重合体は、単位（ｅ）を有することで、本共重合体の膜の基材への密着性が優れる。
　式（ｅ）中、Ｘ６は、例示も好ましい範囲もＸ１と同様であり、Ｃ（Ｘ６）２＝ＣＸ６－は、ＣＨ２＝ＣＨ－またはＣＨ２＝Ｃ（ＣＨ３）－であることが特に好ましい。
　Ｒ１０の炭素数が２以上の場合、アルキレン基は直鎖構造でも分岐構造でもよいが、直鎖構造が好ましい。Ｒ１０は、単量体が入手容易な点から単結合が特に好ましい。 By having the unit (e), the present copolymer has excellent adhesion of the copolymer film to the substrate.
In formula (e), X 6 has the same examples and preferred ranges as X 1 , and C (X 6 ) 2 ═CX 6 — represents CH 2 ═CH— or CH 2 ═C (CH 3 ) —. It is particularly preferred.
When R 10 has 2 or more carbon atoms, the alkylene group may have a linear structure or a branched structure, but a linear structure is preferred. R 10 is particularly preferably a single bond from the viewpoint that a monomer is easily available.
　単量体（ｅ）として最も好ましいのは、以下の化合物である。
　ＣＨ２＝ＣＨ－ＣＯＯＨ
　ＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯＨ Most preferred as the monomer (e) are the following compounds.
CH 2 = CH-COOH
CH 2 ═C (CH 3 ) —COOH
（共重合体の組成）
　共重合体（１）において、全単位に対する単位（ａ）と単位（ｂ）との合計の割合は６０～９０質量％であり、６５～８５質量％が好ましく、７０～８０質量％が特に好ましい。共重合体（１）において、単位（ａ）と単位（ｂ）との合計に対する単位（ａ）の割合は３０～７０質量％であり、４０～６０質量％が好ましく、４５～５５質量％が特に好ましい。
　共重合体（２）において、全単位に対する単位（ａ）の含有量は６０～９０質量％であり、６５～８５質量％が好ましく、７０～８０質量％が特に好ましい。
　本共重合体において、全単位に対する単位（ｃ）の割合は１０～４０質量％であり、１０～３０質量％が特に好ましい。
　本共重合体において、全単位に対する単位（ｄ）と単位（ｅ）との合計の割合は、０．１～５質量％が好ましく、０．１～３質量％が特に好ましい。
　本共重合体において、全単位に対する単位（ｄ）の割合は０．１～５質量％が好ましく、０．１～３質量％が特に好ましい。
　本共重合体において、全単位に対する単位（ｅ）の割合は０．１～５質量％が好ましく、０．１～３質量％が特に好ましい。 (Composition of copolymer)
In the copolymer (1), the total ratio of the unit (a) and the unit (b) to the whole unit is 60 to 90% by mass, preferably 65 to 85% by mass, particularly preferably 70 to 80% by mass. . In the copolymer (1), the ratio of the unit (a) to the total of the units (a) and (b) is 30 to 70% by mass, preferably 40 to 60% by mass, and 45 to 55% by mass. Particularly preferred.
In the copolymer (2), the content of the unit (a) with respect to all units is from 60 to 90% by mass, preferably from 65 to 85% by mass, particularly preferably from 70 to 80% by mass.
In the present copolymer, the ratio of the unit (c) to the total units is 10 to 40% by mass, and 10 to 30% by mass is particularly preferable.
In the present copolymer, the total ratio of the unit (d) and the unit (e) to the whole unit is preferably from 0.1 to 5% by mass, particularly preferably from 0.1 to 3% by mass.
In the present copolymer, the ratio of the unit (d) to all units is preferably from 0.1 to 5% by mass, particularly preferably from 0.1 to 3% by mass.
In the present copolymer, the ratio of the unit (e) to the whole unit is preferably from 0.1 to 5% by mass, particularly preferably from 0.1 to 3% by mass.
　本共重合体（１）の好ましい様態は、全単位に対する単位（ａ）と単位（ｂ）との合計の割合が６０～９０質量％、単位（ａ）と単位（ｂ）との合計に対する単位（ａ）の割合が４０～６０質量％、全単位に対する単位（ｃ）の割合が１０～４０質量％、全単位に対する単位（ｄ）と単位（ｅ）との合計の割合は、０．１～５質量％、全単位に対する単位（ｄ）の割合が０．１～５質量％、全単位に対する単位（ｅ）の割合が０．１～５質量％であり、最も好ましい様態は、全単位に対する単位（ａ）と単位（ｂ）との合計の割合が７０～８０質量％、単位（ａ）と単位（ｂ）との合計に対する単位（ａ）の割合が４５～５５質量％、全単位に対する単位（ｃ）の割合が１０～３０質量％、全単位に対する単位（ｄ）と単位（ｅ）との合計の割合は、０．１～３質量％、全単位に対する単位（ｄ）の割合が０．１～３質量％、全単位に対する単位（ｅ）の割合が０．１～３質量％である。
　本共重合体（２）の好ましい様態は、全単位に対する単位（ａ）の割合が６０～９０質量％、全単位に対する単位（ｃ）の割合が１０～４０質量％、全単位に対する単位（ｄ）と単位（ｅ）との合計の割合は、０．１～５質量％、全単位に対する単位（ｄ）の割合が０．１～５質量％、全単位に対する単位（ｅ）の割合が０．１～５質量％であり、最も好ましい様態は、全単位に対する単位（ａ）の割合が７０～８０質量％、全単位に対する単位（ｃ）の割合が１０～３０質量％、全単位に対する単位（ｄ）と単位（ｅ）との合計の割合は、０．１～３質量％、全単位に対する単位（ｄ）の割合が０．１～３質量％、全単位に対する単位（ｅ）の割合が０．１～３質量％である。 A preferred embodiment of the present copolymer (1) is that the total ratio of the unit (a) and the unit (b) to the whole unit is 60 to 90% by mass, and the unit is based on the total of the unit (a) and the unit (b). The ratio of (a) is 40 to 60% by mass, the ratio of unit (c) to all units is 10 to 40% by mass, and the total ratio of units (d) and units (e) to all units is 0.1 5% by mass, the ratio of the unit (d) to the whole unit is 0.1 to 5% by mass, and the ratio of the unit (e) to the whole unit is 0.1 to 5% by mass. The ratio of the total of the unit (a) and the unit (b) to 70 to 80% by mass, the ratio of the unit (a) to the total of the unit (a) and the unit (b) is 45 to 55% by mass, the total unit The ratio of unit (c) to 10 to 30% by mass of the total of unit (d) and unit (e) with respect to all units If the 0.1 to 3 wt%, the proportion of 0.1 to 3% by weight of units (d) to all the units, the proportion of the unit (e) to all the units is 0.1 to 3 wt%.
A preferred embodiment of the present copolymer (2) is that the ratio of the unit (a) to the total unit is 60 to 90% by mass, the ratio of the unit (c) to the total unit is 10 to 40% by mass, the unit (d ) And unit (e) are 0.1 to 5% by mass, the unit (d) is 0.1 to 5% by mass with respect to all units, and the unit (e) is 0% with respect to all units. 1 to 5% by mass, and the most preferable embodiment is that the ratio of the unit (a) to the total unit is 70 to 80% by mass, the ratio of the unit (c) to the total unit is 10 to 30% by mass, and the unit to the total unit. The total ratio of (d) and unit (e) is 0.1 to 3% by mass, the ratio of unit (d) to all units is 0.1 to 3% by mass, and the ratio of unit (e) to all units Is 0.1 to 3% by mass.
（溶媒）
　本剤が溶媒を含む場合、本剤中の本共重合体の濃度は、０．１～２０質量％が好ましく、１～１０質量％がより好ましく、１～５質量％が特に好ましい。本剤が溶媒と溶媒以外の任意成分とを含む場合、本剤の固形分濃度は０．１～２０質量％が好ましく、１～１０質量％がより好ましく、２～５質量％が特に好ましい。本共重合体の濃度や固形分濃度が０．１～２０質量％の範囲内であると、膜厚が充分厚く造膜性に優れるため、本剤を用いて形成される膜が、撥水性や滑水性に優れた膜厚の膜となりやすい。特に、１～１０質量％の範囲内であると、泥脱落性、氷・霜付着防止性が充分に発揮される好適な膜厚の膜となりやすい。
　本剤が溶媒を含む場合、本剤中の溶媒の含有量は、８０～９９．９質量％が好ましく、９０～９９質量％がより好ましく、９５～９８質量％が特に好ましい。 (solvent)
When the agent contains a solvent, the concentration of the copolymer in the agent is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, and particularly preferably 1 to 5% by mass. When the agent contains a solvent and an optional component other than the solvent, the solid content concentration of the agent is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass. When the copolymer concentration or solid content concentration is in the range of 0.1 to 20% by mass, the film is sufficiently thick and has excellent film forming properties. It is easy to form a film with excellent film slidability. In particular, when it is in the range of 1 to 10% by mass, a film having a suitable film thickness that can sufficiently exhibit mud drop-off property and ice / frost adhesion prevention property tends to be obtained.
When the agent contains a solvent, the content of the solvent in the agent is preferably 80 to 99.9% by mass, more preferably 90 to 99% by mass, and particularly preferably 95 to 98% by mass.
　溶媒としては、本共重合体を溶解可能であればよく、公知の各種の溶剤の中から適宜選択できる。
　溶媒としては、フッ素原子含有率が６０質量％未満の含フッ素溶媒が好ましく、５５質量％未満の含フッ素溶媒が特に好ましい。たとえばｍ－キシレンヘキサフロリド（以下、「ｍ－ＸＨＦ」とも記す。）、ｐ－キシレンヘキサフロリド等が挙げられる。なお、フッ素原子含有率（以下、「Ｆ含有率」とも記す。）は、下式（Ｉ）により求められる。
　（Ｆ含有率）＝（（分子中のフッ素原子の数）×１９）／（分子量）×１００・・・（Ｉ） The solvent is not particularly limited as long as the copolymer can be dissolved, and can be appropriately selected from various known solvents.
As the solvent, a fluorine-containing solvent having a fluorine atom content of less than 60% by mass is preferable, and a fluorine-containing solvent having a content of less than 55% by mass is particularly preferable. Examples thereof include m-xylene hexafluoride (hereinafter also referred to as “m-XHF”), p-xylene hexafluoride, and the like. The fluorine atom content (hereinafter also referred to as “F content”) is determined by the following formula (I).
(F content) = ((number of fluorine atoms in the molecule) × 19) / (molecular weight) × 100 (I)
〔物品〕
　本発明の物品は、本剤から形成された膜を基材の表面に有する。 [Goods]
The article of the present invention has a film formed from this agent on the surface of the substrate.
　前記膜の厚さは、１００～１，０００ｎｍが好ましく、１２０～４００ｎｍが特に好ましい。膜の厚さが前記範囲内であれば、充分な撥水性や滑水性が発揮されやすく、さらに１２０ｎｍ以上であれば、良好な泥脱落性、氷・霜付着防止性が発現しやすい。
　膜の厚さは、Ｊ．Ａ・ウーラム社製に代表されるエリプソメータでの測定により求められる。 The thickness of the film is preferably from 100 to 1,000 nm, particularly preferably from 120 to 400 nm. If the thickness of the film is within the above range, sufficient water repellency and water slidability are likely to be exhibited, and if it is 120 nm or more, good mud removal and ice / frost adhesion prevention properties are likely to be exhibited.
The thickness of the membrane is It is calculated | required by the measurement with an ellipsometer represented by the product made from A. Woollam.
（基材）
　本発明における基材は、撥水性や滑水性、そのうちでも特に泥脱落性や氷・霜付着防止性の付与が求められている基材であれば特に限定されない。基材の材料としては、金属、樹脂、ガラス、サファイア、セラミック、石、木材、繊維、これらの２種以上の複合材料等が挙げられる。 (Base material)
The base material in the present invention is not particularly limited as long as it is required to impart water repellency and water slidability, and in particular, provision of mud detachability and ice / frost adhesion prevention. Examples of the base material include metals, resins, glass, sapphire, ceramics, stones, wood, fibers, and composite materials of two or more of these.
（物品の製造方法）
　本発明の物品は、たとえば、溶媒を含む本剤を基材の表面に塗布し、乾燥させて膜を形成する方法により製造できる。
　本剤の塗布方法としては、公知のウェットコーティング法を利用でき、たとえばディップコート法、スピンコート法、ワイプコート法、スプレーコート法、スキージーコート法、ダイコート法、インクジェット法、フローコート法、ロールコート法、キャスト法、ラングミュア・ブロジェット法、グラビアコート法等が挙げられる。
　乾燥方法としては、溶媒の沸点以上の温度で加熱する方法が好ましい。ただし、基材の材質等によって加熱乾燥が困難な場合には、加熱を回避して乾燥すべきである。加熱条件は、本剤の組成や塗布面積等に応じて選択すればよい。 (Product manufacturing method)
The article of the present invention can be produced, for example, by a method in which the present agent containing a solvent is applied to the surface of a substrate and dried to form a film.
As a coating method of this agent, a known wet coating method can be used, for example, dip coating method, spin coating method, wipe coating method, spray coating method, squeegee coating method, die coating method, inkjet method, flow coating method, roll coating. Method, casting method, Langmuir-Blodgett method, gravure coating method and the like.
As a drying method, a method of heating at a temperature equal to or higher than the boiling point of the solvent is preferable. However, when heat drying is difficult due to the material of the substrate, etc., heating should be avoided to dry. What is necessary is just to select a heating condition according to a composition, the application area, etc. of this agent.
（作用効果）
　本発明の物品が基材の表面に有する膜は、本剤から形成された膜であるため、撥水性や滑水性を有し、特に泥脱落性や氷・霜付着防止性に優れる。 (Function and effect)
Since the film | membrane which the article of this invention has on the surface of a base material is a film | membrane formed from this agent, it has water repellency and water slidability, and is especially excellent in mud fall-off property and ice / frost adhesion prevention property.
　以下、実施例を示して本発明を詳細に説明する。ただし、本発明は以下の記載によっては限定されない。「％」は、特に規定のない限り、「質量％」を示す。
　後述する例１～６のうち、例１～２は実施例、例３～６が比較例である。
　各例で使用した評価方法および材料を以下に示す。 Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following description. “%” Indicates “mass%” unless otherwise specified.
Among examples 1 to 6 described later, examples 1 and 2 are examples, and examples 3 to 6 are comparative examples.
The evaluation methods and materials used in each example are shown below.
〔評価方法〕
（数平均分子量（Ｍｎ））
　重合体の数平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）法によるポリメタクリル酸メチル（ＰＭＭＡ）換算分子量である。 〔Evaluation methods〕
(Number average molecular weight (Mn))
The number average molecular weight of a polymer is a polymethyl methacrylate (PMMA) conversion molecular weight by a gel permeation chromatography (GPC) method.
（水接触角）
　２５℃、４０％ＲＨの環境下、後述する膜付きガラス基板の膜の表面にイオン交換水の約２μＬを滴下して、接触角計（協和界面科学社製ＤＭ－５００）で接触角（水接触角）を測定した。この値が大きいものほど、撥水性が高いことになる。結果を表１に示す。 (Water contact angle)
In an environment of 25 ° C. and 40% RH, about 2 μL of ion-exchanged water is dropped on the surface of a glass substrate with a film to be described later, and the contact angle (water Contact angle) was measured. The larger this value, the higher the water repellency. The results are shown in Table 1.
（水転落角）
　２５℃、４０％ＲＨの環境下、後述する膜付きガラス基板の膜の表面にイオン交換水の５μＬを滴下し、膜付きガラス基板を水平面に対して０度から９０度まで、１．６度／秒の速度で傾けた。この際、水滴が転がり始めたときの膜付きガラス基板の水平面に対する傾斜角度を接触角計（協和界面科学社製ＤＭ－５００）を用いて測定し、水転落角とした。この値が小さいほど、滑水性が高いことになる。９０度傾けても水滴が滑落しないものは「転落せず」と記載した。結果を表１に示す。 (Water falling angle)
Under an environment of 25 ° C. and 40% RH, 5 μL of ion-exchanged water is dropped on the surface of the film-coated glass substrate described later, and the film-coated glass substrate is 1.6 degrees from 0 to 90 degrees with respect to the horizontal plane. Tilt at a speed of / sec. At this time, the inclination angle of the film-coated glass substrate with respect to the horizontal plane when water droplets began to roll was measured using a contact angle meter (DM-500 manufactured by Kyowa Interface Science Co., Ltd.), and the water drop angle was obtained. The smaller this value, the higher the lubricity. Those in which water droplets did not slide even when tilted by 90 degrees were described as “no falls”. The results are shown in Table 1.
（泥脱落性評価試験）
　後述する組成物を、銅基板上にスピンコート法（毎分１，０００回転、３０秒間）により塗布し、１００℃に温度調節したオーブン内で１０分間乾燥させて厚さ１５０μｍの膜を形成し、膜付き銅基板を得た。
　続いてＪＩＳ試験用紛体１－８種（関東ローム焼成品の粉体）と水とを、質量比１：０．６６で混合して、飽和泥水を作製した。
　上記で膜付き銅基板を角度調整可能な台上に水平（０度）に設置して、マイクロピペットを用いて、飽和泥水を１００μＬ滴下した。次いで、膜付き銅基板上の飽和泥水が流れ始めるまで、台の角度を５度ずつ上げた。この際、飽和泥水滴が転がり始めたときの膜付き銅基板の水平面に対する傾斜角度を接触角計（協和界面科学社製ＤＭ－５００）を用いて測定し、泥水転落角とした。この値が小さいほど、泥脱落性が高いことになる。
　また、飽和泥水滴が流れた角度では、飽和泥水滴が流れ始めた時点から、基板上から落ちる時点までの秒数をストップウォッチで測定して、その結果から飽和泥水の移動速度（泥水移動速度）も算出した。結果を表１に示す。
　なお、組成物を塗工しない銅基板について同様の試験を行ったところ、飽和泥水が基板に付着して転落しなかった。 (Mud removal test)
The composition to be described later is applied on a copper substrate by spin coating (1,000 rpm, 30 seconds) and dried in an oven adjusted to a temperature of 100 ° C. for 10 minutes to form a film having a thickness of 150 μm. A copper substrate with a film was obtained.
Subsequently, JIS test powders 1-8 (powdered Kanto loam powder) and water were mixed at a mass ratio of 1: 0.66 to prepare saturated mud water.
The copper substrate with a film was placed horizontally (0 degree) on a table whose angle can be adjusted, and 100 μL of saturated mud was dropped using a micropipette. Next, the angle of the platform was increased by 5 degrees until the saturated mud on the copper substrate with film started to flow. At this time, the tilt angle of the film-coated copper substrate with respect to the horizontal plane when the saturated mud water droplets started to roll was measured using a contact angle meter (DM-500, manufactured by Kyowa Interface Science Co., Ltd.), and the muddy water fall angle was obtained. The smaller this value, the higher the mud shedding.
In addition, at the angle at which the saturated mud droplets flow, the number of seconds from when the saturated mud droplets start flowing to when they fall from the substrate is measured with a stopwatch. ) Was also calculated. The results are shown in Table 1.
In addition, when the same test was done about the copper substrate which does not apply a composition, saturated muddy water adhered to the substrate and did not fall.
（氷・霜付着防止性評価試験）
　長さ４０ｃｍ、外径１２．７ｍｍのＳＵＳ製配管に後述する組成物をディップ法で塗工し、膜付き配管を得た。
　恒温恒湿室内（２５℃、４０％ＲＨ）で、膜付き配管をチラーに接続し、－１０℃までチラー内部の冷媒温度を下げ、その時の配管表面状態を観察した。評価基準は以下とした。結果を表１に示す。Ａ（良好）：着氷なしＢ（可）：一部に薄い着氷ありＣ（不可）：全体的に薄い着氷ありＤ（不可）：全体的に着氷ありＥ（不可）：全体が完全に氷結
　なお、組成物を塗工しない長さ４０ｃｍ、外径１２．７ｍｍのＳＵＳ製配管について同様の試験を行ったところ、全体が完全に氷結した（すなわち、評価基準のＥ）。 (Ice / frost adhesion prevention test)
A composition described later was applied to a SUS pipe having a length of 40 cm and an outer diameter of 12.7 mm by a dip method to obtain a pipe with a film.
In a constant temperature and humidity room (25 ° C., 40% RH), the membrane-coated pipe was connected to the chiller, the refrigerant temperature inside the chiller was lowered to −10 ° C., and the pipe surface condition at that time was observed. The evaluation criteria were as follows. The results are shown in Table 1. A (good): No icing B (possible): Some thin icing C (not possible): Overall thin icing D (not possible): Overall icing E (not possible): Overall Completely icing When a similar test was performed on a SUS pipe having a length of 40 cm and an outer diameter of 12.7 mm where the composition was not applied, the whole was completely frozen (that is, evaluation standard E).
〔材料〕
（単量体）
　共重合体の製造に用いた単量体を以下に示す。
単量体（ａ－１）：ＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯ－ＣＨ２－ＣＦ３
単量体（ｂ－１）：ＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯ－（ＣＨ２）２－（ＣＦ２）５ＣＦ３
単量体（ｃ－１）：「Ｘ－２２－２４２６」（商品名、信越化学社製。前記式（ｃ１）において、Ｘ３がすべて水素原子、Ｒ４がトリメチレン基、Ｒ５、Ｒ６がすべてメチル基、Ｒ７はエポキシ基を有する有機基、ｍの平均値は１５６である化合物）
単量体（ｄ－１）：ＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯ－ＣＨ２－ＯＣＯ－Ｃ（ＣＨ３）＝ＣＨ２
単量体（ｅ－１）：ＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯＨ 〔material〕
(Monomer)
The monomers used for the production of the copolymer are shown below.
Monomer (a-1): CH 2 ═C (CH 3 ) —COO—CH 2 —CF 3
Monomer (b-1): CH 2 ═C (CH 3 ) —COO— (CH 2 ) 2 — (CF 2 ) 5 CF 3
Monomer (c-1): “X-22-2426” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd. In the formula (c1), X 3 is all hydrogen atoms, R 4 is a trimethylene group, R 5 , R 6 Are all methyl groups, R 7 is an organic group having an epoxy group, and the average value of m is 156)
Monomer (d-1): CH 2 ═C (CH 3 ) —COO—CH 2 —OCO—C (CH 3 ) ═CH 2
Monomer (e-1): CH 2 ═C (CH 3 ) —COOH
〔例１〕
　各単量体を表１の比率（質量％）で、かつ合計が１００ｇになるように、１Ｌ重合槽に仕込んだ。次いで、開始剤（和光純薬社製Ｖ－６０１）の１ｇ、および重合溶媒として使用するｍ－ＸＨＦの３９９ｇを仕込んだ。７０℃２４時間の反応を行い、共重合体（Ａ）を含む溶液を得た。なお、共重合体（Ａ）における各単位の含有量（質量％）は、重合に使用した単量体がすべて共重合体を構成するとみなした値である。すなわち、共重合体（Ａ）の各単位の含有量（質量％）は、表１に記載の各単量体の含有量と同じである。
　次いで、得られた溶液をｍ－ＸＨＦでさらに希釈して、共重合体（Ａ）の濃度が２質量％の組成物（Ａ）を得た。
　次いで、組成物（Ａ）をガラス基板上にスピンコート法（毎分１，０００回転、３０秒間）により塗布し、１００℃に温度調節したオーブン内で１０分間乾燥させて厚さ１５０ｎｍの膜を形成し、膜付きガラス基板を得た。
　共重合体（Ａ）の水接触角および水転落角、泥脱落性評価試験および氷・霜付着防止性評価試験結果を表１に示す。 [Example 1]
Each monomer was charged in a 1 L polymerization tank so that the ratio (mass%) in Table 1 was 100 g in total. Next, 1 g of an initiator (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) and 399 g of m-XHF used as a polymerization solvent were charged. Reaction was performed at 70 ° C. for 24 hours to obtain a solution containing the copolymer (A). In addition, content (mass%) of each unit in a copolymer (A) is the value considered that all the monomers used for superposition | polymerization comprise a copolymer. That is, the content (mass%) of each unit of the copolymer (A) is the same as the content of each monomer described in Table 1.
Next, the obtained solution was further diluted with m-XHF to obtain a composition (A) having a copolymer (A) concentration of 2% by mass.
Next, the composition (A) is applied onto a glass substrate by spin coating (1,000 revolutions per minute, 30 seconds) and dried in an oven adjusted to a temperature of 100 ° C. for 10 minutes to form a film having a thickness of 150 nm. The film-formed glass substrate was obtained.
Table 1 shows the results of the water contact angle and water falling angle, mud drop-off property evaluation test and ice / frost adhesion prevention test result of the copolymer (A).
〔例２～６〕
　例１と同様に共重合体、組成物および膜付きガラス基板を得て、各評価を行った。結果を表１に示す。 [Examples 2 to 6]
A copolymer, a composition and a glass substrate with a film were obtained in the same manner as in Example 1, and each evaluation was performed. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の結果から、本発明の共重合体（１）に該当する例１の共重合体、および、本発明の共重合体（２）に該当する例２の共重合体は、水接触角および水転落角が低く、泥脱落性に優れ、氷・霜付着防止性にも優れることを分かった。
　例１の水転落角は例２の水転落角と比較するとかなり低い。これは、単位（ｂ－１）中の炭素数６のペルフルオロアルキル基の方が単位（ａ－１）中の炭素数１のペルフルオロアルキル基よりも結晶性が高いために運動性が低くなり、水滴を移動させにくくしているためと考えられる。
　さらに、全単位に対する単位（ａ－１）と単位（ｂ－１）との合計の割合が７８質量％と同じの共重合体用いた例１、３および５を比較した。単位（ａ－１）と単位（ｂ－１）との合計に対する単位（ａ－１）の割合が３０～７０質量％である例１のみ、水接触角および水転落角が低く、泥脱落性に優れ、氷・霜付着防止性にも優れることを確認した。これは、単位（ｂ－１）中の炭素数６のペルフルオロアルキル基の間に配置される単位（ａ－１）中の炭素数１のペルフルオロアルキル基がスペーサの役割を果たすため、炭素数６のペルフルオロアルキル基の結晶性が低下して、その結果、膜の表面における炭素数６のペルフルオロアルキル基の運動性が増すことが原因と考えられる（Ａ．Ｈｏｚｕｍｉ，　Ｃ．Ｕｒａｔａ，　Ｓｙｎｔｈｅｓｉｏｌｏｇｙ　２０１４，７，１９０～１９８）。 From the results in Table 1, the copolymer of Example 1 corresponding to the copolymer (1) of the present invention and the copolymer of Example 2 corresponding to the copolymer (2) of the present invention were found to have a water contact angle. It was also found that the water falling angle is low, the mud dropping property is excellent, and the ice / frost adhesion preventing property is also excellent.
The water falling angle of Example 1 is considerably lower than that of Example 2. This is because the perfluoroalkyl group having 6 carbon atoms in the unit (b-1) has higher crystallinity than the perfluoroalkyl group having 1 carbon atom in the unit (a-1), and the mobility becomes low. This is thought to be due to the difficulty in moving the water droplets.
Furthermore, Examples 1, 3 and 5 were compared in which the same proportion of the total of units (a-1) and units (b-1) with respect to all units was 78% by mass. Only in Example 1 where the ratio of the unit (a-1) to the total of the unit (a-1) and the unit (b-1) is 30 to 70% by mass, the water contact angle and the water falling angle are low, and the mud shedding property It was confirmed that it was excellent in ice and frost adhesion prevention. This is because the perfluoroalkyl group having 1 carbon atom in the unit (a-1) arranged between the perfluoroalkyl groups having 6 carbon atoms in the unit (b-1) serves as a spacer. The crystallinity of the perfluoroalkyl group is reduced, and as a result, the mobility of the C 6 perfluoroalkyl group on the surface of the film is increased (A. Hozumi, C. Urata, Synthesis 2014, 7 190-198).
　本発明の表面処理剤は、泥脱落性や氷・霜付着防止性が求められるまたは必要とされる各種の用途に用いることができる。泥脱落性に着目すると、自動車、自転車、バイク、カーペットや革靴、外装材等の泥脱落性を付与する表面処理剤として使用可能と考えられる。氷・霜付着防止性に着目すると、エア・コンディショナー等の空調設備のフィンやフィルター、冷凍庫や冷蔵庫、屋外で使用する機器一般、室外機やビニールハウス等の着氷や着雪を防止するための表面処理剤として使用可能と考えられる。
　なお、２０１６年１２月２６日に出願された日本特許出願２０１６－２５１１４９号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The surface treating agent of the present invention can be used for various applications where mud dropping properties and ice / frost adhesion preventing properties are required or required. Focusing on mud shedding, it can be used as a surface treatment agent that imparts mud shedding to automobiles, bicycles, motorcycles, carpets, leather shoes, and exterior materials. Focusing on the prevention of ice and frost adhesion, fins and filters of air conditioners such as air conditioners, freezers and refrigerators, general equipment used outdoors, outdoor units and greenhouses to prevent icing and snow accretion It can be used as a surface treatment agent.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2016-251149 filed on Dec. 26, 2016 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims (13)

  1. 　下記単位（ａ）と下記単位（ｃ）と任意に下記単位（ｂ）とを含み、単位（ａ）と単位（ｂ）との合計に対する単位（ａ）の割合が３０～１００質量％である共重合体であって、共重合体中の全単位に対する単位（ａ）と単位（ｂ）との合計の割合が６０～９０質量％であり、かつ、共重合体中の全単位に対する単位（ｃ）の割合が１０～４０質量％である共重合体を含むことを特徴とする表面処理剤。
    　単位（ａ）：式（ａ）で表される単量体に由来する単位。
    　Ｃ（Ｘ１）２＝ＣＸ１－ＣＯＯ－Ｒ１－ＲＦ１・・・（ａ）
    〔式（ａ）中、３つのＸ１はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ１は炭素数１～６のアルキレン基であり、ＲＦ１は炭素数１～３のペルフルオロアルキル基である。〕
    　単位（ｂ）：式（ｂ）で表される単量体に由来する単位。
    　Ｃ（Ｘ２）２＝ＣＸ２－ＣＯＯ－Ｒ２－ＲＦ２・・・（ｂ）
    〔式（ｂ）中、３つのＸ２はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ２は炭素数１～６のアルキレン基であり、ＲＦ２は炭素数４～６のペルフルオロアルキル基である。〕
    　単位（ｃ）：式（ｃ）で表される単量体に由来する単位。
    　Ｃ（Ｘ３）２＝ＣＸ３－ＣＯＯ－Ｒ３・・・（ｃ）
    〔式（ｃ）中、３つのＸ３はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ３はオルガノポリシロキサン鎖を有する基である。〕     The following unit (a), the following unit (c), and optionally the following unit (b) are included, and the ratio of the unit (a) to the total of the unit (a) and the unit (b) is 30 to 100% by mass. A copolymer, wherein the total proportion of the unit (a) and the unit (b) with respect to all the units in the copolymer is 60 to 90% by mass, and the unit with respect to all the units in the copolymer ( A surface treatment agent comprising a copolymer having a ratio of c) of 10 to 40% by mass.
    Unit (a): A unit derived from the monomer represented by formula (a).
    C (X 1 ) 2 = CX 1 —COO—R 1 —R F1 (a)
    [In the formula (a), three X 1 s are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom; R 1 is an alkylene group having 1 to 6 carbon atoms; F1 is a perfluoroalkyl group having 1 to 3 carbon atoms. ]
    Unit (b): a unit derived from the monomer represented by formula (b).
    C (X 2 ) 2 = CX 2 —COO—R 2 —R F2 (b)
    [In the formula (b), three X 2 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom; R 2 is an alkylene group having 1 to 6 carbon atoms; F2 is a C 4-6 perfluoroalkyl group. ]
    Unit (c): a unit derived from the monomer represented by the formula (c).
    C (X 3 ) 2 = CX 3 —COO—R 3 (c)
    [In the formula (c), three X 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 3 is a group having an organopolysiloxane chain. ]
  2. 　前記単位（ａ）と単位（ｂ）との合計に対する単位（ａ）の割合が３０～７０質量％である、請求項１に記載の表面処理剤。 The surface treating agent according to claim 1, wherein the ratio of the unit (a) to the total of the unit (a) and the unit (b) is 30 to 70% by mass.
  3. 　前記共重合体が単位（ｂ）を含まない共重合体である、請求項１に記載の表面処理剤。 The surface treatment agent according to claim 1, wherein the copolymer is a copolymer containing no unit (b).
  4. 　前記単位（ｃ）が下式（ｃ１）で表される単量体に由来する単位である、請求項１～３のいずれか一項に記載の表面処理剤。
    　Ｃ（Ｘ３）２＝ＣＸ３－ＣＯＯ－Ｒ４－（Ｓｉ（Ｒ５）２Ｏ）ｍ－Ｓｉ（Ｒ６）２－Ｒ７・・・（ｃ１）
    〔式（ｃ１）中、３つのＸ３はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ４は炭素数１～６のアルキレン基であり、２つのＲ５はそれぞれ独立に炭素数１～３のアルキル基であり、２つのＲ６はそれぞれ独立に炭素数１～３のアルキル基であり、Ｒ７は官能性基を有していてもよい１価の有機基であり、ｍは１０～８００の整数である。〕     The surface treating agent according to any one of claims 1 to 3, wherein the unit (c) is a unit derived from a monomer represented by the following formula (c1).
    C (X 3 ) 2 = CX 3 —COO—R 4 — (Si (R 5 ) 2 O) m —Si (R 6 ) 2 —R 7 (c1)
    [In the formula (c1), three X 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, R 4 is an alkylene group having 1 to 6 carbon atoms, Each R 5 is independently an alkyl group having 1 to 3 carbon atoms, two R 6 are each independently an alkyl group having 1 to 3 carbon atoms, and R 7 may have a functional group It is a monovalent organic group, and m is an integer of 10 to 800. ]
  5. 　前記Ｒ７がエポキシ基を有する有機基である、請求項４に記載の表面処理剤。 The surface treating agent according to claim 4, wherein R 7 is an organic group having an epoxy group.
  6. 　前記共重合体がさらに単位（ａ）、単位（ｂ）および単位（ｃ）以外の単量体単位の少なくとも１種を含み、該単量体単位の合計の割合が、共重合体中の全単位に対して０．１～５質量％である、請求項１～５のいずれか一項に記載の表面処理剤。 The copolymer further contains at least one monomer unit other than the unit (a), the unit (b) and the unit (c), and the total proportion of the monomer units is the total amount in the copolymer. The surface treating agent according to any one of claims 1 to 5, wherein the amount is 0.1 to 5% by mass with respect to the unit.
  7. 　前記単位（ａ）、単位（ｂ）および単位（ｃ）以外の単量体単位の少なくとも一部が、下記単位（ｄ）である、請求項６に記載の表面処理剤。
    　単位（ｄ）：式（ｄ）で表される単量体に由来する単位。
    　Ｃ（Ｘ４）２＝ＣＸ４－ＣＯＯ－Ｒ９－ＯＣＯ－ＣＸ５＝Ｃ（Ｘ５）２・・・（ｄ）
    〔式（ｄ）中、３つのＸ４はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、３つのＸ５はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ９は炭素数１～６のアルキレン基である。〕     The surface treating agent according to claim 6, wherein at least a part of the monomer units other than the unit (a), the unit (b) and the unit (c) is the following unit (d).
    Unit (d): a unit derived from the monomer represented by formula (d).
    C (X 4 ) 2 = CX 4 —COO—R 9 —OCO—CX 5 = C (X 5 ) 2 ... (D)
    [In the formula (d), three X 4 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and three X 5 are each independently a hydrogen atom, having 1 to 3 carbon atoms. 3 is an alkyl group, a chlorine atom or a fluorine atom, and R 9 is an alkylene group having 1 to 6 carbon atoms. ]
  8. 　前記単位（ａ）、単位（ｂ）および単位（ｃ）以外の単量体単位の少なくとも一部が、下記単位（ｅ）である、請求項６に記載の表面処理剤。
    　単位（ｅ）：式（ｅ）で表される単量体に由来する単位。
    　Ｃ（Ｘ６）２＝ＣＸ６－Ｒ１０－ＣＯＯＨ・・・（ｅ）
    〔式（ｅ）中、３つのＸ６はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ１０は単結合または炭素数１～１０のアルキル基である。〕     The surface treating agent according to claim 6, wherein at least a part of the monomer units other than the unit (a), the unit (b) and the unit (c) is the following unit (e).
    Unit (e): a unit derived from the monomer represented by formula (e).
    C (X 6 ) 2 = CX 6 -R 10 -COOH (e)
    [In the formula (e), three X 6 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 10 is a single bond or an alkyl group having 1 to 10 carbon atoms. is there. ]
  9. 　前記単位（ａ）、単位（ｂ）および単位（ｃ）以外の単量体単位として下記単位（ｄ）と下記単位（ｅ）とを含む、請求項６に記載の表面処理剤。
    　単位（ｄ）：式（ｄ）で表される単量体に由来する単位。
    　Ｃ（Ｘ４）２＝ＣＸ４－ＣＯＯ－Ｒ９－ＯＣＯ－ＣＸ５＝Ｃ（Ｘ５）２・・・（ｄ）
    〔式（ｄ）中、３つのＸ４はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、３つのＸ５はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ９は炭素数１～６のアルキレン基である。〕
    　単位（ｅ）：式（ｅ）で表される単量体に由来する単位。
    　Ｃ（Ｘ６）２＝ＣＸ６－Ｒ１０－ＣＯＯＨ・・・（ｅ）
    〔式（ｅ）中、３つのＸ６はそれぞれ独立に水素原子、炭素数１～３のアルキル基、塩素原子またはフッ素原子であり、Ｒ１０は単結合または炭素数１～１０のアルキル基である。〕     The surface treating agent according to claim 6, comprising the following unit (d) and the following unit (e) as monomer units other than the unit (a), the unit (b) and the unit (c).
    Unit (d): a unit derived from the monomer represented by formula (d).
    C (X 4 ) 2 = CX 4 —COO—R 9 —OCO—CX 5 = C (X 5 ) 2 ... (D)
    [In the formula (d), three X 4 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and three X 5 are each independently a hydrogen atom, having 1 to 3 carbon atoms. 3 is an alkyl group, a chlorine atom or a fluorine atom, and R 9 is an alkylene group having 1 to 6 carbon atoms. ]
    Unit (e): a unit derived from the monomer represented by formula (e).
    C (X 6 ) 2 = CX 6 -R 10 -COOH (e)
    [In the formula (e), three X 6 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a chlorine atom or a fluorine atom, and R 10 is a single bond or an alkyl group having 1 to 10 carbon atoms. is there. ]
  10. 　さらに溶媒を含む、請求項１～９のいずれか一項に記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 9, further comprising a solvent.
  11. 　前記表面処理剤が、基材の被処理面に前記共重合体の膜を形成することにより、基材表面に、未処理面と比較して、水性物質の付着性を抑制しかつ付着した水性物質の脱落性を向上させる特性を付与する、表面処理剤である、請求項１～１０のいずれか一項に記載の表面処理剤。 The surface treatment agent forms a film of the copolymer on the surface to be treated of the substrate, thereby suppressing the adhesion of the aqueous substance and adhering to the surface of the substrate as compared with the untreated surface. The surface treatment agent according to any one of claims 1 to 10, which is a surface treatment agent that imparts a property of improving the detachability of a substance.
  12. 　請求項１～１１のいずれか一項に記載の表面処理剤から形成された共重合体の膜を基材表面に有することを特徴とする物品。 An article comprising a copolymer film formed from the surface treating agent according to any one of claims 1 to 11 on a substrate surface.
  13. 　前記膜が、該膜の表面に氷および霜が付着し難い特性、該膜の表面に付着した水性の泥が脱落しやすい特性、または前記２つの特性の両方を有する、請求項１２に記載の物品。 13. The film according to claim 12, wherein the film has a characteristic that ice and frost do not easily adhere to the surface of the film, a characteristic that aqueous mud adhering to the surface of the film easily falls off, or both of the two characteristics. Goods.
PCT/JP2017/046444 2016-12-26 2017-12-25 Surface treatment agent WO2018123978A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0384069A (en) * 1989-08-28 1991-04-09 Ishikawajima Harima Heavy Ind Co Ltd Ice accretion-preventing paint
JP2007284644A (en) * 2006-04-20 2007-11-01 Agc Seimi Chemical Co Ltd Coating composition
JP2011516617A (en) * 2008-03-31 2011-05-26 ダイキン工業株式会社 Fluorosilicone dispersion and fluorine-containing silicon-containing surface treatment agent
WO2011129015A1 (en) * 2010-04-16 2011-10-20 株式会社ネオス Imparting agent for antifouling properties
JP2013185072A (en) * 2012-03-08 2013-09-19 Agc Seimi Chemical Co Ltd Water-slippery surface treating agent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0384069A (en) * 1989-08-28 1991-04-09 Ishikawajima Harima Heavy Ind Co Ltd Ice accretion-preventing paint
JP2007284644A (en) * 2006-04-20 2007-11-01 Agc Seimi Chemical Co Ltd Coating composition
JP2011516617A (en) * 2008-03-31 2011-05-26 ダイキン工業株式会社 Fluorosilicone dispersion and fluorine-containing silicon-containing surface treatment agent
WO2011129015A1 (en) * 2010-04-16 2011-10-20 株式会社ネオス Imparting agent for antifouling properties
JP2013185072A (en) * 2012-03-08 2013-09-19 Agc Seimi Chemical Co Ltd Water-slippery surface treating agent

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