WO2018123978A1 - Agent de traitement de surface - Google Patents

Agent de traitement de surface 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
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English (en)
Japanese (ja)
Inventor
龍二郎 山崎
歩 鈴木
知弘 高橋
好彦 坂根
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旭硝子株式会社
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Publication of WO2018123978A1 publication Critical patent/WO2018123978A1/fr

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    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Combustion & Propulsion (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention fournit un matériau qui permet de former un film doté d'excellentes propriétés de détachement de boue et propriétés anti-adhésion sur verglas et gelée blanche. Plus précisément, l'invention concerne un agent de traitement de surface qui est caractéristique en ce qu'il consiste en un copolymère contenant une unité (a) ayant un groupe perfluoroalkyle de 1 à 3 atomes de carbone, une unité (c) ayant un groupe avec une chaîne organopolysiloxane, et de manière facultative une unité (b) ayant un groupe perfluoroalkyle de 4 à 6 atomes de carbone, la proportion d'unité (a) par rapport au total de la masse de l'unité (a) et de l'unité (b), est comprise entre 30 et 100% en masse. La proportion totale d'unité (a) et d'unité (b) par rapport à l'ensemble des unités dans le copolymère, est comprise entre 60 et 90% en masse, et la proportion d'unité (c) par rapport à l'ensemble des unités dans le copolymère, est comprise entre 10 et 40% en masse.
PCT/JP2017/046444 2016-12-26 2017-12-25 Agent de traitement de surface WO2018123978A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0384069A (ja) * 1989-08-28 1991-04-09 Ishikawajima Harima Heavy Ind Co Ltd 着氷防止塗料
JP2007284644A (ja) * 2006-04-20 2007-11-01 Agc Seimi Chemical Co Ltd コーティング組成物
JP2011516617A (ja) * 2008-03-31 2011-05-26 ダイキン工業株式会社 フルオロシリコーン分散液および含フッ素含ケイ素表面処理剤
WO2011129015A1 (fr) * 2010-04-16 2011-10-20 株式会社ネオス Agent antisalissure
JP2013185072A (ja) * 2012-03-08 2013-09-19 Agc Seimi Chemical Co Ltd 滑水性表面処理剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0384069A (ja) * 1989-08-28 1991-04-09 Ishikawajima Harima Heavy Ind Co Ltd 着氷防止塗料
JP2007284644A (ja) * 2006-04-20 2007-11-01 Agc Seimi Chemical Co Ltd コーティング組成物
JP2011516617A (ja) * 2008-03-31 2011-05-26 ダイキン工業株式会社 フルオロシリコーン分散液および含フッ素含ケイ素表面処理剤
WO2011129015A1 (fr) * 2010-04-16 2011-10-20 株式会社ネオス Agent antisalissure
JP2013185072A (ja) * 2012-03-08 2013-09-19 Agc Seimi Chemical Co Ltd 滑水性表面処理剤

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