Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
  • C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D171/02—Polyalkylene oxides

Definitions

• the present invention relates to a composition.
• the wear resistance of the film is required.
• Patent Document 1 discloses (A) a hydrolyzable group-containing silane modified with a fluorooxyalkylene group-containing polymer and / or a partial hydrolysis-condensation product thereof, and an average of the component (A).
• a fluorine-containing coating agent comprising (B) a fluorooxyalkylene group-containing polymer having an average molecular weight equal to or lower than the molecular weight is disclosed.
• Patent Document 2 (A) a hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof and (B) a fluoropolyether-polysiloxane copolymer are modified.
• a fluorine-containing coating agent containing the hydrolyzable group-containing silane and / or a partially hydrolyzed condensate thereof is disclosed.
• Patent Document 1 is evaluated for wear resistance, there is still room for improvement, and Patent Document 2 has not been examined for wear resistance. Further, in addition to wear resistance, visibility may be required for a film having water and oil repellency, but these physical properties have not been sufficiently expressed.
• the present invention has been made in view of the above problems, and an object of the present invention is to provide a composition capable of obtaining a water- and oil-repellent film having good wear resistance and visibility.
• the present invention provides a compound (A) in which a monovalent group having a perfluoropolyether structure and a hydrolyzable group are bonded to a silicon atom, in a number average molecular weight of 0.05 to 0.15% by mass.
• A a polyalkylene glycol having a molecular weight of 10,000 to 30,000, wherein a hydrogen atom of the OH group may be substituted with a fluoroalkyl group, and a hydrogen atom of at least a part of the alkylene group is substituted with a fluorine atom
• B is a composition containing 0.02 to 0.15% by mass.
• composition of the present invention preferably further contains a fluorinated solvent (C) having a molecular weight of 1000 or less.
• the hydrolyzable group possessed by the compound (A) is preferably at least one selected from the group consisting of an alkoxy group, an acetoxy group and a halogen atom.
• the compound (A) is also preferably at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2).
• Rf represents a fluorine atom or an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms
• Each Rf 2 independently represents a fluorine atom or an alkyl group having 1 to 20 carbon atoms substituted by one or more fluorine atoms
• Each R 3 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• Each R 4 independently represents an alkyl group having 1 to 20 carbon atoms
• Each D is independently —O—, —COO—, —OCO—, —NR—, —NRCO—, —CONR— (where R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom).
• Each E independently represents an alkoxy group, an acetoxy group, or a halogen atom; a2, b2, c2, d2, and e2 are each independently an integer of 0 to 600, and the total value of a2, b2, c2, d2, and e2 is 13 or more, n is an integer of 1 to 3,
• the order of the repeating units a2, b2, c2, d2, and e2 and parenthesized is arbitrary in the formula as long as at least a part of the repeating units are arranged in the order in which the perfluoropolyether structure is formed.
• Rf represents a fluorine atom or an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms
• Each Rf 3 independently represents a fluorine atom or an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms
• Each R 5 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• Each R 6 independently represents an alkyl group having 1 to 20 carbon atoms
• G is independently —O—, —COO—, —OCO—, —NR—, —NRCO—, —CONR— (where R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms).
• Each J independently represents an alkoxy group, an acetoxy group, or a halogen atom
• Each Y independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• Each Z independently represents a hydrogen atom or a halogen atom
• a3, b3, c3, d3, and e3 are each independently an integer of 0 to 600, and the total value of a3, b3, c3, d3, and e3 is 13 or more
• h3 is an integer of 0 or more and 2 or less
• p is an integer of 1 to 3
• q is an integer from 1 to 20
• the order of the repeating units a3, b3, c3, d3, e3 and parenthesized is arbitrary in the formula as long as at least a part of the repeating units are arranged in the order of forming the perfluoropolyether structure.
• composition of the present invention preferably further contains a hydrolyzable oligomer (D2), and the hydrolyzable oligomer (D2) is more preferably a compound represented by the following formula (10).
• each X independently represents a hydrolyzable group, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms, and g1 is 0 or more and 100 or less. Is an integer]
• the present invention also includes a film formed from any of the compositions described above.
• the compound (A) characterized by a perfluoropolyether structure and the polyalkylene glycol (B) having a number average molecular weight of 10,000 to 30,000 are each contained in a predetermined amount.
• the film obtained from this composition has water and oil repellency and is excellent in wear resistance and visibility.
• the composition of the present invention contains a compound (A) characterized by a perfluoropolyether structure and a predetermined polyalkylene glycol (B) having a number average molecular weight of 10,000 to 30,000.
• the perfluoropolyether structure of the compound (A) can exhibit water and oil repellency, and the polyalkylene glycol (B) that satisfies the predetermined requirements can be used, whereby the wear resistance and visibility of the coating can be improved.
• the compound (A) may be any compound containing fluorine and capable of forming a film matrix by bonding with the compound (A) or other monomers through a polymerization reaction (particularly polycondensation reaction).
• the compound (A) is preferably a compound containing a fluorine-containing group and a hydrolyzable group.
• the compound (A) a monovalent group having a perfluoropolyether structure and a hydrolyzable group are preferable.
• a compound in which a group is bonded to a silicon atom is used.
• the perfluoropolyether structure is a structure in which all hydrogen atoms of a polyalkylene ether group or a polyalkylene glycol dialkyl ether residue are replaced with fluorine atoms, a perfluoro polyalkylene ether group, or a perfluoro polyalkylene glycol dialkyl. It can also be called an ether residue.
• the perfluoropolyether structure has water and oil repellency.
• the number of carbon atoms contained in the longest straight chain portion of the perfluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, and more preferably 20 or more.
• the upper limit of the carbon number is not particularly limited, and may be about 200, for example.
• the monovalent group having the perfluoropolyether structure is bonded to a silicon atom.
• An appropriate linking group may be present on the side where the perfluoropolyether structure is bonded to the silicon atom, and the perfluoropolyether structure may be directly bonded to the silicon atom without the linking group.
• the linking group for example, a hydrocarbon group such as an alkylene group or an aromatic hydrocarbon group, a (poly) alkylene glycol group, or a group in which a part of these hydrogen atoms is substituted with F, and these are appropriately linked. And the like.
• the carbon number of the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 10 or less.
• a plurality of silicon atoms may be bonded to one linking group, and a plurality of perfluoroalkyl groups or perfluoropolyether groups may be bonded to one linking group.
• the number of monovalent groups having the perfluoropolyether structure bonded to the silicon atom may be one or more, may be 2 or 3, but is preferably 1 or 2. It is particularly preferred.
• a hydrolyzable group is bonded to a silicon atom, and the hydrolyzable group is separated from each other or between the compound (A) and the group through the hydrolysis / dehydration condensation reaction. It has an action of binding active hydrogen (such as hydroxyl group) on the surface of the material.
• active hydrogen such as hydroxyl group
• examples of such a hydrolyzable group include an alkoxy group (particularly an alkoxy group having 1 to 4 carbon atoms), an acetoxy group, a halogen atom (particularly a chlorine atom), and the like.
• Preferred hydrolyzable groups are an alkoxy group and a halogen atom, and a methoxy group, an ethoxy group, and a chlorine atom are particularly preferable.
• the number of hydrolyzable groups bonded to the silicon atom may be one or more, and may be 2 or 3. However, 2 or 3 is preferable, and 3 is particularly preferable.
• different hydrolyzable groups may be bonded to the silicon atom, but the same hydrolyzable group is bonded to the silicon atom.
• the total number of fluorine-containing groups bonded to silicon atoms (monovalent groups having a perfluoropolyether structure) and hydrolyzable groups is usually 4, but may be 2 or 3 (particularly 3). .
• an alkyl group particularly an alkyl group having 1 to 4 carbon atoms
• a hydrogen atom, an isocyanate group, or the like can be bonded to the remaining bonds.
• the monovalent group having a perfluoropolyether structure of the compound (A) may be linear or have a side chain.
• Examples of the compound (A) include a compound represented by the following formula (1).
• Rf represents a fluorine atom or an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms.
• Rf is preferably an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms.
• Rf 2 each independently represents a fluorine atom or an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms.
• Rf 2 is preferably each independently a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms, more preferably all fluorine atoms.
• R 3 each independently represents a hydrogen atom or a lower alkyl group.
• Each R 3 is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably all hydrogen atoms.
• Each R 4 independently represents an alkyl group having 1 to 20 carbon atoms.
• R 4 is preferably an alkyl group having 1 to 5 carbon atoms.
• Each D independently represents —O—, —COO—, —OCO—, —NR—, —NRCO— or —CONR— (where R represents a hydrogen atom, a lower alkyl group or a lower fluorine-containing alkyl group).
• R represents a hydrogen atom, a lower alkyl group or a lower fluorine-containing alkyl group.
• D is preferably each independently —COO—, —O— or —OCO—, more preferably —O—.
• E represents a hydrolyzable group each independently.
• E is preferably an alkoxy group having 1 to 4 carbon atoms, an acetoxy group, or a halogen atom, and particularly preferably a methoxy group, an ethoxy group, or a chlorine atom.
• a2, b2, c2, d2, and e2 are each independently an integer of 0 to 600, and the total value of a2, b2, c2, d2, and e2 is 13 or more.
• the order of the repeating units a2, b2, c2, d2, e2 and parenthesized is arbitrary in the formula as long as they are arranged in the order of forming a perfluoropolyether structure at least partially,
• the repeating unit enclosed in parentheses with b2 on the most fixed end side (side bonded to the silicon atom of the fluorine-containing group) is the repeating unit enclosed in parentheses with a2 on the most free end side Repeating units located on the free end side, more preferably the most fixed end side b2 or d2 and parenthesized, the most free end side a2 or c2 parenthesis Located on the free end side of the repeating unit.
• n is an integer of 1 or more and 3 or less. n is preferably 2 or
• Rf is a perfluoroalkyl group having 1 to 5 carbon atoms
• Rf 2 is all fluorine atom
• D is all —O—
• E is methoxy group, ethoxy group, or chlorine atom (particularly methoxy group) Or ethoxy group)
• a2 c2 and d2 are all 0, n is 3, and e2 is preferably 4 or more and 600 or less.
• Examples of the compound (A) represented by the formula (1) include a compound represented by the following formula (1-1).
• R 10 is a perfluoroalkyl group having 1 to 5 carbon atoms
• R 11 is a perfluoroalkylene group having 1 to 5 carbon atoms
• R 12 is 1 carbon atom.
• R 13 is an alkylene group having 1 to 3 carbon atoms
• R 14 is an alkyl group having 1 to 3 carbon atoms
• z2 and z3 are both 1 to 3 It is an integer
• z1 is a value set so that the compound represented by the formula (1-1) can maintain a liquid at normal pressure.
• Rf represents a fluorine atom or an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms.
• Rf is preferably an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms.
• Rf 3 each independently represents a fluorine atom or an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms.
• Rf 3 is preferably each independently a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms, more preferably all fluorine atoms.
• R 5 each independently represents a hydrogen atom or a lower alkyl group.
• R 5 is preferably each independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably all hydrogen atoms.
• R 6 independently represents an alkyl group having 1 to 20 carbon atoms.
• R 6 is preferably an alkyl group having 1 to 5 carbon atoms.
• G independently represents —O—, —COO—, —OCO—, —NR—, —NRCO— or —CONR— (R represents a hydrogen atom, a lower alkyl group or a lower fluorine-containing alkyl group).
• G is preferably each independently —COO—, —O—, —OCO—, more preferably all —O—.
• J independently represents a hydrolyzable group. J is preferably an alkoxy group, an acetoxy group, or a halogen atom, and particularly preferably a methoxy group, an ethoxy group, or a chlorine atom.
• Y each independently represents a hydrogen atom or a lower alkyl group.
• Y is preferably independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably all hydrogen atoms.
• Z each independently represents a hydrogen atom or a halogen atom.
• Z is preferably a hydrogen atom.
• a3, b3, c3, d3, and e3 are each independently an integer of 0 or more and 600 or less, and the total value of a3, b3, c3, d3, and e3 is 13 or more.
• a3, c3 and d3 are each independently 1/2 or less of b3, more preferably 1/4 or less, more preferably c3 or d3 is 0, and particularly preferably c3 and d3 are 0. It is.
• e3 is preferably not less than 1/5 of the total value of a3, b3, c3, and d3, and not more than the total value of a3, b3, c3, and d3.
• b3 is preferably 20 or more and 600 or less, more preferably 20 or more and 200 or less, and still more preferably 50 or more and 200 or less.
• e3 is preferably 4 or more and 600 or less, more preferably 4 or more and 200 or less, and still more preferably 10 or more and 200 or less.
• the total value of a3, b3, c3, d3, and e3 is preferably 20 or more and 600 or less, preferably 20 or more and 200 or less, and more preferably 50 or more and 200 or less.
• h3 is an integer of 0 or more and 2 or less, preferably 0 or more and 1 or less, q is an integer of 1 or more and 20 or less, preferably 1 or more and 18 or less. More preferably, it is 2 or more and 15 or less.
• each repeating unit with parentheses a3, b3, c3, d3, e3 is arbitrary in the formula as long as it is at least partially arranged in the order of forming a perfluoropolyether structure
• the repeating unit enclosed in parentheses with b3 on the most fixed end side is the repeating unit enclosed in parentheses with a3 on the most free end side
• p is an integer of 1 to 3, preferably 2 to 3, more preferably 3.
• lower means having 1 to 4 carbon atoms.
• Rf is a perfluoroalkyl group having 1 to 5 carbon atoms
• Rf 3 is all fluorine atom
• G is all —O—
• J is methoxy group, ethoxy group, or chlorine atom (particularly methoxy group or Ethoxy group)
• Y and Z are all hydrogen atoms
• a3 is 0,
• b3 is 30 to 150 (more preferably 80 to 140)
• e3 is 30 to 60
• c3 and d3 are 0, and
• h3 is 0 or more and 1 or less ( In particular, 0)
• p is 3, and q is preferably 1 to 10.
• Examples of the compound (A) represented by the above formula (2) include a compound of the following formula (2-1).
• R 20 is a perfluoroalkyl group having 2 to 6 carbon atoms
• R 21 and R 22 are each independently a perfluoroalkylene group having 2 to 6 carbon atoms
• 23 is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms
• R 24 is an alkyl group having 1 to 3 carbon atoms.
• R 20 , R 21 , R 22 and R 23 each independently preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
• x1 is 5 to 70
• x2 is 1 to 5
• x3 is 1 to 10.
• x1 is preferably 10 to 60, more preferably 20 to 50
• x2 is preferably 1 to 4, more preferably 1 to 3, and
• x3 is preferably 1 to 8, and more preferably 1 to 6.
• the content of the compound (A) in the composition of the present invention is 0.05 to 0.15% by mass.
• the content of the compound (A) is less than 0.05% by mass, good water / oil repellency cannot be obtained.
• the content of the compound (A) exceeds 0.15% by mass HAZE becomes high and visibility is lowered.
• the lower limit of the content of the compound (A) is preferably 0.06% by mass or more, and more preferably 0.07% by mass or more.
• the upper limit of the content of the compound (A) is preferably 0.13% by mass or less, more preferably 0.11% by mass or less.
• the hydrogen atom of the OH group may be substituted with a fluoroalkyl group, and at least a part of the alkylene groups are substituted with fluorine atoms.
• the hydrogen atom of the OH group is substituted, it is preferably substituted with a fluoroalkyl group, more preferably substituted with a perfluoroalkyl group, and further substituted with a trifluoromethyl group. preferable.
• it is preferable that at least a part of the hydrogen atoms of the alkylene group is substituted with fluorine atoms, and particularly it contains a perfluorooxyalkylene unit.
• the hydrogen atom of the OH group is substituted with a trifluoromethyl group
• the polyalkylene glycol in which all the hydrogen atoms of the alkylene group are substituted with fluorine atoms, or the hydrogen atom of the OH group is not substituted
• Polyalkylene glycols in which only some of the hydrogen atoms of the alkylene group are substituted with fluorine atoms are preferred.
• Examples of the polyalkylene glycol (B) include a compound represented by the following formula (3).
• a, b, c and d are all symbols representing repeating units, and the range can be appropriately set within the range where the liquid can be maintained at normal pressure. Moreover, the repeating units enclosed by a, b, c, and d may be repeated at random.
• X is an alkyl group having 1 to 16 carbon atoms in which one or more hydrogen atoms may be substituted with fluorine atoms
• Y is a carbon in which one or more hydrogen atoms may be substituted with fluorine atoms. Represents an alkoxy group of formula 1 to 16, or an OH group.
• — (OC 4 F 8 ) — represents — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-and-(OCF Any of (CF 3 ) CF (CF 3 )) — may be used, and — (OCF 2 CF 2 CF 2 CF 2 ) — is preferred.
• — (OC 3 F 6 ) — is any of — (OCF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 ) — and — (OCF 2 CF (CF 3 )) —. Of these, — (OCF 2 CF 2 CF 2 ) — is preferable. — (OC 2 F 4 ) — may be either — (OCF 2 CF 2 ) — or — (OCF (CF 3 )) —.
• X is preferably an alkyl group having 1 to 3 carbon atoms (especially a trifluoromethyl group) in which one or more hydrogen atoms may be substituted by fluorine atoms
• Y is preferably one or more hydrogen atoms. Is an alkoxy group having 1 to 3 carbon atoms (particularly a trifluoromethoxy group) or an OH group which may be substituted with a fluorine atom.
• examples of the polyalkylene glycol (B) include a compound represented by the following formula (4).
• p, q, m, and n are all symbols representing repeating units, and the range can be appropriately set within the range where the liquid can be maintained at normal pressure. Further, the repeating unit enclosed by p and the repeating unit enclosed by q may be repeated at random.
• the polyalkylene glycol (B) has a number average molecular weight of 10,000 to 30,000.
• the number average molecular weight is less than 10,000, the wear resistance of the resulting film is deteriorated.
• the number average molecular weight exceeds 30000, HAZE becomes high and visibility is lowered.
• the lower limit of the number average molecular weight of the polyalkylene glycol (B) is preferably 11000 or more, more preferably 12000 or more.
• the upper limit of the number average molecular weight is preferably 25000 or less, more preferably 20000 or less.
• the content of polyalkylene glycol (B) in the composition of the present invention is 0.02 to 0.15% by mass.
• the lower limit of the content of polyalkylene glycol (B) is preferably 0.03% by mass or more, and more preferably 0.04% by mass or more.
• the upper limit of the content of polyalkylene glycol (B) is preferably 0.13% by mass or less, and more preferably 0.10% by mass or less.
• composition of the present invention preferably further contains a fluorine-based solvent (C) having a molecular weight of 1000 or less in addition to the above-described compound (A) and polyoxyalkylene glycol (B).
• C fluorine-based solvent having a molecular weight of 1000 or less in addition to the above-described compound (A) and polyoxyalkylene glycol (B).
• the fluorinated solvent (C) for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated aromatic solvent or the like can be used, and the boiling point is particularly preferably 100 ° C. or higher.
• the fluorinated ether solvent is preferably a hydrofluoroether such as fluoroalkyl (especially a perfluoroalkyl group having 2 to 6 carbon atoms) -alkyl (especially methyl group or ethyl group) ether.
• fluoroalkyl especially a perfluoroalkyl group having 2 to 6 carbon atoms
• -alkyl especially methyl group or ethyl group
• ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether examples include Novec (registered trademark) 7200 (manufactured by 3M, molecular weight of about 264, boiling point: 76 ° C.).
• the fluorinated amine solvent an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group is preferred, and a third in which all hydrogen atoms of ammonia are substituted with fluoroalkyl groups (particularly perfluoroalkyl groups).
• Secondary amines are preferred, and specific examples include tris (heptafluoropropyl) amine represented by the following formula (7), and Florinate (registered trademark) FC-3283 (molecular weight: about 521, boiling point: 128 ° C.) corresponds to this.
• fluorinated aromatic solvent examples include 1,3-bis (trifluoromethylbenzene) (boiling point: about 116 ° C.) represented by the following formula (8).
• hydrochlorofluorocarbons such as Asahi Clin AK225 (Asahi Glass Co., Ltd.), hydrofluorocarbons such as Asahi Clin AC2000 (Asahi Glass Co., Ltd.) and the like can be used.
• the molecular weight of the fluorine-based solvent (C) is preferably 900 or less, more preferably 800 or less, and the lower limit is not particularly limited, but is about 300, for example.
• the content of the fluorinated solvent (C) in the composition of the present invention is, for example, 90% by mass or more, more preferably 93% by mass or more, and further preferably 95% by mass or more.
• composition of the present invention may contain at least one of fluoroalkylsilane (D1) and hydrolyzable silane oligomer (D2).
• D1 and (D2) may be high boiling point compounds exhibiting a predetermined vapor pressure. That is, (D1) and (D2) are preferably high-boiling compounds whose vapor pressure at a temperature of 100 ° C. is 1 atm or less.
• a high boiling point compound does not need to have a boiling point, when it has a boiling point, the compound in which the boiling point becomes 100 degreeC or more corresponds to the said compound.
• the temperature at which the vapor pressure is 1 atm or higher is 110 ° C. or higher, more preferably 120 ° C. or higher, and still more preferably 130 ° C. or higher.
• the upper limit of the temperature at which the vapor pressure becomes 1 atm or higher is not particularly limited, and may be a compound that starts decomposition before the vapor pressure becomes 1 atm or more.
• the fluoroalkylsilane (D1) is preferably a compound in which a hydrolyzable group is bonded to the silicon atom of the fluoroalkylsilane.
• the fluoroalkyl group of the fluoroalkylsilane is preferably a group having a fluoroalkyl group at the end, and particularly preferably a group having a terminal being a perfluoroalkyl group such as a trifluoromethyl group.
• fluoroalkyl group examples include fluoromethyl group, fluoroethyl group, fluoropropyl group, fluorobutyl group, fluoropentyl group, fluorohexyl group, fluoroheptyl group, fluorooctyl group, fluorononyl group, fluorodecyl group, fluoro Examples thereof include a fluoroalkyl group having 1 to 12 carbon atoms such as an undecyl group and a fluorododecyl group.
• hydrolyzable group In the case where a hydrolyzable group is bonded to the silicon atom of the fluoroalkylsilane of (D1), examples of the hydrolyzable group include the same hydrolyzable groups as exemplified for the compound (A), Preferred hydrolyzable groups are an alkoxy group and a halogen atom, and a methoxy group, an ethoxy group, and a chlorine atom are particularly preferable. When there are a plurality of hydrolyzable groups, they may be the same or different, but are preferably the same.
• the total number of fluoroalkyl groups and hydrolyzable groups bonded to the silicon atom is preferably 4.
• the number of fluoroalkyl groups is 3, the number of hydrolyzable groups is 1, the fluoroalkyl group and
• the number of hydrolyzable groups may be 2 and the number of fluoroalkyl groups may be 1 and the number of hydrolyzable groups may be 3, but the number of fluoroalkyl groups is 1 and the number of hydrolyzable groups is 3 is preferred.
• the total number of fluoroalkyl groups and hydrolyzable groups bonded to the silicon atom may be 2 or 3 (especially 3). In the case of 3 or less, the remaining bonds include, for example, alkyl groups (especially An alkyl group having 1 to 4 carbon atoms), a hydrogen atom, a cyano group, or the like can be bonded.
• the combination of the fluoroalkyl group and the hydrolyzable group is not particularly limited, and may be any of those including or not including formula (9) described below, but preferably a combination of a fluoroalkyl group and an alkoxy group (Fluoroalkylalkoxysilanes, etc., especially fluoroalkyltrialkoxysilanes, etc.), combinations of fluoroalkyl groups and halogen atoms (fluoroalkylhalosilanes, etc., especially fluoroalkyltrihalosilanes).
• the fluoroalkylsilane (D1) is more preferably a compound represented by the following formula (9) for ease of synthesis.
• Rf 1 each independently represents a fluorine atom or an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms;
• Each R 1 independently represents a hydrogen atom or a lower alkyl group;
• Each R 2 independently represents an alkyl group having 1 to 20 carbon atoms;
• Each A independently represents —O—, —COO—, —OCO—, —NR—, —NRCO—, —CONR— (where R represents a hydrogen atom, a lower alkyl group, or a lower fluorine-containing alkyl group; Represent)
• Each B independently represents a hydrolyzable group;
• a1, b1, c1, d1, and e1 are each independently an integer of 0 to 100,
• the order of each repeating unit with a1, b1, c1, d1, e1 and parentheses is arbitrary in the formula, The total value of a1, b1, c1, d1, and e
• Rf 1 is preferably a fluorine atom or a perfluoroalkyl having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms).
• R 1 is preferably a hydrogen atom or alkyl having 1 to 4 carbon atoms.
• R 2 is preferably an alkyl group having 1 to 5 carbon atoms.
• A is preferably —O—, —COO—, or —OCO—.
• B is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group or a chlorine atom.
• a1 is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 2.
• b1 is preferably from 0 to 15, more preferably from 0 to 10.
• c1 is preferably 0 to 5, more preferably 0 to 2.
• d1 is preferably from 0 to 4, more preferably from 0 to 2.
• e1 is preferably 0 to 4, more preferably 0 to 2.
• m is preferably 2 to 3, and more preferably 3.
• the total value of a1, b1, c1, d1, and e1 is preferably 3 or more, more preferably 5 or more, and preferably 80 or less, more preferably 50 or less, and still more preferably 20 or less.
• Rf 1 is a fluorine atom or a perfluoroalkyl having 1 to 6 carbon atoms
• R 1 is a hydrogen atom
• B is a methoxy group or an ethoxy group
• c1, d1, and e1 are all 0
• M is 3
• a1 is preferably 1 to 5
• b1 is preferably 0 to 6.
• Examples of the fluoroalkylsilane (D1) include CF 3 —Si— (OCH 3 ) 3 and C j F 2j + 1 —Si— (OC 2 H 5 ) 3 (j is an integer of 1 to 12).
• C 4 F 9 —Si— (OC 2 H 5 ) 3 C 6 F 13 —Si— (OC 2 H 5 ) 3
• C 8 F 17 —Si— (OC 2 H 5 ) 3 is preferred.
• CF 3 (CF 2 ) m — (CH 2 ) n SiCl 3 , CF 3 (CF 2 ) m — (CH 2 ) n Si (OCH 3 ) 3 , CF 3 (CF 2 ) m — (CH 2 ) n Si (OC 2 H 5 ) 3 may also be mentioned (m is 1 to 10, preferably 3 to 7, and n is 1 to 5, preferably 2 to 4. ).
• the hydrolyzable silane oligomer (D2) has a silane compound having two or more hydrolyzable groups, preferably two or more (particularly three) hydrolyzable groups and a fluorine-containing group (particularly a lower fluorine-containing alkyl group).
• the number of silicon atoms (condensation number) contained in the oligomer is, for example, 3 or more, preferably 5 or more, and more preferably 7 or more.
• the condensation number is preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less.
• Examples of the hydrolyzable group possessed by the oligomer include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, preferably a methoxy group and an ethoxy group.
• the oligomer may have one or more of these hydrolyzable groups, and preferably has one.
• hydrolyzable silane oligomer (D2) examples include a compound represented by the following formula (10).
• Each X independently represents a hydrolyzable group, a lower alkyl group, or a lower fluorine-containing alkyl group; g1 is an integer of 0 or more and 100 or less. In the formula (10), “lower” means having 1 to 4 carbon atoms.
• hydrolyzable group examples include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
• At least one of X is a hydrolyzable group (particularly ethoxy group or methoxy group), and g1 is preferably 0 or more and 10 or less, more preferably 0 or more and 7 or less. It is also preferred that at least one of X is a lower fluorine-containing alkyl group.
• hydrolyzable silane oligomer examples include (H 5 C 2 O) 3 —Si— (OSi (OC 2 H 5 ) 2 ) 4 OC 2 H 5 , (H 3 CO) 2 Si (CH 2 CH 2 CF 3 )-(OSSiOCH 3 (CH 2 CH 2 CF 3 )) 4 —OCH 3 and the like.
• the content of (D1) and (D2) in the composition of the present invention is 0.01 to 0.5% by mass. Preferably there is.
• the composition of the present invention may further contain a silanol condensation catalyst.
• silanol condensation catalyst include inorganic acids such as hydrochloric acid and nitric acid, organic acids such as acetic acid, metal complexes such as titanium complexes (for example, ORGATICS TC-750 manufactured by Matsumoto Fine Chemical) and tin complexes, and metal alkoxides.
• the amount of the silanol condensation catalyst is, for example, 0.00001 to 0.1% by mass, preferably 0.00002 to 0.01% by mass, and more preferably 0.0005 to 0.001% by mass.
• composition of the present invention is an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, an anti-bioadhesive agent, a deodorant and a pigment as long as the effects of the present invention are not impaired.
• various additives such as a flame retardant and an antistatic agent may be contained.
• antioxidants examples include the following phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and hindered amine-based antioxidants.
• 3,3′-thiodipropionic acid di-n-dodecyl ester 3,3′-thiodipropionic acid di-n-tetradecyl ester, 3,3′-thiodipropionic acid di-n-octadecyl ester, Sulfur-based antioxidants such as tetrakis (3-dodecylthiopropionic acid) pentaerythrityl ester.
• tris (2,4-di-t-butylphenyl) phosphite bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methyl) Phenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonite, bis- [2,4-di -Phosphorous antioxidants such as t-butyl, (6-methyl) phenyl] ethyl phosphite.
• sebacic acid bis (2,2,6,6-tetramethyl-4-piperidyl) ester (melting point 81-86 ° C), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (melting point 58 ° C)
• rust preventive examples include alkanolamines, quaternary ammonium salts, alkanethiols, imidazolines, sodium metavanadate, bismuth citrate, phenol derivatives, polyalkenylamines, alkylimidazoline derivatives, dianoalkylamines, carboxylic acid amides.
• UV absorber / light stabilizer examples include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl]- 2H-benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, methyl -3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (4,6-Diphenyl-1,3,5-triazin-2-yl) -5 [(hexyl) oxy] -phen And UV absorbers / light stabilizers such as diol and 2-ethoxy-2'-ethy
• Antifungal / antibacterial agents include, for example, 2- (4-thiazolyl) benzimidazole, sorbic acid, 1,2-benzisothiazolin-3-one, (2-pyridylthio-1-oxide) sodium, dehydroacetic acid, 2- Methyl-5-chloro-4-isothiazolone complex, 2,4,5,6-tetrachlorophthalonitrile, methyl 2-benzimidazolecarbamate, methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamate, mono or dibromo Antifungal / antibacterial agents such as cyanoacetamides, 1,2-dibromo-2,4-dicyanobutane, 1,1-dibromo-1-nitropropanol and 1,1-dibromo-1-nitro-2-acetoxypropane It may contain.
• 2- (4-thiazolyl) benzimidazole sorbic acid
• biofouling inhibitor examples include tetramethylthiuram disulfide, bis (N, N-dimethyldithiocarbamate) zinc, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, dichloro-N-(( Dimethylamino) sulfonyl) fluoro-N- (P-tolyl) methanesulfenamide, pyridine-triphenylborane, N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) sulfamide, thiocyanic acid first Copper (1), cuprous oxide, tetrabutylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zinc ethylenebisdithiocarbamate, 2,3,5,6-tetrachloro-4- (Methylsulfonyl) pyridine, N- (2,4,6-trichlor
• deodorant examples include lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylenediamine polyacetic acid, alkane-1,2-dicarboxylic acid, alkene-1,2-dicarboxylic acid, cycloalkane- Organic acids such as 1,2-dicarboxylic acid, cycloalkene-1,2-dicarboxylic acid, naphthalenesulfonic acid; fatty acid metals such as zinc undecylenate, zinc 2-ethylhexanoate, zinc ricinoleate; iron oxide, iron sulfate , Zinc oxide, zinc sulfate, zinc chloride, silver oxide, copper oxide, metal (iron, copper, etc.) chlorophyllin sodium, metal (iron, copper, cobalt etc.) phthalocyanine, metal (iron, copper, cobalt etc.) tetrasulfonic acid phthalocyanine , Titanium dioxide, visible light responsive titanium dioxide (
• the pigment examples include carbon black, titanium oxide, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, perylene or perinone pigment, quinophthalone pigment, diketopyrrolo-pyrrole pigment, dioxazine pigment, disazo condensation pigment And benzimidazolone pigments.
• flame retardant examples include flame retardants such as decabromobiphenyl, antimony trioxide, phosphorus flame retardant, and aluminum hydroxide.
• antistatic agent examples include quaternary ammonium salt type cationic surfactants, betaine type amphoteric surfactants, alkyl phosphate type anionic surfactants, primary amine salts, secondary amine salts, Cationic surfactants such as tertiary amine salts, quaternary amine salts and pyridine derivatives, sulfated oils, soaps, sulfated ester oils, sulfated amide oils, sulfated ester salts of olefins, fatty alcohol sulfate esters, alkyl Anionic surfactants such as sulfate esters, fatty acid ethyl sulfonates, alkyl naphthalene sulfonates, alkyl benzene sulfonates, oxalate ester sulfonates and phosphate ester salts, partial fatty acid esters of polyhydric alcohols, fatty alcohols Ethylene
• the content of the various additives is, for example, 0.01 to 70% by mass, preferably 0.8%, based on the total weight of the composition of the present invention.
• Lubricants may also be contained in the composition of the present invention.
• composition of the present invention is applied to a substrate and left in the air or heated and dried (for example, at 120 to 180 ° C. for 10 to 60 minutes) to take in moisture in the air and hydrolyze the hydrolyzable group. And a siloxane bond is formed.
• the obtained film may be further heated and dried.
• a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, or the like can be adopted as a method for applying the composition to the substrate.
• the film thickness of the obtained film is, for example, about 4 to 10 nm.
• the transparent film obtained from the composition of the present invention has water and oil repellency and is excellent in wear resistance and visibility.
• the transparent film of the present invention has a contact angle measured by the ⁇ / 2 method at a water droplet volume of 3.0 ⁇ l, usually 100 ° or more, preferably 110 ° or more, and the upper limit is not limited, but is, for example, 120 ° or less.
• the transmittance (HAZE) measured using a haze meter according to JIS K 7136 can be 0.2% or less, preferably 0.15% or less, and more preferably 0.10% or less.
• the lower limit of HAZE is, for example, 0.03%.
• the substrate to which the composition of the present invention is applied is not particularly limited, and may be either an organic material or an inorganic material, the shape may be flat or curved, or a three-dimensional combination of many surfaces. It may be a mechanical structure.
• the organic material include thermoplastic resins such as acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, polyolefin resin, and polyvinyl alcohol; phenol resin, urea resin, melamine resin, epoxy
• thermosetting resins such as resins, unsaturated polyesters, silicone resins, and urethane resins.
• the inorganic material include metals such as iron, silicon, copper, zinc, and aluminum, alloys containing these metals, ceramics, and glass.
• the substrate may be subjected to easy adhesion treatment in advance.
• easy adhesion treatment include hydrophilic treatment such as corona treatment, plasma treatment, and ultraviolet treatment.
• primer treatment with a resin, a silane coupling agent, tetraalkoxysilane, or the like may be used.
• a layer formed using a composition for forming an underlayer containing a component (E) composed of a compound represented by the following formula (11) and / or a partially hydrolyzed condensate thereof is preferable.
• each X 2 independently represents a halogen atom, an alkoxy group or an isocyanate group.
• X 2 is preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms or an isocyanate group, and the four X 2 are preferably the same.
• Si (NCO) 4 , Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 and the like are preferably used as such a compound represented by the formula (11).
• a component may be used individually by 1 type and may use 2 or more types together.
• the component (E) contained in the primer layer forming composition may be a partially hydrolyzed condensate of the compound represented by the above formula (11).
• the partial hydrolysis-condensation product of the compound represented by the above formula (11) can be obtained by applying a general hydrolysis-condensation method using an acid or a base catalyst.
• the degree of condensation (degree of multimerization) of the partially hydrolyzed condensate needs to be such that the product is dissolved in the solvent.
• the component (E) may be a compound represented by the above formula (11) or a partial hydrolysis condensate of the compound represented by the above formula (11).
• the underlayer-forming composition comprises the above component (E), a compound represented by the following formula (12) (sometimes referred to as compound (12)) and / or a partial hydrolysis condensate thereof (F). Or a partial hydrolysis-condensation product of the component (E) and the component (F) (however, the component (E) and / or the compound (12) may be included). There may be.
• the compound represented by the formula (12) is a compound having hydrolyzable silyl groups or silanol groups at both ends with a divalent organic group interposed therebetween.
• examples of the hydrolyzable group represented by X 3 include the same groups or atoms as X 2 described above.
• X 3 is preferably an alkoxy group or an isocyanate group, and particularly preferably an alkoxy group.
• the alkoxy group an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable. These are appropriately selected and used according to the purpose of manufacture, application and the like.
• a plurality of X 3 present in the formula (12) may be the same group or different groups, and the same group is preferable from the viewpoint of availability.
• the component contained in the primer layer forming composition may be a partially hydrolyzed condensate of the compound represented by the formula (12).
• the partially hydrolyzed condensate of the compound represented by the formula (12) can be obtained by the same method as described in the production of the partially hydrolyzed condensate of the compound represented by the formula (11).
• the degree of condensation (degree of multimerization) of the partially hydrolyzed condensate must be such that the product is dissolved in the solvent.
• the component (F) may be a compound represented by the formula (12) or a partially hydrolyzed condensate of the compound represented by the formula (12), which is represented by the formula (12).
• It may be a mixture of a compound and a partial hydrolysis condensate thereof, for example, a partial hydrolysis condensate of the compound including an unreacted compound represented by the formula (12).
• a commercial item as a compound shown by the said Formula (12), and its partial hydrolysis-condensation product, It is possible to use such a commercial item for this invention.
• various polysilazanes capable of obtaining an oxide film containing silicon as a main component similar to the above formula (11) may be used for the underlayer.
• the primer layer-forming composition usually contains an organic solvent in addition to the solid content as a layer constituent component in consideration of economy, workability, ease of controlling the thickness of the resulting primer layer, and the like.
• the organic solvent is not particularly limited as long as it dissolves the solid content contained in the primer layer forming composition.
• Examples of the organic solvent include the same compounds as the solvent used in the composition of the present invention.
• the organic solvent is not limited to one kind, and two or more kinds of solvents having different polarities and evaporation rates may be mixed and used.
• the composition for primer layer formation contains the partial hydrolysis-condensation product and the partial hydrolysis-condensation product, you may include the solvent used in order to manufacture these.
• the composition for forming a primer layer even if it does not contain a partial hydrolysis condensate or partial hydrolysis cocondensate, in order to promote the hydrolysis cocondensation reaction, It is also preferable to blend a catalyst such as an acid catalyst that is generally used. Even when a partially hydrolyzed condensate or a partially hydrolyzed cocondensate is included, when the catalyst used for the production thereof does not remain in the composition, it is preferable to add a catalyst.
• the underlayer-forming composition may contain water for the above-mentioned components to undergo a hydrolysis condensation reaction or a hydrolysis cocondensation reaction.
• the underlayer using the primer layer forming composition As a method for forming the underlayer using the primer layer forming composition, a known method for an organosilane compound-based surface treatment agent can be used.
• the composition for forming the underlayer is applied to the surface of the substrate by methods such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, and hand coating, and is necessary in the air or in a nitrogen atmosphere.
• the base layer can be formed by curing after drying according to the above. Curing conditions are appropriately controlled depending on the type and concentration of the composition used.
• the thickness of the primer layer is not particularly limited as long as it can provide moisture resistance to the transparent film formed thereon, can also provide adhesion to the substrate, and can also barrier alkali and the like from the substrate.
• the transparent film obtained by the composition of the present invention is a display device such as a touch panel display, an optical element, a semiconductor element, a building material, a nanoimprint technique, a solar cell, a metal product such as a window glass of an automobile or a building, a cooking utensil, tableware, etc.
• the film can be suitably formed on ceramic products, plastic automobile parts and the like, which is industrially useful. It can also be used for fishing nets, insect catching nets, water tanks, and the like. Furthermore, it can be used for various indoor facilities such as kitchens, bathrooms, washstands, mirrors, toilet articles, ceramics such as chandeliers and tiles, artificial marble, and air conditioners.
• It can also be used as an antifouling treatment for jigs, inner walls, pipes and the like in factories. It is also suitable for goggles, glasses, helmets, slingshots, textiles, umbrellas, play equipment, soccer balls and the like. Furthermore, it can also be used as an anti-adhesive agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots.
• the film obtained in the example of the present invention was measured by the following method.
• Example 1 A compound a (number average molecular weight of about 8000) represented by the following formula (13) was synthesized by the method described in Synthesis Examples 1 and 2 of JP-A-2014-15609.
• n 43 and m is an integer of 1-6.
• Compound a represented by the above formula (13) as the compound (A), fluorine oil as the compound (B), Fomblin (registered trademark) M60 (manufactured by Solvay, number average molecular weight 12500), FC as the main solvent (C) -3283 (Fluorinert, manufactured by 3M) was mixed and stirred at room temperature to obtain a composition.
• the ratio of compound a is 0.08% by mass
• the ratio of fluorine oil M60 is 0.02% by mass.
• composition was applied to pre-treated silica glass (Eagle XG, manufactured by Corning) using a spin coater (MS-A100, manufactured by Mikasa) at 3000 rpm / min, 20 seconds, 200 ⁇ l (composition) Spin coating was performed under the conditions of Then, it dried on 150 degreeC and 30min conditions, and obtained the transparent film on the silica glass.
• silica glass is immersed in a 10% by mass aqueous sodium hydroxide solution, subjected to ultrasonic cleaning for 20 minutes, rinsed with pure water, and then subjected to ultrasonic cleaning for 10 minutes with pure water. And a process of drying at 60 ° C. for 1 hour so that no moisture remains on the surface.
• Example 2 A transparent film was produced on silica glass in the same manner as in Example 1 except that the ratio of the fluorine oil M60 was changed to 0.05% by mass.
• Example 3 A transparent film was produced on silica glass in the same manner as in Example 1 except that the ratio of the fluorine oil M60 was changed to 0.1% by mass.
• Comparative Example 1 0.05% by mass of the compound a represented by the above formula (13) as the compound (A), fluorine oil represented by the following formula (14), Fomblin (registered trademark) M03 (manufactured by Solvay, number average molecular weight) 4000) and 0.05% by mass of Novec (registered trademark) 7200 (manufactured by 3M) as a main solvent (C) were mixed and stirred at room temperature to obtain a composition. Thereafter, a transparent film was produced on silica glass in the same manner as in Example 1.
• Comparative Example 2 A transparent film was produced on silica glass in the same manner as in Example 1 except that the ratio of the fluorine oil M60 was 0.005% by mass, and Novec7200 was used as the main solvent (C) instead of FC-3283.
• Comparative Example 3 A transparent film was produced on silica glass in the same manner as in Comparative Example 2 except that 0.02% by mass of fluorine oil M03 was used instead of fluorine oil M60.
• Comparative Example 4 A transparent film was produced on silica glass in the same manner as in Example 1 except that the ratio of the fluorine oil M60 was 0.2% by mass.
• Table 1 shows the results of Examples and Comparative Examples.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Inorganic Chemistry (AREA)
• Paints Or Removers (AREA)
• Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
• Polyethers (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=60160807

Family Applications (1)

Country Status (5)

Cited By (4)

Families Citing this family (3)

Citations (6)

Family Cites Families (2)

• 2017
  • 2017-04-26 JP JP2017087220A patent/JP6914711B2/ja not_active Expired - Fee Related
  • 2017-04-26 KR KR1020187034259A patent/KR20190003632A/ko not_active Ceased
  • 2017-04-26 WO PCT/JP2017/016587 patent/WO2017188330A1/ja not_active Ceased
  • 2017-04-26 TW TW106113962A patent/TW201809066A/zh unknown
  • 2017-04-26 CN CN201780025924.9A patent/CN109071935B/zh not_active Expired - Fee Related

Patent Citations (6)

Also Published As

Similar Documents

Legal Events