Classifications

• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
  • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
  • C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/10—Metal compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
• • 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
  • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/10—Block or graft copolymers containing polysiloxane sequences
• • 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
  • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic

Definitions

• the present invention relates to a composition.
• a composition containing a compound having a perfluoropolyether structure is used as an antifouling coating agent, an adhesive, a water / oil repellent coating agent and the like.
• Patent Document 1 describes a method for producing an antifouling substrate by applying a photocurable hard coat agent composition to a substrate surface made of a resin and curing the composition, and then treating with an antifouling coating agent.
• an antifouling coating agent perfluoropolyether-modified silane is disclosed.
• Patent Document 2 discloses an adhesive composition containing a linear polyfluoro compound having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain.
• Patent Document 3 discloses a coating agent composition containing a fluorine-containing silicon compound containing a perfluoropolyether residue, and the film obtained from this coating agent composition is less likely to be water-based and oily. Is described.
• the present invention is a composition containing a compound having a perfluoropolyether structure, which forms a film having excellent adhesion between a film obtained from this composition and a substrate and having good sliding properties such as water droplets.
• the object is to provide a possible composition.
• the present invention relates to a first organosilicon compound (A) in which a monovalent group having a perfluoropolyether structure and a hydrolyzable group are bonded to a silicon atom, and a hydrolyzable group bonded to a silicon atom. And a second organosilicon compound (B) having no perfluoropolyether structure and a compound having a metal element belonging to Group 13 of the periodic table.
• the compound having a metal element belonging to Group 13 of the periodic table is preferably a complex having a metal element belonging to Group 13 of the periodic table.
• the first organosilicon compound (A) is preferably represented by the following formula (a1).
• Rf a1 is a divalent perfluoropolyether structure in which both ends are oxygen atoms
• R 11, R 12, and R 13 are each independently an alkyl group having 1 to 20 carbon atoms
• R 11 there are a plurality may be different plural R 11 are each
• R 12 is more if present may be different plurality of R 12 each may be the case where R 13 there are a plurality of different plural R 13 are each E 1, E 2, E 3 , E 4, and E 5 are each independently a hydrogen atom or a fluorine atom
• E 1 there are a plurality may be different plurality of E 1, respectively, when the E 2 there are a plurality of different plurality of E 2 each and may be, may be different in a plurality of E 3 respectively when the E 3 there are a plurality
• E 4 there are a plurality may be different plurality of E 4 respectively
• G 1 and G 2 are each independently a divalent to decavalent organosiloxane group having
• the second organosilicon compound (B) preferably contains a compound represented by the following formula (b1).
• Rf b10 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom
• R b11, R b12, R b13 , R b14 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R b11 there are a plurality differ plurality of R b11 each may, if R b12 there are a plurality may be different plural R b12 each may be the case where R b13 there are a plurality of different plural R b13 are each if R b14 there are multiple May have different R b14 s , Rf b11, Rf b12, Rf b13 , Rf b14 are each independently one or more hydrogen atoms is an alkyl group or a fluorine atom carbon number of 1 to 20 substituted by a fluorine atom, Rf b11, R
• R is a hydrogen atom, a fluorine-containing alkyl group of the alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, if a 1 there are a plurality may be different plurality of a 1, respectively,
• a 2 is a hydrolyzable group, if A 2 there are a plurality may be different plurality of A 2, respectively, b11, b12, b13, b14, b15 are each independently an integer of 0-100.
• c is an integer of 1 to 3, Rf b10 -, - Si (A 2) c (R b15) 3-c, b11 amino - ⁇ C (R b11) ( R b12) ⁇ -, b12 amino - ⁇ C (Rf b11) ( Rf b12) ⁇ -, B13- ⁇ Si (R b13 ) (R b14 ) ⁇ -, b14- ⁇ Si (Rf b13 ) (Rf b14 ) ⁇ -, b15 -A 1 -are Rf b10- , —Si (A 2 ) c (R b15 ) 3-c is terminated, does not form a polysiloxane structure, does not form a perfluoropolyether structure, and —O— is not linked to —O— or —F. As long as they are combined in any order.
• the metal compound is preferably an Al compound, more preferably an Al complex.
• the ratio of the metal compound to the total of the first organosilicon compound (A) and the second organosilicon compound (B) is preferably 0.6 to 5.0 mol% in terms of molar ratio. In terms of mass ratio, it is preferably 0.1 to 2.0% by mass.
• the present invention also includes a covering provided with a film formed by curing the above-described composition of the present invention. Moreover, the manufacturing method of the said coating body characterized by hardening a composition at normal temperature is also contained in this invention.
• the composition of the present invention comprises a first organic silicon compound (A) in which a monovalent group having a perfluoropolyether structure and a hydrolyzable group are bonded to a silicon atom, and a hydrolyzable bonded to a silicon atom. Since the second organosilicon compound (B) having a decomposable group and not having a perfluoropolyether structure and a compound having a metal element belonging to Group 13 of the periodic table are contained, the resulting film is a substrate. In addition to excellent adhesion to (especially an iron-based substrate), the effect of excellent sliding properties is achieved.
• the composition of the present invention contains specific organosilicon compounds (A) and (B) and a compound having a specific metal (hereinafter sometimes referred to as “metal compound”). Some metal compounds are known as catalysts for accelerating the reaction rate of the condensation reaction.
• the present inventors, together with specific organosilicon compounds (A) and (B), are metal elements belonging to Group 13 of the periodic table. It was clarified that the adhesion between the film obtained from this composition and the base material is improved by using a composition containing a compound having the following. Moreover, when the composition contains the organosilicon compound (B) together with the organosilicon compound (A), the resulting film has good sliding properties.
• the organosilicon compounds (A) and (B) and the metal compound in the present invention will be described in order.
• the first organosilicon compound (A) (hereinafter sometimes simply referred to as “compound (A)”) contains fluorine and undergoes a polymerization reaction (particularly heavy) with the compounds (A) or other monomers.
• a compound capable of forming a film matrix by bonding through a condensation reaction specifically, a compound in which a monovalent group having a perfluoropolyether structure and a hydrolyzable group are bonded to a silicon atom. .
• the perfluoropolyether structure is a structure in which all hydrogen atoms of a polyoxyalkylene group are replaced with fluorine atoms, and can be said to be a perfluoropolyoxyalkylene group.
• the perfluoropolyether structure can impart water repellency to the resulting film.
• 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 still 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 include hydrocarbon groups such as alkylene groups and aromatic hydrocarbon groups, (poly) alkylene glycol groups, groups in which at least some of these hydrogen atoms are substituted with fluorine atoms, and these are suitable. And a group linked to.
• the number of carbon atoms of the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 15 or less, and more preferably 2 or more and 10 or less.
• a plurality of silicon atoms may be bonded to one linking group, and a plurality of perfluoropolyether structures 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 derived from a hydroxy group on the surface of the material.
• 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.
• the total number of monovalent groups having a perfluoropolyether structure and hydrolyzable groups bonded to silicon atoms is usually 4, but may be 2 or 3 (particularly 3). In the case of 3 or less, for example, 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.
• the monovalent group having a perfluoropolyether structure may further have a silicon atom and a hydrolyzable group bonded to the silicon atom.
• the number average molecular weight of the compound (A) is not particularly limited, but is preferably 2,000 or more and 50,000 or less, for example.
• the lower limit of the number average molecular weight of the compound (A) is preferably 4,000 or more, more preferably 6,000 or more, still more preferably 7,000 or more, and the upper limit is preferably 40,000 or less, more preferably 20 15,000 or less, more preferably 15,000 or less.
• Compound (A) can be represented, for example, by the following formula (a1).
• Rf a1 is a divalent perfluoropolyether structure in which both ends are oxygen atoms
• R 11 , R 12 , and R 13 are each independently (that is, R 11 , R 12, and R 13 may be the same or different from each other), and an alkyl group having 1 to 20 carbon atoms
• the case where R 11 there are a plurality may be different plurality of R 11 each may be the case where R 12 there are a plurality of different plural R 12 are each, if R 13 there are a plurality of May have a plurality of different R 13 s
• E 1, E 2, E 3 , E 4, and E 5 is, independently represents a hydrogen atom or a fluorine atom
• E 2 may be the case where there are plural different multiple E 2 respectively, when the E 3 there are a plurality may be different plurality of E 3 respectively, the plurality of E if E 4 there are are are
• Rf a1 is preferably —O— (CF 2 CF 2 O) e4 — or —O— (CF 2 CF 2 CF 2 O) e5 — (e4 is preferably 1 to 85, and e5 is 25 to 25 70, more preferably 35 to 50).
• R 11 , R 12 , and R 13 are each independently preferably an alkyl group having 1 to 10 carbon atoms
• L 1 and L 2 are preferably each independently a divalent linking group having 1 to 5 carbon atoms and containing a fluorine atom
• G 1 and G 2 are each independently preferably a divalent to pentavalent organosiloxane group having a siloxane bond
• J 1 , J 2 , and J 3 are each independently preferably a methoxy group, an ethoxy group, or — (CH 2 ) e6 —Si (OR 14 ) 3
• a10 is preferably 0 to 5 (more preferably 0 to 3)
• a11 is preferably 0,
• a12 is preferably 0 to 7 (more preferably 0 to 5)
• a14 is preferably 1 to 6 (more preferably 1).
• a15 is preferably 0, a16 is preferably 0 to 6, a21 to a23 are all preferably 0 or 1 (more preferably all are 0), and d11 is preferably 1 to 5 (more preferably 1).
• To 3) and d12 are preferably 0 to 3 (more preferably 0 or 1), and all of e1 to e3 are preferably 3.
• Rf a1 in the above formula (a1) is —O— (CF 2 CF 2 CF 2 O) e5 —, e5 is 35 to 50, and both L 1 and L 2 are carbon.
• a perfluoroalkylene group of 1 to 3 E 1 , E 2 , E 3 are all hydrogen atoms, E 4 , E 5 are hydrogen atoms or fluorine atoms, J 1 , J 2 , J 3 are each a methoxy group or an ethoxy group (particularly a methoxy group), a10 is 1 to 3, a11 is 0, a12 is 0 to 5, a13 is 1, and a14 is 2 to 5.
• A15 is 0, a16 is 0 to 6, a21 to a23 are each independently 0 or 1 (more preferably, a21 to a23 are all 0), d11 is 1, and d12 It is preferable to use a compound wherein is 0 or 1 and all of e1 to e3 are 3. There.
• Rf a1 is —O— (CF 2 CF 2 CF 2 O) 43 —
• L 1 and L 2 is — (CF 2 ) —
• E 1 , E 2 and E 3 are all hydrogen atoms
• E 5 is a fluorine atom
• J 1 and J 2 are both methoxy groups
• a10 is 2
• a11 is 0, a12 is 0 to 5
• a13 is 1
• a14 is 3
• a15 is 0, a16 is 0, a21 and a22 are all 0, d11 is 1, d12 is 0, e1, All of e2 are 3.
• Rf a1 in the above formula (a1) is —O— (CF 2 CF 2 CF 2 O) e5 —, e5 is 25 to 40, L 1 is a fluorine atom or an oxygen atom.
• J 2 is — (CH 2 ) e6 —Si (OCH 3 ) 3 , e6 is 2 to 4, a10 is 1 to 3, a11 is 0, a12 is 0, a13 Is 0, a14 is 2 to 5, a15 is 0, a16 is 0, and a21 to a23 are each independently 0 or 1 (more preferably, a21 to a23 are all 0 It is also preferable to use a compound in which d11 is 1, d12 is 0, and e2 is 3.
• the compound (A) can also be represented by the following formula (a2-1).
• Rf a21 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom
• Rf a22 , Rf a23 , Rf a24 , and Rf a25 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a plurality of Rf a22.
• Rf a22 are each different if Rf a23 there are a plurality may be different plurality of Rf a23, respectively, a plurality of Rf a24 If Rf a24 are present in plural even if well, if Rf a25 there are a plurality may be different plurality of Rf a25 respectively, R 20, R 21, R 22 , R 23 are each independently hydrogen atom or an alkyl group having 1 to 4 carbon atoms, even if the R 20 there are a plurality of different plural R 20 are each well, if R 21 there are a plurality may be different plurality of R 21 each may be the case where R 22 there are a plurality of different plural R 22 are each, if R 23 there are a plurality of The plurality of R 23 may be different from each other, R 24 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R 24 there are a plurality of different plural R 24 are each, M 1 is a hydrogen
• a repeating unit ie,- ⁇ C (R 20 ) (R 21 ) ⁇ -
• f11 the total number of the repeating units.
• the repeating units that are parenthesized with each of f12, f13, f14, f15, and f16.
• Rf a21 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, still more preferably 1 to 1 carbon atom. 5 perfluoroalkyl groups.
• Rf a22 , Rf a23 , Rf a24 and Rf a25 are preferably each independently a fluorine atom or an alkyl group having 1 to 2 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and more preferably Are all fluorine atoms.
• R 20 , R 21 , R 22 and R 23 are preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably all hydrogen atoms.
• R 24 is preferably an alkyl group having 1 to 5 carbon atoms.
• M 1 is preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably all hydrogen atoms.
• M 2 is preferably a hydrogen atom.
• M 3 is preferably —C ( ⁇ O) —O—, —O—, —O—C ( ⁇ O) —, and more preferably all —O—.
• M 4 is preferably an alkoxy group or a halogen atom, particularly preferably a methoxy group, an ethoxy group or a chlorine atom.
• f11, f13 and f14 are each 1 ⁇ 2 or less of f12, more preferably 1 ⁇ 4 or less, more preferably f13 or f14 is 0, and particularly preferably f13 and f14 are 0.
• F15 is preferably 1/5 or more of the total value of f11, f12, f13, and f14, and is not more than the total value of f11, f12, f13, and f14.
• f12 is preferably 20 or more and 600 or less, more preferably 20 or more and 200 or less, still more preferably 50 or more and 200 or less (more preferably 30 to 150, particularly 50 to 150, most preferably 80 to 140).
• f15 is preferably 4 or more and 600 or less, more preferably 4 or more and 200 or less, still more preferably 10 or more and 200 or less (more preferably 30 to 60).
• the total value of f11, f12, f13, f14, and f15 is preferably 20 or more and 600 or less, more preferably 20 or more and 200 or less, and further preferably 50 or more and 200 or less.
• F16 is preferably 1 or more and 18 or less. More preferably, they are 1 or more and 15 or less, More preferably, they are 1 or more and 10 or less.
• F17 is preferably 0 or more and 1 or less.
• G1 is preferably 2 or more and 3 or less, and more preferably 3.
• f11- ⁇ C (R 20 ) (R 21 ) ⁇ -, f12- ⁇ C (Rf a22 ) (Rf a23 ) ⁇ -, f13- ⁇ Si (R 22 ) (R 23 ) ⁇ - , F14- ⁇ Si (Rf a24 ) (Rf a25 ) ⁇ -, f15 -M 3- may be arbitrarily selected in the formula as long as at least a part thereof is arranged in the order of forming a perfluoropolyether structure.
• the repeating unit ie,- ⁇ C (Rf a22 ) (Rf a23 ) ⁇ -
• the repeating unit attached with f12 on the most fixed end side (side bonded to the silicon atom) and enclosed in parentheses is It is located on the free end side with respect to the repeating unit (ie,- ⁇ C (R 20 ) (R 21 ) ⁇ -) attached with f11 on the most free end side, and more preferably on the most fixed end side.
• f14 i.e., - ⁇ C (Rf a22 (Rf a23) ⁇ -, and - ⁇ Si (Rf a24) ( Rf a25) ⁇ -
• f13 i.e., - ⁇ C ( R 20 ) (R 21 ) ⁇ -and- ⁇ Si (R 22 ) (R 23 ) ⁇ -).
• Rf a21 is a perfluoroalkyl group having 1 to 5 carbon atoms
• Rf a22 , Rf a23 , Rf a24 and Rf a25 are all fluorine atoms
• M 3 is all —O—.
• M 4 is all a methoxy group, an ethoxy group or a chlorine atom (particularly a methoxy group or an ethoxy group), M 1 and M 2 are both hydrogen atoms, f11 is 0, and f12 is 30 to 150 (more Preferably, 80 to 140), f15 is 30 to 60, f13 and f14 are 0, f17 is 0 or more and 1 or less (particularly 0), g1 is 3, and f16 is 1 to 10.
• the compound a used as the compound (A) is represented by the above formula (a2-1).
• Rf a1 is C 3 F 7 —
• Rf a22 and Rf a23 are both fluorine atoms.
• the compound (A) can also be represented by the following formula (a2-2).
• Rf a26 , Rf a27 , Rf a28 , and Rf a29 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or fluorine atoms, and a plurality of Rf a26 are present.
• Rf a26 are each different if Rf a27 there are a plurality may be different plurality of Rf a27, respectively, a plurality of Rf a28 If Rf a28 are present in plural even if well, if Rf a29 there are a plurality may be different plurality of Rf a29 respectively, R 25, R 26, R 27 , R 28 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, even if the R 25 there are a plurality of different plurality of R 25 each well, if R 26 there are a plurality may be different plurality of R 26 each may be the case where R 27 there are a plurality of different plural R 27 are each, if R 28 there are a plurality of The plurality of R 28 may be different from each other, R 29, R 30 are each independently an alkyl group having 1 to 20 carbon atoms, if R 29 there are a plurality may be different plurality of R 29 each,
• R is a hydrogen atom, a fluorine-containing alkyl group of the alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, if M 7 there are a plurality may be different plurality of M 7, respectively, M 5, M 9 are each independently hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if M 5 there are a plurality may be different plurality of M 5, respectively, M 9 are multiple If present, multiple M 9s may be different from each other, M 6 and M 10 are each independently a hydrogen atom or a halogen atom, M 8, M 11 are each independently a hydrolysable group, if M 8 there are a plurality may be different plurality of M 8, respectively, of a plurality if M 11 there are a plurality of M 11 may be different, f21, f22, f23, f24, and f25 are each independently an integer of 0 to 600, and the total value of f21, f22, f23
• Rf a26 , Rf a27 , Rf a28 and Rf a29 are all fluorine atoms
• M 7 is all —O—
• M 8 and M 11 are all methoxy, ethoxy or A chlorine atom (particularly a methoxy group or an ethoxy group)
• M 5 , M 6 , M 9 and M 10 are all hydrogen atoms
• f21 is 0, f22 is 30 to 150 (more preferably 80 to 140)
• the compound (A) includes a compound represented by the following formula (a3).
• R 30 is a perfluoroalkyl group having 2 to 6 carbon atoms
• R 31 and R 32 are each independently a perfluoroalkylene group having 2 to 6 carbon atoms
• R 33 is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms
• R 34 is an alkyl group having 1 to 3 carbon atoms.
• R 30 , R 31 , R 32 and R 33 each independently preferably have 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
• h1 is 5 to 70
• h2 is 1 to 5
• h3 is 1 to 10.
• h1 is preferably 10 to 60, more preferably 20 to 50
• h2 is preferably 1 to 4, more preferably 1 to 3, and
• h3 is preferably 1 to 8, and more preferably 1 to 6.
• Examples of the compound (A) also include a compound represented by the following formula (a4).
• R 40 is a perfluoroalkyl group having 2 to 5 carbon atoms
• R 41 is a perfluoroalkylene group having 2 to 5 carbon atoms
• R 42 is a group having 2 to 5 carbon atoms.
• R 43 and R 44 are each independently an alkylene group having 2 to 5 carbon atoms
• R 45 is a methyl group or an ethyl group.
• k1, k2, and k3 are each independently an integer of 1 to 5.
• the second organosilicon compound (B) is a compound having a hydrolyzable group bonded to a silicon atom and not having a perfluoropolyether structure. Since the second organosilicon compound has a hydrolyzable group, it can undergo a condensation reaction with the hydrolyzable group of the first organosilicon compound (A) or with active hydrogen such as a hydroxyl group on the substrate surface. Examples of the hydrolyzable group include an alkoxy group (particularly an alkoxy group having 1 to 4 carbon atoms) or a halogen atom.
• the second organosilicon compound (B) preferably does not have a polyether structure.
• Examples of the compound (B) include a compound represented by the following formula (b1).
• Rf b10 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom
• R b11, R b12, R b13 , R b14 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R b11 there are a plurality differ plurality of R b11 each may, if R b12 there are a plurality may be different plural R b12 each may be the case where R b13 there are a plurality of different plural R b13 are each if R b14 there are multiple May have different R b14 s , Rf b11, Rf b12, Rf b13 , Rf b14 are each independently one or more hydrogen atoms is an alkyl group or a fluorine atom carbon number of 1 to 20 substituted by a fluorine atom, Rf b11, R
• R is a hydrogen atom, a fluorine-containing alkyl group of the alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, if a 1 there are a plurality may be different plurality of a 1, respectively,
• a 2 is a hydrolyzable group, if A 2 there are a plurality may be different plurality of A 2, respectively, b11, b12, b13, b14, b15 are each independently an integer of 0-100.
• c is an integer of 1 to 3, Rf b10 -, - Si (A 2) c (R b15) 3-c, b11 amino - ⁇ C (R b11) ( R b12) ⁇ -, b12 amino - ⁇ C (Rf b11) ( Rf b12) ⁇ -, B13- ⁇ Si (R b13 ) (R b14 ) ⁇ -, b14- ⁇ Si (Rf b13 ) (Rf b14 ) ⁇ -, b15 -A 1 -are Rf b10- , —Si (A 2 ) c (R b15 ) 3-c is terminated, does not form a polysiloxane structure, does not form a perfluoropolyether structure, and —O— is not linked to —O— or —F.
• Rf b10 is preferably each independently a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms).
• R b11, R b12, R b13 , R b14 is preferably a hydrogen atom.
• R b15 is preferably an alkyl group having 1 to 5 carbon atoms.
• a 1 is preferably —O—, —C ( ⁇ O) —O—, or —O—C ( ⁇ O) —.
• a 2 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.
• b11 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.
• b12 is preferably from 0 to 15, and more preferably from 0 to 10.
• b13 is preferably 0 to 5, more preferably 0 to 2.
• b14 is preferably 0 to 4, more preferably 0 to 2.
• b15 is preferably 0 to 4, more preferably 0 to 2.
• c is preferably 2 to 3, more preferably 3.
• the total value of b11, b12, b13, b14, b15 is preferably 3 or more, preferably 5 or more, more preferably 80 or less, more preferably 50 or less, and still more preferably 20 or less.
• Rf b10 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms
• R b11 and R b12 are both hydrogen atoms
• a 2 is a methoxy group or an ethoxy group
• b11 is 1 to 5
• b12 is 0 to 5
• b13, b14, and b15 are all 0, and c is preferably 3.
• both Rf b11 and Rf b12 are fluorine atoms.
• Specific examples of the compound represented by the formula (b1) include CF 3 —Si— (OCH 3 ) 3 , C j F 2j + 1 —Si— (OC 2 H 5 ) 3 (j is 1 to 12).
• C 4 F 9 —Si— (OC 2 H 5 ) 3 , C 6 F 13 —Si— (OC 2 H 5 ) 3 , C 7 F 15 —Si— (OC 2 H 5 ) 3 and C 8 F 17 —Si— (OC 2 H 5 ) 3 are 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. ).
• CF 3 (CF 2 ) p — (CH 2 ) q —Si— (CH 2 CH ⁇ CH 2 ) 3 can also be mentioned (p is 2 to 10, preferably 2 to 8, and q Are all 1 to 5, preferably 2 to 4).
• R 60 is a perfluoroalkyl group having 3 to 8 carbon atoms
• R 61 is an alkylene group having 1 to 5 carbon atoms
• R 62 is an alkyl group having 1 to 3 carbon atoms. It is.
• it is also preferable to use a compound having a boiling point of 100 ° C. or higher (preferably 300 ° C. or lower).
• examples of the compound (B) include compounds represented by the following formula (b2).
• X 1 , X 2 , X 3 and X 4 are each independently a hydrolyzable group, an alkyl group having 1 to 4 carbon atoms, or one or more hydrogen atoms substituted by fluorine
• the alkyl group having 1 to 4 carbon atoms, the three X 1 s may be different from each other, the three X 2 s may be different from each other, and when a plurality of X 3 are present, They may be different, and when there are multiple X 4 s , they may be different, At least one of X 1 , X 2 , X 3 , and X 4 is a hydrolyzable group;
• b21 is an integer of 0 or more and 100 or less.
• Examples of the hydrolyzable group for X 1 , X 2 , X 3 and X 4 include alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group.
• X 1 , X 2 , X 3 and X 4 are preferably all alkoxy groups, or at least one of X 1 , X 2 , X 3 and X 4 is substituted with one or more hydrogen atoms. It is also preferred that the alkyl group has 1 to 4 carbon atoms.
• Examples of the compound represented by the formula (b2) 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.
• Metal compound As the metal compound, a compound of a metal element belonging to Group 13 of the periodic table is used. Examples of the metal element belonging to Group 13 of the periodic table include aluminum (Al), gallium (Ga), indium (In), thallium (Tl), and the like, preferably aluminum.
• the metal compound is preferably a complex of a metal element belonging to Group 13 of the periodic table, and more preferably a metal complex having a chelate ligand.
• an Al compound is preferable, and an Al complex is more preferable.
• Al compounds include aluminum inorganic compounds such as aluminum hydroxide and aluminum oxide; aluminum alcoholates such as aluminum secondary butoxide, aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum trisethylacetoacetate, aluminum dioxide Isopropylate monosecondary butyrate, aluminum isopropylate, aluminum ethylate, aluminum ethyl acetoacetate diisopropylate, aluminum alkyl acetoacetate diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate) , Cyclic aluminum oxide isopropyl They include Al complexes such as over preparative, among them aluminum tris (ethylacetoacetate) are most preferred.
• gallium compound examples include gallium inorganic compounds such as gallium hydroxide and gallium oxide; and gallium complexes such as tris (2,4-pentanedionato) gallium (III).
• indium compound examples include indium inorganic compounds such as indium tin oxide; and indium complexes such as tris (2,4-pentanedionato) indium (III).
• the composition of the present invention includes a first organosilicon compound (A), a second organosilicon compound (B), and a compound of a metal belonging to Group 13 of the periodic table and a fluorinated solvent (C).
• a fluorinated solvent (C) for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent (particularly a fluorinated aromatic solvent) or the like can be used.
• a fluorinated solvent for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent (particularly a fluorinated aromatic solvent) or the like can be used.
• a fluorinated solvent for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent (particularly a fluorinated aromatic solvent) or the like can be used.
• a fluorinated solvent for example, a fluorinated
• the fluorinated ether solvent is preferably a hydrofluoroether such as fluoroalkyl (especially a perfluoroalkyl group having 2 to 6 carbon atoms) -alkyl (particularly a methyl group or ethyl group) ether, such as ethyl nonafluorobutyl ether or ethyl nona. Fluoroisobutyl ether is mentioned. Examples of ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether 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, and Florinate (registered trademark) FC-3283 (molecular weight of about 521, boiling point 128 ° C.) corresponds to this.
• the fluorinated hydrocarbon solvent include 1,3-bis (trifluoromethylbenzene) (boiling point: about 116 ° C.).
• hydrochlorofluorocarbons such as Asahiklin (registered trademark) AK225 (manufactured by Asahi Glass Co., Ltd.), hydrofluorocarbons such as Asahiclin (registered trademark) AC2000 (manufactured by Asahi Glass Co., Ltd.), etc. 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 total content of the first organosilicon compound (A) and the second organosilicon compound (B) in 100% by mass of the composition of the present invention is preferably 0.05% by mass or more, more preferably 0.08. It is at least mass%, more preferably at least 0.10 mass%, preferably at most 10 mass%, more preferably at most 5 mass%, still more preferably at most 1 mass%.
• the mass ratio of the first organosilicon compound (A) to the second organosilicon compound (B) in the composition of the present invention is preferably 0.5 or more, more preferably 1.0 or more, and 4 0.0 or less is preferable, and 3.5 or less is more preferable.
• the ratio of the metal compound of the present invention is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, and still more preferably 0.00% or more as a ratio with respect to the total of the compound (A) and the compound (B). 6 mol% or more, particularly preferably 1.0 mol% or more, most preferably 1.5 mol% or more, and preferably 6.0 mol% or less, more preferably 5.0 mol% or less. More preferably, it is 4.5 mol% or less, more preferably 3.5 mol% or less, particularly preferably 3.0 mol% or less, and most preferably 2.5 mol% or less.
• the mass ratio is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the total of the compound (A) and the compound (B). It is preferably 0.4% by mass or more, particularly preferably 0.5% by mass or more, and preferably 2.0% by mass or less, more preferably 1.7% by mass or less, and further preferably 1.3% by mass. % Or less, particularly 1.2% by mass or less, and most preferably 0.9% by mass or less.
• the metal compound is an Al complex
• the ratio of the metal complex to the total of the compound (A) and the compound (B) is preferably 0.6 to 5.0 mol% (by mass ratio, 0.2 to 1.8 mass% is preferable)
• the ratio is preferably 1.4 mol% to 2.5 mol% (that is, 0.5 to 0.9 mass%).
• composition of the present invention is a silanol condensation catalyst, antioxidant, rust inhibitor, ultraviolet absorber, light stabilizer, fungicide, antibacterial agent, bioadhesion inhibitor, Various additives such as odorants, pigments, flame retardants and antistatic agents may be contained.
• 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, but the surface is preferably a metal or an alloy. More preferably, a metal such as iron, silicon, copper, zinc, and aluminum or an alloy containing these metals is used, and in particular, a base material that is iron or an iron alloy (particularly stainless steel represented by “SUS” in the JIS standard). In this case, the effect of excellent adhesion between the composition of the present invention and the substrate can be maximized. Therefore, the covering body provided with the film
• the substrate is preferably washed with an alkaline cleaning solution.
• an aqueous sodium hydroxide solution may be used.
• commercially available products such as Escreen W-3000L (manufactured by Sasaki Chemical Co., Ltd.) and Escreen AL-13 (manufactured by Sasaki Chemical Co., Ltd.) are available.
• a cleaning agent or a liquid containing thioglycolic acid may be used.
• the substrate may be subjected to an easy adhesion treatment, and the easy adhesion treatment may be performed after the previous cleaning.
• the 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 performed, or a glass film such as polysilazane may be applied to the substrate in advance.
• the composition of the present invention is applied and dried to form a film on the substrate.
• the method for applying the composition of the present invention include a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, a gravure coating method, hand coating (soaking a liquid into a cloth, And a spraying method (a method of applying a liquid as it is to a target using a dropper or the like) and spraying (a method of applying to a target using a spray).
• hand coating, pouring, spraying, and spray coating are preferable.
• the conditions after the composition of the present invention is applied to the substrate are not particularly limited, and may be left at room temperature and in the atmosphere, for example, for 1 hour or more. In this invention, normal temperature is 5 degreeC or more and 60 degrees C or less.
• the coating of the present invention can be produced particularly in the temperature range of 15 to 40 ° C. Thereafter, it may be further heated and dried at a temperature of 50 to 300 ° C., preferably 100 to 200 ° C. for about 10 to 60 minutes.
• the thickness of the film obtained from the composition of the present invention can be, for example, about 1 nm to 100 nm. Preferably they are 5 nm or more and 100 nm or less. Further, the film obtained from the composition of the present invention has water repellency, and the contact angle measured by the droplet method (analysis method: ⁇ / 2 method) at a liquid volume of 3 ⁇ L is, for example, 110 to 125 °. Degree.
• the sliding angle measured by a sliding method (analysis method: contact method) with a liquid amount of 6.0 ⁇ L and a sliding determination distance: 0.25 mm can be 50 ° or less, preferably 48 ° or less (the lower limit is not limited). 30 degrees).
• the SUS base material stainless steel base material
• the fabric was impregnated with an alkaline cleaner, and the surface of the SUS substrate was modified by wiping. Then, the substrate was allowed to stand for 30 minutes with the substrate surface moistened with the alkaline cleaner. Subsequently, the alkaline detergent on the surface was washed away with running water and dried with air.
• Example 1 As the first organosilicon compound (A), a compound represented by the following formula (1) (hereinafter referred to as compound a), and as the second organosilicon compound (B), FAS13E (C 6 F 13 —C 2 H 4 — Si (OC 2 H 5 ) 3 , boiling point 220 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) and FC-3283 (C 9 F 21 N, manufactured by Fluorinert, 3M) as a solvent were mixed and stirred at room temperature for a predetermined time.
• compound a a compound represented by the following formula (1)
• FC-3283 C 9 F 21 N, manufactured by Fluorinert, 3M
• the obtained solution was applied onto SUS304 manufactured by Shiraimatsu Kikai Co., Ltd., which was treated by the above-described substrate cleaning method, using a spray coater manufactured by Apiros Co., Ltd. Then, it left still at normal temperature for 3 hours, and obtained the transparent film on the SUS base material.
• Example 2 Except that the ratio of the added Al complex was 1.4 mol% (that is, the mass ratio of the Al complex to the total of the compounds (A) and (B) was 0.5 mass%), the same as in Example 1, A transparent film was obtained on a SUS substrate.
• Example 3 Except that the ratio of the added Al complex was 2.5 mol% (that is, the mass ratio of the Al complex to the total of the compounds (A) and (B) was 0.9 mass%), the same as in Example 1, A transparent film was obtained on a SUS substrate.
• Example 4 Except that the ratio of the added Al complex was 4.2 mol% (that is, the mass ratio of the Al complex to the total of the compounds (A) and (B) was 1.4 mass%), the same as in Example 1, A transparent film was obtained on a SUS substrate.
• Example 5 Except that the ratio of the added Al complex was 5.0 mol% (that is, the mass ratio of the Al complex to the total of the compounds (A) and (B) was 1.8 mass%), the same as in Example 1, A transparent film was obtained on a SUS substrate.
• Comparative Example 1 A transparent film was obtained on the SUS substrate in the same manner as in Example 1 except that the metal complex was not added.
• Comparative Example 2 Example except that the compound (B) was not used and the ratio of the added Al complex was 2.5 mol% with respect to the compound (A) (that is, 0.9 mass% with respect to the compound (A)). In the same manner as in Example 1, a transparent film was obtained on a SUS substrate.
• composition of the present invention can be applied to various members such as a metal member, a plastic member, a ceramic member, and a glass member, and in particular, a member whose surface used for automobiles, cooking utensils, shelves, work tables, tools, etc. is metal. It is possible to form a water-repellent film with high adhesive strength and is industrially useful.

Landscapes

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

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=63252597

Family Applications (1)

Country Status (5)

Families Citing this family (4)

Citations (2)

Family Cites Families (8)

• 2018
  • 2018-02-16 CN CN201880010265.6A patent/CN110268018A/zh active Pending
  • 2018-02-16 KR KR1020197027521A patent/KR20190116476A/ko not_active Ceased
  • 2018-02-16 WO PCT/JP2018/005417 patent/WO2018155325A1/ja active Application Filing
  • 2018-02-20 JP JP2018028136A patent/JP6993894B2/ja not_active Expired - Fee Related
  • 2018-02-21 TW TW107105713A patent/TWI762582B/zh not_active IP Right Cessation

Patent Citations (2)

Also Published As

Similar Documents

Legal Events