WO2010101146A1 - Composition pour agent de revêtement - Google Patents

Composition pour agent de revêtement Download PDF

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Publication number
WO2010101146A1
WO2010101146A1 PCT/JP2010/053336 JP2010053336W WO2010101146A1 WO 2010101146 A1 WO2010101146 A1 WO 2010101146A1 JP 2010053336 W JP2010053336 W JP 2010053336W WO 2010101146 A1 WO2010101146 A1 WO 2010101146A1
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Prior art keywords
group
fluoropolymer
repeating unit
agent composition
coating agent
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PCT/JP2010/053336
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English (en)
Japanese (ja)
Inventor
俊 齋藤
祥 増田
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旭硝子株式会社
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Priority to JP2011502761A priority Critical patent/JPWO2010101146A1/ja
Publication of WO2010101146A1 publication Critical patent/WO2010101146A1/fr

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    • 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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • 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

Definitions

  • the present invention relates to a coating agent composition used for forming a coating film on the surface of a substrate, more specifically, a fluorine-containing coating agent that provides a highly weather-resistant coating film excellent in graffiti removal, decontamination, and ink repellency.
  • the present invention relates to a composition, a method for producing a cured coating film formed from the coating agent composition, and a coated article having the cured coating film.
  • Fluorine-containing coating compositions such as paints, hard coats, and substrate protective coatings are excellent in weather resistance and UV resistance, so they can be used as maintenance-free high-performance coatings for high-rise buildings, large structures, ships, etc. , Used in a wide range of vehicles, residential properties, bridges, etc.
  • a felt pen used for graffiti is generally composed mainly of ink in which a dye or a pigment is dispersed in an organic solvent or water. Since the ink easily penetrates into fine irregularities in the coating film, once the ink adheres to the coating film, it is difficult to completely remove the ink, and it is difficult to return to the original state. There was no other way than repainting and erasing. Conventionally, as a means for easily removing graffiti, methods of Patent Documents 1 and 2 below in which graffiti-removable fluorine paint is applied to a wall surface or the like have been proposed.
  • fluororesin paints have been switched to weak solvent-type fluororesin paints, which are environmentally friendly paints, due to the impact on the base (old paint film) during repairs and the burden on the global environment.
  • the fluororesin used in the weak solvent type fluororesin coating has a low hydroxyl value in the resin due to the problem of solubility in the weak solvent.
  • the coating film formed from the fluororesin coating has a problem that the crosslinking density is low and the coating film surface hardness is low.
  • the coating film is formed from a fluororesin coating material in which an antifouling component is blended in the coating material, if the ink adheres to the coating film by graffiti or the like, the ink is easily added to the coating film. Invading and its removal was not easy.
  • Patent Document 1 discloses a fluororesin coating composition in which a silicone-modified acrylic resin having a hydroxyl group at a terminal and a matting agent are blended with a fluororesin.
  • the coating composition has a low surface gloss of the coating film due to the effect of the matting agent, and is unsuitable for applications requiring high coating gloss.
  • the surface of the coating film was rough due to the effect of the matting agent, and it was not easy to remove the ink component adhering to the coating film surface.
  • Patent Document 2 discloses a fluororesin coating composition in which a liquid polydialkylsiloxane containing an amino group and a curing agent are blended with a fluororesin.
  • the coating film formed from the coating composition has a problem that the surface hardness may be insufficient, and the coating film is damaged by a brush or the like used for wiping off the dirt component.
  • An object of the present invention is to provide a fluorine-containing coating agent composition that provides a highly weather-resistant coating film excellent in graffiti removal, contamination removal, and ink repellency.
  • the inventors have prepared a fluorine-containing polymer (A) containing a hydrolyzable silyl group, a curing agent (B), a phosphate ester catalyst (C), an organic solvent (D), and a non-fluorine having an organosiloxane group.
  • the fluorine-containing coating agent containing the polymer (E) was found to give a highly weather-resistant coating film excellent in graffiti removal, contamination removal, and ink repellency after curing, and the present invention was completed. .
  • Curing agent (B) comprising the following fluoropolymer (A), a compound represented by the following formula (2) and / or a partially hydrolyzed condensate thereof, phosphate ester curing catalyst (C), organic A coating agent composition comprising a solvent (D) and a non-fluorine polymer (E) having an organosiloxane chain.
  • the repeating unit (A2) polymerizes a repeating unit based on a monomer comprising a reaction product of a hydroxyl group of the hydroxyl group-containing monomer and an isocyanate group of the compound represented by the following formula (1a), or a hydroxyl group-containing monomer.
  • the ratio of the repeating unit (A1) to the total content of the repeating unit (A1) and the repeating unit (A2) in the fluoropolymer (A) is 10 to 99 mol%, and the repeating unit (A2)
  • the ratio of the total of the repeating units (A1) and the repeating units (A2) is 1 to 90 mol% and the total content of all the repeating units in the fluoropolymer (A) is
  • the non-fluorine polymer (E) having an organosiloxane chain is at least one selected from the group consisting of a silicone resin, a silicone-modified epoxy resin, a silicone-modified phenol resin, a silicone-modified acrylic resin, and a silicone-modified polyester resin.
  • a method for producing a cured coating film wherein the coating agent composition according to any one of [1] to [10] is applied to an article surface and cured.
  • a coating agent composition that provides a highly weather-resistant coating film excellent in graffiti removal, contamination removal, and ink repellency.
  • the repeating unit obtained directly by polymerization and the repeating unit obtained by reacting the repeating unit obtained by polymerization with another compound are collectively referred to as “unit”.
  • the compound represented by the formula (1a) is referred to as the compound (1a)
  • the group represented by the formula (1) is referred to as the group (1)
  • the unit (A1) based on the fluoroolefin is simply referred to as the unit (A1).
  • Other units may be similarly described.
  • the coating agent composition of the present invention comprises a fluorine-containing polymer (A), a curing agent (B), a phosphate ester curing agent (C), an organic solvent (D), and a non-fluorine polymer having an organosiloxane chain ( E).
  • the fluorine-containing polymer (A) is a fluorine-containing polymer containing a unit (A2) having a unit (A1) of a fluoroolefin and a group (1).
  • the fluoropolymer (A) is a unit of a monomer in which an alkyl group and a polymerizable unsaturated group are linked by an ether bond or an ester bond (hereinafter referred to as “alkyl group-containing monomer”) as an optional component.
  • alkyl group-containing monomer a monomer in which an alkyl group and a polymerizable unsaturated group are linked by an ether bond or an ester bond
  • alkyl group-containing monomer a hydroxyl group-containing monomer unit (A4), and other units may be included.
  • the unit (A1) is a fluoroolefin unit.
  • a fluoroolefin is a compound in which one or more hydrogen atoms of an unsaturated hydrocarbon compound are substituted with fluorine atoms, and a part or all of the remaining hydrogen atoms may be substituted with chlorine atoms. It is a sex compound.
  • the number of hydrogen atoms substituted with fluorine atoms (hereinafter referred to as “fluorine addition number”) is preferably 2 or more, and more preferably 3 to 4. When the fluorine addition number is 2 or more, the weather resistance of the coating film is sufficient.
  • the fluoroolefin is preferably a fluoroolefin having 2 to 3 carbon atoms such as tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, etc., from the viewpoint of the weather resistance and solvent resistance of the coating film. Tetrafluoroethylene and chlorotrifluoroethylene (hereinafter referred to as “CTFE”) are more preferable.
  • CTFE chlorotrifluoroethylene
  • the unit (A1) may be only one type or a combination of two or more types.
  • the unit (A2) is a unit having a group (1).
  • X 1 is an alkoxy group having 1 to 5 carbon atoms, preferably an ethoxy group or a methoxy group. Within this range the number of carbon atoms in X 1, the alcohol component generated by a condensation reaction is less likely to remain in the coating film after curing, water resistance of the coating film, the solvent resistance is improved.
  • R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably a monovalent hydrocarbon group.
  • the monovalent hydrocarbon group preferably has 1 to 5 carbon atoms, more preferably 1 or 2. Specifically, a methyl group or an ethyl group is preferable.
  • the group (1) does not become too bulky, and the condensation reaction of the alkoxy group (X 1 ) proceeds smoothly when the coating film is cured.
  • the condensation reaction of the alkoxy group (X 1 ) is sufficiently advanced, the coating film is sufficiently cured, the surface hardness of the coating film is sufficiently high, and the graffiti removal property, stain resistance, and weather resistance are good.
  • n is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.
  • m is an integer of 1 to 5, preferably 2 to 5, and more preferably 2 to 4.
  • the group (1) includes a urethane-bonded nitrogen atom having the formula: — (CH 2 ) 3 Si (OCH 3 ) 3 , — (CH 2 ) 3 Si (OC 2 H 5 ) 3 , — (CH 2 ) 3 Si (CH 3 ) (OCH 3 ) 2 , — (CH 2 ) 3 Si (CH 3 ) (OC 2 H 5 ) 2 , — (CH 2 ) 3 Si (CH 3 ) 2 (OCH 3 ), — (CH 2 ) 3 Si (CH 3 ) 2 (OC 2 H 5 ), — (CH 2 ) 4 Si (OCH 3 ) 3 , — (CH 2 ) 4 Si (OC 2 H 5 ) 3 , — (CH 2 ) 2 A group in which groups represented by Si (OCH 3 ) 3 and — (CH 2 ) 2 Si (OC 2 H 5 ) 3 are bonded is preferable.
  • the unit (A2) is a unit obtained by polymerizing a monomer comprising a reaction product of a hydroxyl group of a hydroxyl group-containing monomer and an isocyanate group of the compound (1a) represented by the following formula, or a unit obtained by polymerizing a hydroxyl group-containing monomer. It is preferably any unit obtained by reacting the isocyanate group of the compound (1a) with a hydroxyl group.
  • the structure of the unit (A2) is determined by the type of the hydroxyl group-containing monomer and the compound (1a) to be combined.
  • hydroxyl group-containing monomer examples include hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,4-cyclohexane dimethanol monovinyl ether; diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol Polyethylene glycol monovinyl ethers such as monovinyl ether; Hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, 1,4-cyclohexanedimethanol monoallyl ether; Diethylene glycol monoallyl ether, tri Polyethylene such as ethylene glycol monoallyl ether and tetraethylene glycol monoallyl ether Lenglycol monoallyl ethers; hydroxyalkyl vinyl esters such as hydroxyacetic acid vinyl ester, 3-hydroxypropionic acid vinyl ester, 4-hydroxybutyric acid vinyl ester; hydroxyacetic acid
  • (meth) acrylic acid shows either acrylic acid or methacrylic acid.
  • the hydroxyl group-containing monomer is polyethylene glycol monovinyl ethers or polyethylene glycol monoallyl ethers
  • the number of polyethylene glycol moieties to be polymerized is preferably 2-20, more preferably 2-15, and even more preferably 2-10.
  • hydroxyalkyl vinyl ethers and polyethylene glycol monovinyl ethers are more preferable because of excellent alternating copolymerization and good weather resistance of the formed coating film. Specifically, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether are more preferable. Only one type of hydroxyl group-containing monomer may be used, or two or more types may be used in combination.
  • R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 or 2. Specifically, a methyl group or an ethyl group is preferable.
  • X 1 is an alkoxy group having 1 to 5 carbon atoms, preferably an ethoxy group or a methoxy group.
  • n is an integer of 1 to 3, preferably 3, m is an integer of 1 to 5, and 2 to 4 is more preferable.
  • Examples of the compound (1a) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, 3-isocyanatepropyldimethylmethoxysilane, 3- Isocyanatepropyldimethylethoxysilane, 4-isocyanatobutyltrimethoxysilane, 4-isocyanatobutyltriethoxysilane, 2-isocyanatoethyltrimethoxysilane, and 2-isocyanatoethyltriethoxysilane are preferred.
  • the compound (1a) is easily available, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane are more preferable. Only 1 type may be used for a compound (1a) and it may use it in combination of 2 or more type.
  • the method for obtaining the unit (A2) is preferably any one of the following method (i) and method (ii).
  • Step (ii) A copolymer having a hydroxyl group in the side chain is obtained by copolymerizing a hydroxyl group-containing monomer, a fluoroolefin, and another monomer as required.
  • the unit (A2) is a polymerized unit obtained by polymerizing a monomer composed of a reaction product of a hydroxyl group-containing monomer and the compound (1a).
  • the monomer include a reaction product of 2-hydroxyethyl vinyl ether and 3-isocyanatopropyltrimethoxysilane, a reaction product of 2-hydroxyethyl vinyl ether and 3-isocyanatepropyltriethoxysilane, and 4-hydroxybutyl.
  • a reaction product of diethylene glycol monovinyl ether and 3-isocyanatopropyltriethoxysilane is preferred.
  • 2-hydroxyethyl vinyl ether and 3-isocyanatopropyl trimethyl are preferred because of the ease of monomer purification, the stability of the fluoropolymer (A), the compatibility with the curing agent component, and the good reactivity.
  • a reaction product of ethoxysilane, a reaction product of 4-hydroxybutyl vinyl ether and 3-isocyanatopropyltriethoxysilane, and a reactive organism of diethylene glycol monovinyl ether and 3-isocyanatopropyltriethoxysilane are more preferable.
  • the monomer used at the time of polymerization may be used alone or in combination of two or more.
  • the unit (A2) is a unit in which the compound represented by the formula (1a) is reacted with the polymerization unit of the hydroxyl group-containing monomer.
  • the unit include a unit obtained by reacting a unit of 2-hydroxyethyl vinyl ether and 3-isocyanatopropyltrimethoxysilane, and a unit of 2-hydroxyethyl vinyl ether and 3-isocyanatepropyltriethoxysilane.
  • the stability of the fluoropolymer (A), the compatibility with the curing agent component, and the reactivity are good, so the unit of 2-hydroxyethyl vinyl ether reacts with 3-isocyanatopropyltriethoxysilane. More preferred are units obtained by reacting 4-hydroxybutyl vinyl ether units with 3-isocyanatopropyltriethoxysilane, and units obtained by reacting diethylene glycol monovinyl ether units with 3-isocyanatopropyltriethoxysilane.
  • the unit (A2) is a combination of 2-hydroxyethyl vinyl ether and 3-isocyanatopropyltriethoxysilane, 4-hydroxybutyl vinyl ether and 3-isocyanate.
  • a structure obtained by a combination with propyltriethoxysilane or a combination of diethylene glycol monovinyl ether and 3-isocyanatepropyltriethoxysilane is more preferable. Only one type of unit (A2) may be used, or a combination of two or more types may be used.
  • how to obtain the unit (A2) may be appropriately selected in view of ease of production, cost, etc., and the method (i) is carried out under polymerization conditions in order to prevent gelation during production.
  • the amount of the compound (1a) is more than 0.1 mol, a sufficient curing reaction occurs and the original performance of the coating film such as weather resistance, solvent resistance and impact resistance can be sufficiently exhibited.
  • the amount of the compound (1a) is less than 10 mol, the compound hardly remains in the coating film in a large amount as an unreacted product, and the water resistance and solvent resistance of the coating film are improved.
  • step (i-1) the reaction between the hydroxyl group and the isocyanate group can be carried out with a yield of almost 100%.
  • the reaction product may be gelled. Therefore, the reaction may be performed under conditions where the conversion rate is lower than 100%.
  • the step (i-2) may be performed after removing the unreacted hydroxyl group-containing monomer from the reaction product, or the step (i-2) is performed while the reaction product still contains the unreacted hydroxyl group monomer. May be.
  • the amount of the unreacted hydroxyl group-containing monomer is small, and the water resistance of the coating is improved by reducing the hydroxyl group content of the fluoropolymer (A) obtained in the step (i-2).
  • step (ii-2) it is preferable that 50 mol% or more of the hydroxyl groups contained in the fluoropolymer (A) are modified by reacting with the isocyanate groups of the compound (1a).
  • the water resistance of the paint is improved.
  • a modification rate of 50 to 70% is preferable from the viewpoint of reducing the cost.
  • step (i-2) is carried out while containing unreacted hydroxyl monomer in step (i-1) of method (i), and in step (ii-2) of method (ii) 100
  • step (ii-2) is carried out while containing unreacted hydroxyl monomer in step (i-1) of method (i), and in step (ii-2) of method (ii) 100
  • the obtained fluoropolymer (A) becomes a polymer containing units based on a hydroxyl group-containing monomer.
  • step (i-1) and step (ii-2) the addition reaction between a hydroxyl group and an isocyanate group is usually performed at room temperature to 100 ° C., preferably 50 to 70 ° C., under an inert atmosphere such as nitrogen. Is preferred.
  • the reaction time can be appropriately changed according to the progress of the reaction, preferably 1 to 24 hours, particularly preferably 3 to 10 hours.
  • an organometallic catalyst such as an organotin compound, an organoaluminum compound, an organozirconium compound, or an organotitanate compound is preferably present for the purpose of promoting the reaction.
  • the proportion of the unit (A1) in the fluoropolymer (A) is preferably from 10 to 99 mol%, more preferably from 30 to 95 mol%, based on the total content of the unit (A1) and the unit (A2). .
  • the proportion of the unit (A1) is less than 10 mol%, the weather resistance of the coating film is lowered, and when it exceeds 99 mol%, the adhesion with the substrate is lowered, which is not preferable.
  • the proportion of the unit (A2) in the fluoropolymer (A) is preferably from 1 to 90 mol%, more preferably from 5 to 70 mol%, based on the total content of the unit (A1) and the unit (A2). .
  • the unit (A2) is 1 mol% or more, the degree of cure of the coating film is sufficiently high, and the weather resistance is also good.
  • the stability of the fluoropolymer (A) is improved, and the pot life of the coating is also sufficient.
  • the total ratio of the unit (A1) and the unit (A2) with respect to all the units in the fluoropolymer (A) is preferably from 30 to 100 mol%, more preferably from 50 to 100 mol%.
  • the ratio of the unit (A1) to the total units in the fluoropolymer (A) is preferably 10 to 90 mol%, more preferably 30 to 70 mol%.
  • Fluoropolymer (A) in the present invention may optionally contain units other than units (A1) and units (A2).
  • units other than the unit (A1) and the unit (A2) a unit (A3) based on an alkyl group-containing monomer and / or a unit (A4) based on a hydroxyl group-containing monomer are preferable.
  • the other unit may be included as needed.
  • the alkyl group-containing monomer has an alkyl group and a polymerizable unsaturated group linked by an ether bond or an ester bond (hereinafter referred to as “linked bond” by combining the ether bond and the ester bond). It is preferably a unit obtained by polymerizing the monomer.
  • the polymerizable unsaturated group is preferably an ethylenically unsaturated group such as a vinyl group, an allyl group, or a 1-propenyl group.
  • the polymerizable unsaturated group and the linking bond preferably have a vinyl ether, allyl ether, vinyl ester, or allyl ester structure. Further, the vinyl group and allyl group of vinyl ester and allyl ester are preferably bonded to an oxygen atom of an ester bond.
  • the alkyl group preferably has 2 to 16 carbon atoms, and more preferably 3 to 10 carbon atoms.
  • the structure of the alkyl group is preferably a linear alkyl group or a branched alkyl group, and may have a cyclic structure such as a cyclopentyl group or a cyclohexyl group in the molecule, and a branched alkyl group is more preferable.
  • a branched alkyl group having 3 to 10 carbon atoms is particularly preferable because the solubility of the fluoropolymer (A) in the weak solvent is good.
  • Monomers that form the unit (A3) by polymerization include vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; allyl ethers such as ethyl allyl ether, butyl allyl ether, and cyclohexyl allyl ether; Vinyl esters such as vinyl acetate, vinyl pivalate, vinyl benzoate and vinyl versatate; allyl esters such as allyl acetate, allyl pivalate, allyl benzoate and allyl versatate are preferred.
  • the monomer forming the unit (A3) improves the solubility of the fluoropolymer (A) in the weak solvent.
  • -Ethylhexyl vinyl ether and vinyl versatate are particularly preferred.
  • the ratio of the unit (A3) to the whole unit is preferably 0 to 70 mol%, more preferably 0 to 65 mol%.
  • the proportion of the unit (A3) is 0 mol%, it means that the unit (A3) is not included.
  • the lower limit is more than 0 mol%, and 0.01 mol% Is preferred.
  • the unit (A3) may be only one type or a combination of two or more types.
  • the preferable thing of the hydroxyl-containing monomer in the unit (A4) based on a hydroxyl-containing monomer is the same as the preferable thing of the hydroxyl-containing monomer used when forming the said unit (A2).
  • the hydroxyl group-containing monomer in the unit (A4) based on the hydroxyl group-containing monomer is more preferably the same as the hydroxyl group-containing monomer used when forming the unit (A2).
  • the unit (A4) based on the hydroxyl group-containing monomer is subjected to the step (i-2) while containing the unreacted hydroxyl monomer in the step (i-1) of the method (i).
  • step (ii-2) of ii) it is obtained by reacting with the isocyanate group of the compound (1a) to modify less than 100 mol% of the hydroxyl group, or a hydroxyl group-containing monomer separately during the polymerization of the fluoropolymer (A) It is preferable to obtain by adding and copolymerizing.
  • the ratio of the unit (A4) to the whole unit is preferably 0 to 30 mol%.
  • the lower limit is more than 0 mol%, and preferably 0.01 mol%. If the ratio of a unit (A4) is this range, sufficient stability of a fluoropolymer (A) can be ensured, and the solubility to an organic solvent will also become favorable.
  • the unit (A4) may be only one type or a combination of two or more types.
  • the fluoropolymer (A) obtained by the method (i) or the fluoropolymer (A) obtained by the method (ii) may be the whole of the fluoropolymer (A).
  • the total ratio of the unit (A2) and the unit (A4) to the unit is preferably 1 to 60 mol%, and more preferably 3 to 50 mol%.
  • the fluoropolymer (A) in the present invention may contain other units in addition to the units (A1) to (A4) (hereinafter referred to as “other units”).
  • the monomer forming the other unit is preferably a monomer composed of a non-fluorine compound, and is preferably a monomer having no hydrolyzable silyl group, hydroxyl group, alkyl vinyl ether group or alkyl vinyl ester group.
  • non-fluorinated olefins such as ethylene, propylene, n-butene and isobutene
  • unsaturated carboxylic acids such as vinyl acetic acid and (meth) acrylic acid
  • vinyl benzoate vinyl para-t-butylbenzoate, etc.
  • Non-fluorinated aromatic group-containing monomers nitrogen-containing monomers such as aminopropyl vinyl ether, diethylaminoethyl vinyl ether, 1-vinyl-2-pyrrolidone, 1-vinylimidazole, methacrylamide, and acrylamide: vinyl phosphoric acid, vinyl phosphoric acid dimethyl ester A phosphorus-containing monomer such as is preferable.
  • the ratio of the other units to the total units is preferably 0 to 5 mol%.
  • Other units may be only one type or a combination of two or more types.
  • the fluoropolymer (A) in the present invention is a polymer containing the unit (A1) and the unit (A2) as essential units, and optionally containing the unit (A3), the unit (A4), and other units. It is preferable.
  • the proportion of each unit constituting the more preferred fluoropolymer (A) is preferably 10 to 90 mol%, as described above, and preferably 30 to 70 mol. % Is more preferable.
  • the ratio of the unit (A3) to the total unit is preferably 5 to 50 mol%, more preferably 10 to 30 mol%.
  • the total ratio of the unit (A2) and the unit (A4) to the total unit is preferably 1 to 60 mol%, and more preferably 3 to 50 mol%. Further, the ratio of the unit (A2) to the total unit is preferably within the range of the preferable ratio of the total of the unit (A2) and the unit (A4) and is 1 to 40 mol%. ) And the unit (A4), and more preferably 3 to 25 mol%.
  • the total ratio of units (A1) to (A4) with respect to all units is preferably 95 to 100 mol%, and more preferably 100 mol%.
  • Preferred unit combinations include CTFE units / unit (A2) / polymer of alkyl vinyl ether units, CTFE units / unit (A2) / hydroxyalkyl vinyl ether units / alkyl vinyl ether units polymer, A polymer of CTFE units / unit (A2) / alkyl vinyl ester units is preferred.
  • the combination which contains 1 or more types of a unit (A3), a unit (A4), and another unit further in these combinations is also preferable.
  • the proportion of each unit constituting the fluorinated polymer (A) is the proportion of each monomer charged in the polymerization reaction for obtaining the fluorinated polymer (A), the reaction conditions, the fluorinated polymer (A) and the compound ( It can be changed depending on the charging ratio and reaction conditions when reacting 1a).
  • the fluorine content of the fluoropolymer (A) is preferably 35% by mass or less. If the fluorine content is within this range, the solubility of the fluoropolymer (A) in the solvent can be sufficiently secured.
  • the step (i-2) and the step (ii-1) can be performed by a known method.
  • a normal radical polymerization method can be employed, and as the polymerization form, solution polymerization, suspension polymerization, emulsion polymerization, or the like can be employed.
  • the reaction temperature during the polymerization is appropriately changed depending on the radical polymerization initiator to be used, but it is usually preferably 0 to 130 ° C.
  • the reaction time is preferably between 1 and 50.
  • the solvent include ion-exchanged water; alcohol solvents such as ethanol, butanol and propanol; saturated hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; methyl ethyl ketone Ketone solvents such as cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as cyclopentyl methyl ether can be used.
  • radical polymerization initiator examples include peroxydicarbonates such as diisopropyl peroxydicarbonate and di-n-propyl peroxydicarbonate; peroxydicarbonates such as t-hexyl peroxypivalate and t-butyl peroxypivalate. Oxyesters; ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide; 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, etc.
  • Peroxyketals peroxycarbonate esters such as t-hexylperoxy-n-butyl carbonate and t-butylperoxy-n-propyl carbonate; diacyl peroxides such as isobutyryl peroxide and lauroyl peroxide Id like; dicumyl peroxide, dialkyl peroxides such as di -t- butyl peroxide and the like can be used.
  • polymerization can be carried out in water and in the presence of an anionic or nonionic emulsifier using an initiator such as a water-soluble peroxide, a persulfate, or a water-soluble azo compound.
  • an initiator such as a water-soluble peroxide, a persulfate, or a water-soluble azo compound.
  • Examples of the copolymer having a hydroxyl group in the side chain obtained in step (ii-1) include Lumiflon (manufactured by Asahi Glass Co., Ltd., trade name), fluonate (manufactured by Dainippon Ink Chemical Co., Ltd., trade name), It is also possible to use commercially available fluororesins such as Cefral Coat (manufactured by Central Glass Co., Ltd., trade name), Zaflon (manufactured by Toagosei Co., Ltd., trade name), Zaffle (trade name, manufactured by Daikin Industries, Ltd.), etc. it can.
  • the fluorine-containing polymer (A) preferably has a number average molecular weight (Mn) of 5,000 to 20,000 as measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • Mn number average molecular weight
  • GPC gel permeation chromatography
  • the coating agent composition of this invention contains the compound represented by the following Formula (2) as a hardening
  • R 2 is a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • the monovalent hydrocarbon group as R 2 may have a substituent. That is, some or all of the hydrogen atoms of the monovalent hydrocarbon group may be substituted with a substituent.
  • R 2 is preferably a methyl group, a hexyl group, a decyl group, a phenyl group, or a trifluoropropyl group.
  • X 2 is an alkoxy group having 1 to 10 carbon atoms, preferably a methoxy group or an ethoxy group.
  • a is an integer of 1 to 4, preferably 2 to 4.
  • the compound represented by the formula (2) include tetrafunctional alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane; methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, Trifunctional alkoxysilanes such as phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane; dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxy And bifunctional alkoxysilanes such as silane.
  • tetrafunctional alkoxysilanes such as tetramethoxysilane, tetraethoxysi
  • tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and phenyltrimethoxysilane are preferable from the viewpoint of curing speed and physical properties of the coating film.
  • a part or all of the alkoxy group represented by X 2 is a fluoropolymer (A) and / or an organosiloxane chain.
  • a coating film is formed by reacting with the non-fluorinated polymer (E) having the following.
  • a compound represented by the formula (2) or a partial hydrolysis condensate thereof may be used alone, or a compound represented by the formula (2) and / or a partial hydrolyzate thereof. Two or more of these may be used in combination.
  • the partial hydrolysis-condensation product of the compound represented by the formula (2) is a compound obtained by partially hydrolyzing and condensing the compound represented by the formula (2). Although its overall structure is not clear, it is a polysilicate ester consisting of a skeleton composed of Si—O bonds and an alkoxy group (or a silanol group formed by hydrolysis of the alkoxy group), and the skeleton is linear However, it may be branched and may have a ring structure.
  • the method for producing the partial hydrolysis-condensation product of the compound represented by the formula (2) is not particularly limited, and a known method can be appropriately used. For example, it can be obtained by adding water, an acid and / or a solvent to the compound represented by the formula (2), and partially hydrolyzing and condensing it. Such partially hydrolyzed condensates of alkoxysilane compounds are commercially available in different condensation degrees, structures, and types of alkoxy groups.
  • MKC silicate MS51 trade names “MKC silicate MS51”, “MKC silicate MS51”, “ Effective silica content such as “MKC silicate MS56”, trade names “M silicate 51”, “ethyl silicate 40”, “ethyl silicate 45” manufactured by Tama Chemical Co., Ltd., or about 28-52% by mass, or Examples include “HAS-1”, “HAS-6”, and “HAS-10” manufactured by Colcoat Co., Ltd., in which these are dissolved in ethanol or isopropanol.
  • the “effective silica content” is a value indicating the content of silica in terms of SiO 2 when the polyalkyl silicate contained in the product is 100% by mass.
  • the proportion of the fluoropolymer (A) in the total content of the fluoropolymer (A) and the curing agent (B) is 10 to 90% by mass, 20 It is preferably ⁇ 80% by mass, and more preferably 30 to 70% by mass.
  • the content of the fluorinated polymer (A) is 10% by mass or more, the flexibility of the coating film becomes sufficient, and problems such as generation of cracks in the coating film and decrease in adhesion are less likely to occur.
  • the content of the fluoropolymer (A) is 90% by mass or less, the balance between the content of the fluoropolymer (A) and the curing agent (B) is good, the surface hardness of the coating film becomes good, and the graffiti Removability and decontamination are sufficient.
  • the coating agent composition of the present invention is a phosphate ester-based curing catalyst for the purpose of accelerating the curing reaction, imparting good chemical performance and physical performance to the cured product, and curing at a low temperature in a short time. (C) is contained.
  • Specific examples of the phosphoric ester-based curing catalyst (C) include acidic phosphoric esters such as phosphoric monoesters and phosphoric diesters; addition reaction products of acidic phosphoric esters and amines, and the like.
  • an acidic phosphate ester represented by the following formula (3) and having an acid value in the range of 10 to 800 mgKOH / g is preferable.
  • An acidic phosphate ester having an acid value in the range of 100 to 500 mgKOH / g is more preferable.
  • the acid value of the acidic phosphate is in the range of 10 to 800 mgKOH / g, the pot life of the paint can be sufficiently secured, and the curability of the paint film is improved, resulting in a cured paint film having excellent mechanical properties. Is obtained.
  • R 3 is preferably an alkyl group, cycloalkyl group or aryl group having 3 to 10 carbon atoms, and h is preferably 1 or 2.
  • primary alcohols such as n-propanol, n-butanol, n-hexanol, n-octanol, 2-ethylhexanol; isopropanol, 2-butanol, 2-hexanol, 2-octanol, cyclohexanol, etc.
  • Examples thereof include phosphoric monoesters or phosphoric diesters of secondary alcohols.
  • AP-1 The trade names “AP-1”, “AP-4”, “DP-4”, “MP-4”, “AP-8”, “AP-10”, “MP-10”, etc., manufactured by Daihachi Chemical Industry Co., Ltd. are preferred. . If the acid value of the phosphate ester curing catalyst is 10 mgKOH / g or more, the curing rate of the coating film is sufficient, and if the acid value is 800 mgKOH / g or less, the pot life of the paint is sufficient, and the coating workability is improved. improves.
  • the addition amount of the curing catalyst is usually selected in the range of 0.0001 to 10 parts by mass with respect to 100 parts by mass of the fluoropolymer (A). If the amount of the curing catalyst is 0.0001 part by mass or more, the catalytic effect is sufficiently developed, and if it is 10 parts by mass or less, the finally obtained coating film is not colored. Also, the water resistance is sufficient.
  • acidic phosphate esters may be used alone or in combination of two or more.
  • the organic solvent (D) contained in the coating agent composition of the present invention includes, for example, ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, ethyl butyl ketone, diisobutyl ketone, cyclohexanone, isophorone; methyl acetate, ethyl acetate, n-acetate Esters such as propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate; toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine oil, Solvesso # 100 (registered trademark of Exxon Chemical Co., Ltd.) , Aromatic hydrocarbons such as Solvesso # 150 (registered trademark of Exxon Chemical Co., Ltd.); ethers such as
  • the weak solvent is selected from the group consisting of gasoline, coal tar naphtha, solvent naphtha, petroleum ether, petroleum naphtha, petroleum benzine, turpentine oil, mineral spirit, mineral thinner, petroleum spirit, white spirit, and mineral turpentine. At least one solvent.
  • a solvent corresponding to the PRTR method and HAPs regulations it is preferable to use an ester solvent or a ketone solvent that does not contain an aromatic group.
  • a weak solvent it is preferable to use a paraffinic solvent or a naphthenic solvent.
  • Ketone solvents and ester solvents include ketones such as methyl ethyl ketone, diisobutyl ketone, cyclohexanone and isophorone from the viewpoint of boiling point and resin solubility; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetate Esters such as butyl, isobutyl acetate, and t-butyl acetate can be preferably used, but t-butyl acetate, which is a HAPs regulation compliant solvent, is more preferable.
  • the organic solvent (D) in the present invention it is most preferable to use a weak solvent.
  • a weak solvent As the organic solvent (D), it is possible to reduce the influence on the base (old paint film) during repair and the burden on the global environment.
  • a weak solvent when used as the organic solvent (D), it is generally necessary to lower the polarity of the resin, that is, the hydroxyl value, resulting in a decrease in the number of cross-linked sites. The crosslink density decreases and the hardness of the coating film decreases.
  • the fluoropolymer (A) in the present invention has a characteristic that it is easily dissolved in a low-polarity solvent such as a weak solvent while maintaining a sufficient amount of crosslinking sites. Therefore, when the weak solvent is used as the organic solvent (D), the effect of the present invention is most effectively exhibited.
  • a solvent having an aniline point of 30 ° C. to 70 ° C. is preferable.
  • the lower limit of the aniline point is more preferably 40 ° C, and the upper limit of the aniline point is more preferably 60 ° C.
  • the aniline point exceeds 30 ° C, the old coating film is not affected, and if the aniline point is 70 ° C or less, the solubility of the fluorinated copolymer (A) and the curing agent (B) used in the present invention is improved.
  • the aniline point may be measured according to the aniline point test method described in JIS K 2256.
  • organic solvent (D) a mineral spirit is preferable because the flash point is room temperature or higher.
  • Solvents commonly sold as mineral spirits include, for example, HAWS (manufactured by Shell Japan, aniline point 17 ° C.), Essonaphtha No.
  • the coating agent composition of the present invention uses a weak solvent as the organic solvent (D)
  • the weak solvent is used as a polymerization solvent for the fluoropolymer (A) or polymerized in another solvent. It is preferable that a part or all of the solvent or dispersion medium is replaced with a weak solvent later. Further, the concentration of the obtained composition may be adjusted as necessary, or other components may be added to the composition as necessary.
  • the content of the organic solvent (D) in the coating agent composition of the present invention is appropriately determined in consideration of the solubility of the fluoropolymer (A), the appropriate viscosity when applied as a paint, the coating method, and the like. .
  • the content of the organic solvent (D) is preferably 10 to 150 parts by mass, more preferably 25 to 100 parts by mass with respect to 100 parts by mass of the fluoropolymer (A).
  • the organic solvent (D) contained in the coating agent composition of the present invention may be only one type or a combination of two or more types.
  • Non-fluorine polymer (E) having an organosiloxane chain The non-fluorine polymer (E) having an organosiloxane chain (hereinafter sometimes referred to as a non-fluorine polymer (E)) is a polymer having an organosiloxane chain and containing no fluorine atom.
  • Non-fluorinated polymers (E) include hydroxyl group-containing silicone resins, methoxy group-containing silicone resins, epoxy-modified silicone resins, phenol-modified silicone resins, acrylic-modified silicone resins, polyester-modified silicone resins, alkyd-modified silicone resins, and silicone-modified acrylics. Resin.
  • non-fluorinated polymers (E) preferably have a hydroxyl group. Since the non-fluorinated polymer (E) having a hydroxyl group easily reacts with the fluoropolymer (A) and the curing agent (B), the graffiti removing property, the decontamination property, and the water repellency of the coating film are maintained. Conceivable. More preferably, a hydroxyl group-containing silicone resin and an acrylic modified silicone resin containing a hydroxyl group are used. A silicon-modified acrylic resin containing a hydroxyl group is a graft polymer in which polysiloxane is a side chain and an acrylic polymer is bonded as a main chain. The hydroxyl group-containing silicone resin and the silicon-modified acrylic resin are excellent in terms of compatibility with the fluoropolymer (A) and the curing agent (B).
  • the hydroxyl value of the non-fluorinated polymer (E) reacts easily and sufficiently with the fluorinated polymer (A) and the curing agent (B), resulting in a paint film that maintains graffiti removal, contamination removal, and water repellency. Since it can form, it is preferable that it is 30 mgKOH / g or more, and it is more preferable that it is 60 mgKOH / g or more.
  • the hydroxyl value is preferably 200 mgKOH / g or less, preferably 150 mgKOH / g or less in terms of solubility in an organic solvent and compatibility with the fluoropolymer (A) and the curing agent (B). More preferably.
  • the mass average molecular weight (M w ) of the non-fluorinated polymer (E) is preferably 1,000 or more and 30,000 or less, and more preferably 5,000 or more and 20,000 or less.
  • M w mass average molecular weight
  • the mass average molecular weight is not less than the lower limit of the above range, the decontamination property is excellent.
  • this mass average molecular weight is made below the upper limit of the said range, it is excellent in compatibility with a fluoropolymer (A) and a hardening
  • non-fluorine polymer (E) satisfying these preferable conditions examples include BYK-Silclean 3700 (manufactured by BYK Japan, solid content 25%, hydroxyl value 120 mgKOH / g) and X-22-160AS (Shin-Etsu Chemical Co., Ltd.). Co., Ltd., hydroxyl value 120 mgKOH / g), KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value 62 mgKOH / g), XF42-B0970 (manufactured by Momentive Performance Materials, hydroxyl value 60 mgKOH / g) g).
  • the content of the non-fluorine polymer (E) in the coating agent composition of the present invention is 0.01 to 20% of the non-fluorine polymer (E) with respect to 100 parts by mass of the fluoropolymer (A). 0 parts by mass is preferable, and 0.1 to 10.0 parts by mass is more preferable.
  • the non-fluorine polymer (E) in the coating agent composition of the present invention may be used alone or in combination of two or more.
  • the coating agent composition of the present invention may contain a colorant (pigment or dye), a silane coupling agent for improving the adhesion of the coating film, and the like.
  • a colorant pigment or dye
  • the pigment include inorganic pigments such as carbon black and titanium oxide, and organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone red, indanthrene orange, and isoindolinone-based yellow.
  • the titanium oxide is preferably a surface-coated titanium oxide, and the titanium oxide can be obtained under the trade name “PFC-105” manufactured by Ishihara Sangyo Co., Ltd .; the trade name “D-918” manufactured by Sakai Chemical Co., Ltd.
  • a light stabilizer examples include hindered amine light stabilizers.
  • trade names “MARX LA62” and “MARX LA67” manufactured by Adeka Argus Chemical Co., Ltd .; trade names manufactured by Ciba Specialty Chemicals Co., Ltd. “Tinuvin 292”, “Tinuvin 144”, “Tinuvin-123”, “Tinuvin 440” and the like can be mentioned.
  • ultraviolet absorbers examples include benzophenone compounds, benzotriazole compounds, triazine compounds, and cyanoacrylate compounds.
  • Examples of the compound include “Viosorb130”, “Viosorb582”, “Viosorb583” (manufactured by Kyodo Pharmaceutical Co., Ltd., trade name), “Tinuvin 320”, “Tinuvin 982”, “Tinuvin 1130”, “Tinuvin 400” (above, Ciba Specialty Chemicals, trade name) and the like.
  • Examples of matting agents include ultra fine powder synthetic silica. When a matting agent is used, an elegant semi-gloss and matte finish can be formed.
  • a surfactant may be added to the coating composition of the present invention.
  • Surfactants are effective because they can control the surface tension.
  • the surfactant may be any of nonionic type, cationic type, anionic type, ROLEX ASE (made by Daiichi Kogyo Co., Ltd., trade name), “Surflon”, a fluorosurfactant (made by Asahi Glass Co., Ltd., trade name) Acrylic “Modaflow” (manufactured by Monsanto, trade name), “Leo Fat” series (trade name, manufactured by Kao), and the like.
  • the uniformity of the thickness of the coating film can be improved.
  • the leveling agent include BYK-300 (manufactured by BYK-Chemie, trade name), Floren No. 3 (manufactured by Kyoeisha Chemical Co., Ltd., trade name), Disparon LF 1985 (manufactured by Enomoto Kasei Co., Ltd., trade name) and the like.
  • a dehydrating agent may be added to the coating composition.
  • the dehydrating agent include orthoformates such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate; orthoacetic esters such as trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate; trimethyl orthopropionate, ortho Orthopropionic acid esters such as triethyl propionate and tripropyl orthopropionate; dimethoxymethane, 1,1-dimethoxyethane, 1,1-dimethoxypropane, diethoxyethane, 1,1-diethoxyethane, 1,1- Acetals such as diethoxypropane; 1-methoxy-1-ethanol, 1-methoxy-1-propanol, 1-methoxy-1-butanol, 1-ethoxy-1-ethanol, 1-ethoxy-1-propanol, 1-methoxy-1-propanol Ethoxy-1-
  • the dehydrating agent When a dehydrating agent is blended, the dehydrating agent is added in an amount of 1 to 10 parts by mass with respect to 100 parts by mass of the fluoropolymer.
  • the blending amount of the other components can be appropriately selected within a range not impairing the effects of the present invention.
  • the coating agent composition of this invention can be manufactured by mixing the said essential component and the various additives added as needed.
  • the mixing order and addition order are not particularly limited.
  • the coating agent composition of the present invention may be used as a one-component type paint containing a curing agent (B), or a two-component type in which the curing agent (B) is added immediately before using the paint. It may be used as a paint.
  • any method such as spray coating, brush coating, dipping method, roll coater, flow coater and the like can be applied.
  • the coating composition of the present invention is preferably dried and cured at room temperature when forming a coating film, but in some cases, curing may be accelerated by heating.
  • Hardening apparatuses such as a closed-type hardening furnace and a tunnel furnace which can be continuously hardened, are employable.
  • the heating source is not particularly limited, and can be performed by a method such as hot air circulation, infrared heating, high frequency heating or the like.
  • the temperature and time required for curing vary depending on the type of catalyst and the like, but curing conditions of about 1 to 10 hours are generally preferred at a temperature in the range of 50 to 150 ° C. More preferably, the curing conditions are in the temperature range of 50 to 80 ° C. for 30 minutes to 2 hours.
  • the antifouling component (E) When curing is accelerated by heating, the antifouling component (E) is more easily transferred to the surface of the coating film, and the graffiti removal property, contamination removal property, and water repellency of the coating film are improved, and the Tg of the coating film is further increased. Therefore, when wiping away contaminating components with a brush or the like, the coating film is less likely to be damaged.
  • the material of the article to be painted is not particularly limited, and includes inorganic materials such as concrete, natural stone, and glass; metals such as iron, stainless steel, aluminum, copper, brass, and titanium; organic materials such as plastic, rubber, adhesive, and wood. It is done. Moreover, FRP which is an organic inorganic composite material, resin reinforced concrete, fiber reinforced concrete, etc. are mentioned.
  • the coating agent composition of the present invention is particularly suitable for application to the surface of an already formed coating film.
  • Articles to be painted include transportation equipment such as automobiles, trains and aircraft; civil engineering members such as bridge members and steel towers; industrial equipment such as waterproof sheets, tanks and pipes; building exteriors, doors, window gate members, monuments, poles Building materials such as: Road median strips, guardrails, soundproof walls, light-transmitting plates such as polycarbonate, acrylic, etc .; communication equipment; electrical and electronic parts; solar cell backsheets, solar cell surface protection paints, etc. It is done.
  • chlorotrifluoroethylene 505 g was introduced into the autoclave and the temperature was gradually raised. After reaching 65 ° C., a 50% xylene solution of t-butyl peroxypivalate (7 g) was added over 7 hours. The reaction was stopped after introduction into an autoclave and further stirring for 15 hours.
  • chlorotrifluoroethylene 505 g was introduced into the autoclave and the temperature was gradually raised. After reaching 65 ° C., a 50% xylene solution of t-butyl peroxypivalate (7 g) was added over 7 hours. The reaction was stopped after introduction into an autoclave and further stirring for 15 hours.
  • Examples 1 to 4 Comparative Examples 1 and 2
  • a coating agent composition containing a titanium oxide pigment was prepared. Further, mineral spirits were added so that the viscosity by an Iwata cup (viscosity adjusting device) was 25 seconds to obtain a white enamel paint.
  • the obtained white enamel paint was applied to the surface of a chromate-treated aluminum plate so as to have a film thickness of 50 ⁇ m, and was cured in a thermostatic chamber at 25 ° C. for 1 week. Then, the test board with a coating film was created by making it dry in 80 degreeC oven for 1 hour.
  • AP-8 A mixture of mono-2-ethylhexyl phosphate and di-2-ethylhexyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.).
  • D-918 Titanium oxide pigment (manufactured by Sakai Chemical Co., Ltd.).
  • BYK-300 Leveling agent (manufactured by BYK-Chemie).
  • BYK-Silclean 3700 a hydroxyl group-containing silicon-modified acrylic resin (BYK-Chemie).
  • X-22-160AS hydroxyl group-containing silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Oil-based ink repellency Doodles of red and black oil-based inks are made on the coatings of each test specimen, and the repellency of oil-based inks is evaluated as “ ⁇ ”. “ ⁇ ” and the middle of the evaluation were evaluated as “ ⁇ ”. Furthermore, the same repellency was evaluated after wiping the test plate with ethanol 50 times. 4). Removability of oil-based ink Doodles with red and black oil-based inks were made on the coating film of each test specimen, held in an oven at 50 ° C for 1 hour, and then wiped as BEMCOT (trade name, manufactured by Ozu Sangyo Co., Ltd.) Was wiped dry.
  • BEMCOT trade name, manufactured by Ozu Sangyo Co., Ltd.
  • Carbon contamination test Carbon suspension water (dispersion liquid dispersed in paint shaker for 2 hours by adding glass beads to 5 parts of Carbon Black FW200 from Degussa Huls and 95 parts of deionized water) It was dropped with a dropper until the coating film was concealed, and immediately dried at 50 ° C. for 1 hour. After drying, the sample was allowed to cool to room temperature, and the surface of the test piece was washed with running water under running water until the soiled material did not fall off.
  • Lightness difference ( ⁇ L * ) [Coating film brightness after test (L * 1 ) ⁇ Coating film brightness before test (L * 0 )) ⁇ : Lightness difference ⁇ 5 or more ⁇ : Lightness difference ⁇ 10 or more, less than ⁇ 5 ⁇ : Lightness difference ⁇ 10 or less
  • PG-1M Gelloss meter: Nippon Denshoku Industries Co., Ltd.
  • the weather resistance was evaluated according to the following criteria.
  • ⁇ Gloss retention 80% or more.
  • ⁇ Gloss retention 60% or more and less than 80%.
  • X Gloss retention less than 60%.

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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

Cette invention concerne une composition pour agent de revêtement contenant du fluor, ladite composition produisant une pellicule extrêmement insensible aux intempéries et dotée d'excellentes propriétés protégeant des graffitis, éliminant les poussières et repoussant l'encre. L'agent de revêtement contenant du fluor comprend (A) un polymère fluoré ayant un groupe silyle hydrolysable, (B) un agent de vulcanisation, (C) un catalyseur à base d'ester phosphorique, (D) un solvant organique et (E) un polymère non fluoré comportant un groupe organosiloxane ; cet agent de revêtement produit une pellicule extrêmement insensible aux intempéries dotée d'excellentes propriétés protégeant des graffitis, éliminant les poussières et repoussant l'encre.
PCT/JP2010/053336 2009-03-02 2010-03-02 Composition pour agent de revêtement WO2010101146A1 (fr)

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WO2013175962A1 (fr) * 2012-05-24 2013-11-28 ダイキン工業株式会社 Polymère contenant du fluor et son procédé de fabrication
KR20140093660A (ko) * 2011-10-21 2014-07-28 아사히 가라스 가부시키가이샤 발잉크제의 제조 방법, 네거티브형 감광성 수지 조성물, 격벽 및 광학 소자
JP2015093953A (ja) * 2013-11-13 2015-05-18 旭硝子株式会社 フルオロオレフィン共重合体溶液、その製造方法および塗料組成物

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JPH10306129A (ja) * 1997-11-17 1998-11-17 Asahi Glass Co Ltd 含フッ素共重合体の製造方法
JP2008115343A (ja) * 2006-11-08 2008-05-22 Asia Kogyo Kk 弱溶剤型フッ素樹脂塗料用硬化剤およびこれを用いた２液型フッ素樹脂塗料
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Publication number Priority date Publication date Assignee Title
KR20140093660A (ko) * 2011-10-21 2014-07-28 아사히 가라스 가부시키가이샤 발잉크제의 제조 방법, 네거티브형 감광성 수지 조성물, 격벽 및 광학 소자
KR101902608B1 (ko) 2011-10-21 2018-10-01 에이지씨 가부시키가이샤 발잉크제의 제조 방법, 네거티브형 감광성 수지 조성물, 격벽 및 광학 소자
WO2013175962A1 (fr) * 2012-05-24 2013-11-28 ダイキン工業株式会社 Polymère contenant du fluor et son procédé de fabrication
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JP2015093953A (ja) * 2013-11-13 2015-05-18 旭硝子株式会社 フルオロオレフィン共重合体溶液、その製造方法および塗料組成物

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