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WO2007072826A1 - Solution de copolymere fluore et composition de revetement - Google Patents

Solution de copolymere fluore et composition de revetement Download PDF

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Publication number
WO2007072826A1
WO2007072826A1 PCT/JP2006/325289 JP2006325289W WO2007072826A1 WO 2007072826 A1 WO2007072826 A1 WO 2007072826A1 JP 2006325289 W JP2006325289 W JP 2006325289W WO 2007072826 A1 WO2007072826 A1 WO 2007072826A1
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WIPO (PCT)
Prior art keywords
fluorine
containing copolymer
mass
copolymer solution
solution according
Prior art date
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PCT/JP2006/325289
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English (en)
Japanese (ja)
Inventor
Keisuke Mori
Masakazu Ataku
Hiroki Kamiya
Original Assignee
Asahi Glass Company, Limited
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Filing date
Publication date
Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Publication of WO2007072826A1 publication Critical patent/WO2007072826A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to a high solid content fluorine-containing copolymer solution containing a weak solvent and a coating composition used for coatings.
  • Paints containing fluorine-containing resins have many advantages such as excellent weather resistance and long-term use. However, since these paints contain so-called strong solvents such as toluene and xylene, if the paint is applied directly to an old paint film that has changed over time, it may cause blurring or blistering, or good adhesion can be obtained. There was no problem.
  • a two-component type paint in which a curing agent and a solution containing a resin capable of crosslinking with the curing agent are mixed at the time of use has been used.
  • the resin and the hardener are cross-linked to form a three-dimensional network structure, so that a coating film with high hardness and excellent stain resistance can be obtained.
  • the higher the hydroxyl group content (hydroxyl value) in the resin the higher the hardness of the coating film.
  • Patent Document 1 discloses a weak solvent-type paint using a weak solvent having a weaker dissolving power than a strong solvent.
  • Patent Document 2 proposes a coating composition in which a branched alkyl group and a hydroxyl group are contained in a certain ratio in a fluorine-containing copolymer and the solubility in a weak solvent is improved.
  • Patent Document 1 Japanese Patent Publication No. 8-32847
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-277716 Disclosure of the invention
  • the present invention provides a fluorine-containing copolymer solution for paints that can improve the solubility of a resin in a weak solvent, dissolve in a weak solvent at a higher solid content than before, and form a firm coating film. With the goal.
  • the present invention has the following gist.
  • the number average molecular weight of the fluorinated copolymer is in the range of 7000 to 9000 (1) to (6)
  • a coating composition wherein the content of the curing agent is 1 to 100 parts by mass with respect to 100 parts by mass of the fluorine-containing copolymer in the fluorine-containing copolymer solution.
  • the fluorine-containing copolymer solution of the present invention can be a stable solution at a high solid content with respect to the weak solvent because the fluorine-containing copolymer is excellent in solubility in the weak solvent. . Moreover, the fluorine-containing copolymer solution of the present invention can form a strong coating film. In addition, the coating composition of the present invention can suppress the amount of solvent released to the atmosphere.
  • the fluoroolefin has 2 or more fluorine atoms and 3 to 4 fluorine atoms. If the number of fluorine atoms is 2 or more, the resulting coating film has sufficient weather resistance, which is preferable.
  • fluororefin examples include tetrafluoroethylene, black trifluoroethylene, vinylidene fluoride, hexafluoropropylene and the like, and particularly tetrafluoroethylene and black trifluoroethylene. Ethylene is preferred.
  • a vinyl monomer having no fluorine atom is preferably used as a double bond-containing monomer copolymerizable with fluorephine.
  • H 2 It is a compound having a carbon-carbon double bond represented by H 2.
  • Preferred examples of the bulle monomer include alkyl vinyl ethers, alkyl butyl esters, aryl ethers and (meth) acrylic acid esters having a linear, branched or cyclic alkyl group.
  • the double bond-containing monomer copolymerizable with fluorephine in the present invention includes a double bond-containing monomer having a hydroxyl group (hereinafter referred to as a hydroxyl group-containing monomer) and a branch having 3 or more carbon atoms.
  • a double bond-containing monomer having a hydroxyl group hereinafter referred to as a hydroxyl group-containing monomer
  • a branch having 3 or more carbon atoms Monomer having an alkyl group (hereinafter referred to as branched alkyl group-containing monomer Say. ) Both.
  • the double bond-containing monomer in the present invention is more preferably 10-30 mol% is a hydroxyl group-containing monomer, and 10-: 15 mol% is more preferably a hydroxyl group-containing monomer.
  • a hydroxyl group-containing monomer content of 10 mol% or more is preferable because a sufficient amount of hydroxyl groups is introduced into the fluorine-containing copolymer to obtain a coating film having high hardness. Further, it is preferable that the content of the hydroxyl group-containing monomer is 30 mol% or less because even a high solid content type can maintain a sufficiently low viscosity as the fluorine-containing copolymer solution.
  • the number of carbons in the side chain having a hydroxyl group of the hydroxyl group-containing monomer is not particularly limited, 2 to 10 is preferable, 2 to 6 is more preferable, and 2 to 4 is particularly preferable.
  • hydroxyl group-containing monomer examples include hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether (HEVE) and hydroxymethyl vinyl ether (HMVE); hydroxyalkyl aryl ethers such as hydroxy sheryl ether and ethylene glycol monoallyl ether And (meth) acrylic acid hydroxyalkyl esters such as hydroxyethyl (meth) acrylate. Hydroxyalkyl vinyl ethers are preferred because of excellent copolymerizability and good weather resistance of the formed coating film. Of these, HEVE is preferable.
  • 20 to 80 mol% is a monomer having a branched alkyl group having 3 or more carbon atoms (hereinafter referred to as a branched alkyl group-containing monomer), and 20 to 60 mol. 0/0 and more preferably Re is in the range of branched alkyl group-containing monomer.
  • a branched alkyl group-containing monomer having a branched alkyl group having 3 or more carbon atoms
  • Re is in the range of branched alkyl group-containing monomer.
  • the carbon number of the branched alkyl group in the branched alkyl group-containing monomer is 3 or more
  • Examples of the branched alkyl group-containing monomer include butyl ethers having a branched alkyl group, vinyl esters, aryl ethers, and (meth) acrylic acid esters.
  • Examples of the branched alkyl group include an isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 2_methylhexyl group and the like.
  • branched alkyl group-containing monomer examples include butyl ethers such as 2_ethylhexyl butyl ether (2-EHVE) and tert-butyl vinyl ether (t_BuVE), which are preferable because of their excellent copolymerizability. EHVE is more preferred.
  • the branched alkyl group-containing monomers may be used alone or in combination of two or more.
  • the double bond-containing monomer in the present invention may have a hydroxyl group and a branched alkyl group in one monomer molecule.
  • one monomer functions as both a hydroxyl group-containing monomer and a branched alkyl group-containing monomer.
  • the hydroxyl value of the fluorine-containing copolymer may be in the range of 43 to 60 mgKH / g.
  • the double bond-containing monomer further contains a double bond-containing monomer other than the hydroxyl group-containing monomer and the branched alkyl group-containing monomer within a range not impairing the effects of the present invention. Les, even okay.
  • a monomer having a phenyl group or an alkyl group is preferable.
  • the alkyl group include linear, branched or cyclic alkyl groups.
  • the alkyl group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
  • Preferred examples of the double bond-containing monomer having a phenyl group include butyl esters such as benzoic acid butyl and t_butyl benzoic acid butyl.
  • Examples of the double bond-containing monomer having a cyclic alkyl group include cyclic alkyl butyl ethers such as cyclohexyl butyl ether and cyclohexyl methyl butyl ether, cyclohexyl (meth) acrylate, 3, 3, 5-trimethylcyclo Preferred examples include (meth) acrylic acid cyclic alkyl esters such as hexyl (meth) acrylate, and cyclohexyl ether is more preferred.
  • These other double bond-containing monomers may be used alone or in combination of two or more. Total amount of double bond-containing monomers The proportion of the other double bond-containing monomer in the 0-70 Monore 0/0 Ca, and more preferably from 30 to 60 molar%.
  • the fluorine atom content in the fluorinated copolymer is 10% by mass or more, preferably 20% by mass or more, and more preferably 25% by mass or more in order to obtain good weather resistance of the paint. is there.
  • the fluorine atom content in the fluorinated copolymer is preferably 30% by mass or less. This is because if the fluorine atom content in the fluorine-containing copolymer exceeds 30% by mass, the solubility of the fluorine-containing copolymer in a weak solvent becomes insufficient.
  • the ratio of the polymer units based on fluororefin and the polymer units based on the double bond-containing monomer in the fluorine-containing copolymer is such that the polymer units based on fluoroolefin are 30 to 70 mol 0. / and more preferably 0 is it is preferred tool 40 to 60 mole 0/0.
  • the proportion of polymerized units based on the double bond-containing monomer is more preferably from 70 to 30 mol% is preferred instrument from 60 to 40 mole 0/0.
  • the proportion of the polymer units based on fluoroolefin is 70 mol% or less, the fluorine-containing copolymer has sufficient solubility in a weak solvent, and when it is 30 mol% or more, sufficient weather resistance is obtained. Therefore, it is preferable.
  • the fluorine-containing copolymer in the present invention has a hydroxyl group as a reactive site with the curing agent, and the hydroxyl value in the fluorine-containing copolymer is converted to a chemical reaction equivalent of potassium hydroxide. And 43 to 60 mgKOH / g, preferably 45 to 55 mgKOH / g, based on the total solid content of the fluorinated copolymer.
  • the hydroxyl value is 43 mgK o H / g or more, a highly hard coating can be obtained, and when the hydroxyl value is 60 mgKOH / g or less, a weak solvent is used even if the fluorinated copolymer has a high solid content. Sufficient solubility in water can be realized, and low viscosity can be realized.
  • the fluorine-containing copolymer of the present invention is polymerized into a mixture of fluoroolefin and a double bond-containing monomer containing a predetermined proportion of a hydroxyl group-containing monomer and a branched alkyl group-containing monomer. In the presence or absence of a medium, it can be produced by carrying out a copolymerization reaction by acting a polymerization initiator such as a polymerization initiator or ionizing radiation.
  • a polymerization initiator such as a polymerization initiator or ionizing radiation.
  • the proportion of the amount of fluoroolefin used and the double bond-containing monomer is based on the polymer unit based on fluoroolefin and the double bond-containing monomer in the above-mentioned fluorine-containing copolymer. It is preferable that it is the same as the ratio of a polymerization unit.
  • Examples of the polymerization medium include ketones such as methyl ethyl ketone and methyl isobutyl ketone; acetic acid Examples include esters such as ethyl and n-butyl acetate; aromatic solvents such as xylene and toluene; and aliphatic solvents such as cyclohexanone, solvent naphtha, mineral terpenes, mineralolates, and petroleum naphtha.
  • ethyl 3_ethoxypropionate methylaminoleketone, tert-butyl acetate, 4_black benzotrifluoride, benzotrifluoride, monochrome chlorotoluene, 3,4-dichloro benzotrifluoride, etc. are preferable. Can be mentioned.
  • polymerization initiators 2,2'-azobisisobutyronitrile, 2,2'-azobiscyclohexane carbonate nitrile, 2,2'-azobis (2,4-dimethylvaleronitrile),
  • examples include azo initiators such as 2,2′-azobis (2-methylptyronitrile).
  • ketone peroxides such as cyclohexanone peroxide
  • hydride peroxides such as tert-butyl hydride peroxide
  • disilver oxides such as benzoyl peroxide
  • dialkyl peroxides such as di-tert-butyl peroxide
  • alkyl peresters such as tert-butylperoxybivalate
  • percarbonates such as diisopropylperoxydicarbonate
  • a physical initiator is preferably mentioned.
  • the fluorine-containing copolymer in the present invention has a fluorine atom content of 10% by mass or more, and preferably 20-30% by mass with respect to the total mass of the fluorine-containing copolymer.
  • a fluorine atom content of 10% by mass or more is preferable because the weather resistance of the coating film is sufficient.
  • the fluorine-containing copolymer in the present invention preferably has a number average molecular weight (Mn) of 7000 to 9000 as measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • Mn number average molecular weight
  • GPC gel permeation chromatography
  • the resulting coating film is excellent in weather resistance, and when the Mn is 9000 or less, sufficient dissolution can be achieved even in a high concentration of the fluorine-containing copolymer in the fluorine-containing copolymer solution or coating composition. This is preferable because it can realize low viscosity and low viscosity.
  • the glass transition point (hereinafter referred to as Tg) of the fluorinated copolymer in the present invention is preferably 25 ° C or more, more preferably 30 to 40 ° C.
  • a Tg of 25 ° C. or higher is preferable because a highly hard coating can be obtained.
  • the fluorine-containing copolymer of the present invention has a carboxy group, whereby the dispersibility of the pigment is improved when it is used as a paint.
  • carboxy group in fluorine-containing copolymer In terms of the chemical reaction equivalent of potassium hydroxide, the amount is preferably from 2 to 5 mgK0H / g, more preferably from 5 to 5 mgK0H / g, based on the total mass of the fluorinated copolymer.
  • the carboxy group is obtained, for example, by reacting a polyvalent carboxylic acid or an anhydride thereof with a hydroxyl group in the fluorinated copolymer after the above-described polymerization reaction of fluoroolefin and a double bond-containing monomer. Can be introduced. It can also be introduced by direct polymerization of a double bond-containing monomer having a carboxy group.
  • the fluorine-containing copolymer solution of the present invention may contain various weak solvents.
  • Weak solvents are solvents that are classified as organic solvents of type 3 in the classification of organic solvents according to the Industrial Safety and Health Act, and correspond to any of the following (1) to (3).
  • Solvents such as gasoline, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, petroleum benzine, turpentine, mineral spirits (including mineral thinner, petroleum spirit, white spirit and mineral turpen),
  • the fluorine-containing copolymer solution of the present invention uses a weak solvent selected from the above (1) to (3) as a weak solvent which is a third type organic solvent.
  • the corresponding type 2 organic solvent does not contain more than 5% by mass of the total solvent.
  • Mineral spirits including mineral thinners, petroleum spirits, white spirits and mineral terpenes are preferred as weak solvents because of their flash point above room temperature.
  • the fluorine-containing copolymer solution of the present invention includes CAB (cellulose acetate butyrate), NC (nitrocellulose), etc., in addition to the fluorine-containing copolymer and weak solvent, in order to improve the drying property of the coating film. It may contain. Further, in order to improve the gloss, hardness, and paint workability of the coating film, a coating resin such as a polymer made of acrylic acid or an ester thereof, or polyester may be contained.
  • the fluorine-containing copolymer solution of the present invention preferably has the entire solid content contained in the solvent dissolved therein, but may have some insoluble portions.
  • the amount of the weak solvent in the coating composition is appropriately determined in consideration of the solubility of the fluorinated copolymer, the appropriate viscosity when applied as a coating material, the coating method, and the like.
  • the fluorine-containing copolymer solution of the present invention is used as a two-pack type paint mixed with a curing agent before use.
  • the coating composition of the present invention contains a fluorine-containing copolymer solution and a curing agent.
  • the curing agent is preferably a curing agent capable of crosslinking with a hydroxyl group in the fluorine-containing copolymer.
  • curing for coating materials such as isocyanate curing agents, block isocyanate curing agents, and melamine curing agents. Agents.
  • Examples of the isocyanate curing agent include non-yellowing isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate.
  • Examples of the block isocyanate curing agent include those obtained by blocking the isocyanate group of the isocyanate curing agent with force prolatatam, isophorone, ⁇ -diketone or the like.
  • Examples of the melamine curing agent include melamine etherified with a lower alcohol such as petit melamine melamine, and epoxy-modified melamine.
  • the content of the curing agent in the coating composition of the present invention is 1 to 100 parts by mass with respect to 100 parts by mass of the fluorinated copolymer in the coating composition. Mass parts are more preferred.
  • the obtained coating film has excellent solvent resistance and sufficient hardness, and when the curing agent is 100 parts by mass or less, it has excellent workability and impact resistance. Excellent in properties.
  • the coating composition of the present invention preferably contains another functional compounding agent as necessary.
  • other functional compounding agents include coloring pigments, dyes, silane coupling agents for improving the adhesion of coating films, UV absorbers, curing accelerators, light stabilizers, and matting agents.
  • coloring pigments and dyes include inorganic pigments such as carbon black having good weather resistance and titanium oxide, organic pigments such as phthalocyanine bunoley, phthalocyanine green, quinacridone red, indanthrene orange, and isoindolinone yellow. And dyes.
  • silane coupling agent examples include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 2-2- (aminoethyl) 3-aminopropyltrimethoxysilane, Raid propyl triethoxy silane, butyl triethoxy silane, butyl trimethoxy silane, 3-methacryloxy propyl trimethoxy silane, 3-methacryloxy propyl triethoxy silane, 2- (3, 4_epoxycyclohexenole) ethinoretri Examples include methoxysilane, 3-glycidoxypropyl pyrtrimethoxysilane, 3_mercaptopropyltrimethoxysilane, 3_isocyanate propyltriethoxysilane, methyltriethoxysilane, and methyltrimethoxysilane.
  • Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, triazine-based, and cyanacrylate-based ultraviolet absorbers.
  • Examples of the curing accelerator include acidic catalysts such as dibutyltin dilaurate for isocyanate curing agents, and paratoluenesulfonic acid for melamine curing agents.
  • light stabilizers include hindered amine light stabilizers. Specifically, Ade force stub LA62, Adekastab LA67 (above, manufactured by Adeka Gas Chemical Co., Ltd.), Tinuvin 292, Tinuvin 144, Tinuvin 123, Tinuvin 440 (above Ciba 'Specialty' Chemicals).
  • Examples of the delustering agent include ultra fine powder synthetic silica and the like.
  • An elegant semi-gloss, matte finish can be formed.
  • a coating composition can be produced by mixing the coating composition of the present invention, a curing agent, and a functional compounding agent added as necessary.
  • the order of mixing is not particularly limited, and the coating composition and the curing agent of the present invention in which the coating composition of the present invention and the functional compounding agent are mixed in advance and the curing agent may be mixed therewith. These may be mixed, and then the functional compounding agent may be mixed, or these may be mixed simultaneously.
  • any method such as spray coating, air spray coating, brush coating, dipping method, roll coater, flow coater and the like can be applied.
  • the material of the article to be coated 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. Can be mentioned.
  • organic and inorganic composite materials such as FRP, resin reinforced concrete, fiber reinforced concrete, etc. Also suitable for painting.
  • the 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 Building materials such as monuments and poles; road media such as median strips, guardrails and soundproof walls; communication equipment; electrical and electronic parts.
  • 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
  • road media such as median strips, guardrails and soundproof walls
  • communication equipment electrical and electronic parts.
  • CTFE black-mouthed trifluoroethylene
  • Xylene was distilled off from the xylene solution of the obtained fluorinated copolymer to make the nonvolatile content 60 mass%. Thereafter, 5.8 g of hydrogenated phthalic anhydride was added, and 0.05 g of triethylamine was further applied Q, and then the temperature of the flask was gradually raised. After the temperature in the flask reached 70 ° C, the temperature was maintained for 2 hours.
  • the fluorine-containing copolymer having a number average molecular weight (Mn) of 7100, a hydroxyl value of 50 mgKOH / g, an acid value of 2 mgKOH / g, and Tg of 26 ° C 1089 g of a solid content of A (non-volatile content of 99% by mass or more) was obtained.
  • Mn number average molecular weight
  • a double bond consisting of 235g of CHVE, 332g of neodecanoic acid vinyl ester (V—10) and 99g of HEVE in an autoclave with a stainless steel stirrer with an internal volume of 2000mL Charge the monomer mixture, 670 g of xylene, 189 g of ethanol and 9.5 g of potassium carbonate, and remove dissolved oxygen with nitrogen.
  • the xylene solution of the obtained fluorinated copolymer is treated in the same manner as the fluorinated copolymer A to obtain 1112 g of a solid content (nonvolatile content of 99% by mass or more).
  • the xylene solution of the obtained fluorinated copolymer is treated in the same manner as the fluorinated copolymer A to obtain 1065 g of a solid content (non-volatile content of 99% by mass or more).
  • a double bond-containing monomer consisting of 288 g of cyclohexyl acrylate (CHA), 262 g of 2-EHVE and 130 g of 2-hydroxyethyl acrylate (2-HEA) in an autoclave with a stainless steel stirrer with an internal volume of 2000 mL Charge the mixture, 670 g of xylene, 189 g of ethanol, and 9.5 g of potassium carbonate, and remove dissolved oxygen with nitrogen.
  • CHA cyclohexyl acrylate
  • 2-EHVE 2-EHVE
  • 2-HEA 2-hydroxyethyl acrylate
  • the xylene solution of the obtained fluorinated copolymer is treated in the same manner as the fluorinated copolymer A to obtain 829 g of a solid content (nonvolatile content of 99% by mass or more).
  • the composition of the fluorinated copolymer A was changed except that the composition of the double bond-containing monomer was 208 g of CHVE, 186 g of EVE, and 186 g of hydroxybutyl vinyl ether (HBVE).
  • the solid content of the fluorinated copolymer F having an Mn force of 7200, a hydroxyl value of 49 mgK 0 H / g, an acid value of 2 mg K 0 H / g, and a Tg of 34 ° C (non-volatile content of 99% by mass or more) Of 1074 g.
  • the fluorine-containing copolymer F does not contain a double bond-containing monomer having a branched alkyl group having 3 or more carbon atoms, and therefore does not correspond to the present invention.
  • Table 1 shows the monomer composition (mol%), hydroxyl value, acid value, and Mn of the fluorinated copolymers A to F. Further, the solid content of the obtained fluorinated copolymers A to F was mixed with ethoxyethyl propionate (EEP) or mineral spirit (MS) at a ratio such that the non-volatile content was 75% by mass, and allowed to stand at room temperature for 3 days. The result of confirming the dissolved state after placing is shown.
  • EEP ethoxyethyl propionate
  • MS mineral spirit
  • the obtained white paint was applied to the surface of the aluminum plate with an applicator to a thickness of about 70 ⁇ m and dried at room temperature for 2 weeks to obtain a coating film with a thickness of about 30 zm.
  • the physical properties of the obtained coating film were as shown below.
  • the coating composition using the fluorine-containing copolymer solution of the present invention provides a solution in which a high solid content fluorine-containing copolymer is dissolved in a weak solvent as compared with the conventional fluorine-containing copolymer solution. . Therefore, the coating composition can suppress the amount of solvent released to the atmosphere, is suitable for forming a coating film with high hardness, and is extremely useful in the coating industry. It should be noted that the entire contents of the Japanese Patent Application 2005-366666, filed on December 20, 2005, the claims of Akito, the claims, and the abstract are cited herein as the disclosure of the specification of the present invention. And that is what we take in.

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une solution de copolymère fluoré pour des matériaux de revêtement qui a une teneur en solide élevée et est dissoute dans un mauvais solvant. Cette solution de copolymère fluoré permet de former un film de revêtement ayant une dureté élevée. La présente invention concerne plus spécifiquement une solution de copolymère fluoré contenant un copolymère fluoré et un mauvais solvant, laquelle est caractérisée en ce qu’elle contient de 73 à 90 % en masse du copolymère fluoré. Le copolymère fluoré est un copolymère d'une fluorooléfine possédant deux atomes de fluor ou plus et un monomère contenant une liaison double qui est copolymérisable avec la fluorooléfine, où 10 à 30 % en mole du monomère contenant une liaison double possède un groupe hydroxyle tandis que 20 à 80 % en mole possède un groupe alkyle ramifié possédant trois atomes de carbone ou plus. Le copolymère fluoré a une teneur en fluor non inférieure à 10 % en masse et un indice d’hydroxyle de 43 à 60 mg de KOH/g.
PCT/JP2006/325289 2005-12-20 2006-12-19 Solution de copolymere fluore et composition de revetement WO2007072826A1 (fr)

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JP2005-366666 2005-12-20
JP2005366666A JP2009057391A (ja) 2005-12-20 2005-12-20 塗料用含フッ素共重合体溶液および塗料

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WO2009157449A1 (fr) * 2008-06-23 2009-12-30 旭硝子株式会社 Feuille de dos pour module de cellule solaire et module de cellule solaire
US7919557B2 (en) 2006-09-22 2011-04-05 Asahi Glass Company, Limited Aqueous coating composition, process for producing it and two-pack type curable aqueous coating kit
CN102473770A (zh) * 2009-07-09 2012-05-23 琳得科株式会社 太阳能电池组件用保护片
EP2746322A1 (fr) 2012-12-21 2014-06-25 Agfa-Gevaert Feuille arrière pour modules photovoltaïques
EP2824716A1 (fr) 2013-07-09 2015-01-14 Agfa-Gevaert Feuille arrière pour modules photovoltaïques
EP2824717A1 (fr) 2013-07-09 2015-01-14 Agfa-Gevaert Feuille arrière pour modules photovoltaïques
EP2824713A1 (fr) 2013-07-09 2015-01-14 Agfa-Gevaert Feuille arrière pour modules photovoltaïques
WO2020075726A1 (fr) * 2018-10-09 2020-04-16 Ａｇｃ株式会社 Composition, polymère fluoré et matériau de revêtement contenant ladite composition et ledit polymère fluoré

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CN114634725B (zh) * 2022-03-24 2022-10-28 九牧厨卫股份有限公司 一种用于8k镜面不锈钢的防污薄膜及8k镜面防污不锈钢板的制备方法

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JPH04146945A (ja) * 1990-10-09 1992-05-20 Nippon Carbide Ind Co Inc 重合体の有機溶媒分散液
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US7919557B2 (en) 2006-09-22 2011-04-05 Asahi Glass Company, Limited Aqueous coating composition, process for producing it and two-pack type curable aqueous coating kit
RU2498458C2 (ru) * 2008-06-23 2013-11-10 Асахи Гласс Компани, Лимитед Задний лист для модуля солнечных элементов и модуль солнечных элементов
EP2309551A1 (fr) * 2008-06-23 2011-04-13 Asahi Glass Company, Limited Feuille de dos pour module de cellule solaire et module de cellule solaire
CN102067327A (zh) * 2008-06-23 2011-05-18 旭硝子株式会社 太阳能电池模块用背板及太阳能电池模块
EP2309551A4 (fr) * 2008-06-23 2013-07-10 Asahi Glass Co Ltd Feuille de dos pour module de cellule solaire et module de cellule solaire
WO2009157449A1 (fr) * 2008-06-23 2009-12-30 旭硝子株式会社 Feuille de dos pour module de cellule solaire et module de cellule solaire
JP5348134B2 (ja) * 2008-06-23 2013-11-20 旭硝子株式会社 太陽電池モジュール用バックシートおよび太陽電池モジュール
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EP2746322A1 (fr) 2012-12-21 2014-06-25 Agfa-Gevaert Feuille arrière pour modules photovoltaïques
EP2824716A1 (fr) 2013-07-09 2015-01-14 Agfa-Gevaert Feuille arrière pour modules photovoltaïques
EP2824717A1 (fr) 2013-07-09 2015-01-14 Agfa-Gevaert Feuille arrière pour modules photovoltaïques
EP2824713A1 (fr) 2013-07-09 2015-01-14 Agfa-Gevaert Feuille arrière pour modules photovoltaïques
WO2015003915A1 (fr) 2013-07-09 2015-01-15 Agfa-Gevaert Feuille protectrice arrière pour modules photovoltaïques
WO2015003918A1 (fr) 2013-07-09 2015-01-15 Agfa-Gevaert Plaque arrière pour modules photovoltaïques
WO2020075726A1 (fr) * 2018-10-09 2020-04-16 Ａｇｃ株式会社 Composition, polymère fluoré et matériau de revêtement contenant ladite composition et ledit polymère fluoré

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