Classifications

• • 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
  • C08F214/22—Vinylidene fluoride
  • C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
• • 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
  • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
• • 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
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
  • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
• • 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
  • 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
  • C08F214/26—Tetrafluoroethene
  • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
• • 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
  • C08F214/26—Tetrafluoroethene
  • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/068—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • 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
• • 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
  • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
  • C09D143/04—Homopolymers or copolymers of monomers containing silicon
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic

Definitions

• the present invention is a fluoropolymer having excellent water and oil repellency, excellent characteristics such as chemical resistance and weather resistance, which are the characteristics of fluororesins, and excellent compatibility with acrylic resins, and fluoropolymers thereof. It is related to fluororesin paint and varnish, which are the main components.
• the solvent-soluble fluororesin coating material can generally be obtained by copolymerizing hydroxyalkyl vinyl ether and fluoroolefin, and if necessary, alkyl vinyl ether, alkyl vinyl ester and the like.
• a fluorine-containing copolymer-based coating material contains 40% or more of a hydrocarbon monomer in order to obtain solubility in a general organic solvent. Therefore, the fluorine content in the fluororesin is lowered, and the coating film characteristics such as water repellency and oil repellency and stain resistance required for the fluororesin cannot be sufficiently obtained.
• an organic silicon compound such as silicone oil
• water repellency and oil repellency are improved.
• the silicone oil may bleed out from the surface of the coating film, so that the silicone oil cannot be used.
• a water- and oil-repellent agent a copolymer of a fluorine-containing monomer having a perfluoro group and a monomer containing a silyl group has been studied, but the main skeleton of the copolymer has a fluorine atom. Sufficient weather resistance cannot be obtained because it is not.
• Patent Document 1 a solvent-soluble fluororesin paint or varnish that solves the above problems (Patent Document 1), but it was necessary to further improve the stability. Specifically, there was a need in the industry for long-term storage (3 months or more) after production. When the solution containing the fluorine-containing copolymer was exposed to light, the solution tended to gradually gel. Therefore, when the fluororesin paint or the varnish is put in a container and left to stand, the viscosity tends to increase by the time 6 months or more have passed.
• An object of the present invention is to provide a fluorine-containing copolymer composition having long-term stability, and a fluororesin coating material or varnish using the composition.
• fluoroolefin is 5 to 85 mol%, and one or more kinds of organic silicon selected from the general formulas (1), (2), (3), (4), (5) and (6).
• R 1 , R 2 , and R 3 are hydrogen atom, methyl group, ethyl group, butyl group, phenyl group, -CF 3 , -C 2 H 4 CF 3 , -C (CH 3 ) 3, respectively.
• R 1 , R 2 , and R 3 may be the same or different, respectively.
• R 4 is a hydrogen atom or a methyl group
• R 5 is an ether group
• R 6 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• n is 0 to 10
• m is 0 to 420.
• R 7 is a hydrogen atom or a methyl group
• R 8, R 9, and R 10 are each a hydrogen atom, .R 8 of a methyl group, an ethyl group, a butyl group or a -OSi (CH 3) 3
• R 9 and R 10 may be the same or different, respectively.
• q is 1 It indicates ⁇ 420, and r indicates 1 to 6).
• the fluoropolymer is further composed of one or more polymerization units selected from among alkyl vinyl ethers, alkyl allyl ethers, vinyl esters, methacrylic acid esters and acrylic acid esters [1].
• the composition according to. [3] The composition according to [1] or [2], which comprises the amine compound in an amount of 0.005 to 10 parts by weight per 100 parts by weight of the fluorine-containing copolymer.
• the solvent is contained in an amount of 25 to 1900 parts by weight per 100 parts by weight of the fluorine-containing copolymer.
• composition according to [1] or [2] which comprises.
• [5] (A) The method for producing a composition according to any one of [1] to [4], which comprises a step of copolymerizing the polymerization unit by a solution polymerization method to produce a solution containing a fluorine-containing copolymer.
• step (B) The method according to [5], further comprising a step of adding an amine compound to the solution containing the fluorine-containing copolymer obtained in step (a).
• step (a) The method according to [5] or [6], wherein the copolymerization in step (a) is carried out using at least one selected from the group consisting of ethyl acetate, butyl acetate, xylene, toluene and methyl ethyl ketone as a solvent.
• a varnish or paint comprising the composition according to any one of [1] to [4].
• a varnish or paint consisting of the composition according to any one of [1] to [4] is applied to a gravure coater, a spin coater, a dip coating, a roll coater, a reverse roll coater, a comma coater, a doctor knife coater, and a bar.
• a method used for a coating method selected from the group consisting of coaters, kiss roll coaters, curtain flow coaters, roller coatings, spray coatings, electrostatic spray coatings, rotary screen prints, inkjet coatings, and brush coatings.
• a fluorine-containing copolymer composition having long-term stability and a fluororesin coating material or varnish using the composition are provided.
• the present invention also provides a method for producing the above-mentioned fluorine-containing copolymer composition.
• the above fluororesin paint or varnish is further applied to a gravure coater, a spin coater, a dip coating, a roll coater, a reverse roll coater, a comma coater, a doctor knife coater, a bar coater, a kiss roll coater, and a curtain.
• a coating film to be formed is provided.
• the present invention is characterized in that an amine compound is used as a stabilizer in an amount in a specific range. It is generally known that when an amine compound is added to a reaction system containing an organic silicon compound such as silicone oil, the reaction solution turns yellow. For this reason, amine compounds have not been used as stabilizers for paints or varnishes containing organic silicon compounds. Since the polymerization unit of the fluorine-containing copolymer of the present invention is also an organosilicon compound, it is a high-molecular-weight organosilicon compound, and when an amine compound is used as a stabilizer, there are concerns about problems such as coloring.
• the fluorine-containing copolymer composition of the present invention is also useful as a paint or a varnish.
• fluorine-containing copolymer composition As the polymerization unit, 5 to 85 mol% of fluoroolefin is one or more organic substances selected from the general formulas (1), (2), (3), (4), (5) and (6).
• [Fluorine-containing copolymer] A copolymer of one or more organic silicon compounds selected from the following general formulas (1), (2), (3), (4), (5) and (6) and a fluoroolefin can be used for a long period of time. It has excellent water and oil repellency, repeated decontamination, chemical resistance, and weather resistance, and is useful in various applications.
• the present invention is characterized in that, in addition to the above polymerization units, one or more polymerization units selected from among alkyl vinyl ethers, alkyl allyl ethers, vinyl esters, methacrylic acid esters and acrylic acid esters are further included. Fluorine-containing copolymers are also provided.
• "-COO-" or "-OOC-” means an ester bond.
• R 1 , R 2 , and R 3 are hydrogen atom, methyl group, ethyl group, butyl group, phenyl group, -CF 3 , -C 2 H 4 CF 3 , -C (CH 3 ) 3, respectively. Or -OSi (CH 3 ) 3.
• R 1 , R 2 , and R 3 may be the same or different, respectively.
• R 4 is a hydrogen atom or a methyl group
• R 5 is an ether group (that is, ⁇ O—)
• R 6 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• n is 0 to 10
• m is 0. ⁇ 420, especially 0 ⁇ 160.
• R 7 is a hydrogen atom or a methyl group
• R 8 , R 9 , and R 10 are a hydrogen atom, a methyl group, an ethyl group, and a butyl group (for example, n-butyl group, isobutyl group, and t-butyl group, respectively). , Se-butyl group, etc.) or -OSi (CH 3 ) 3.
• R 8 , R 9 , and R 10 may be the same or different, respectively.
• q is 1 It indicates ⁇ 420, and r indicates 1 to 6).
• R 12 is as defined above.
• the fluoroolefin is an olefin having one or more fluorine atoms in the molecule, and for example, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and the like are preferable. be. These fluoroolefins may be used alone or in combination of two or more.
• organic silicon compounds represented by the general formulas (1), (2), (3), (4), (5) and (6) include vinylpentamethyldisiloxane, vinylphenyldimethylsilane and vinylmethyl.
• An oil, a reactive silicone oil having both ends modified with acrylic, an organic silicon compound represented by the general formulas (7), (8), (9) and (10), and the like are suitable. These organic silicon compounds may be used alone or in combination of two or more. The molecular weight of these organic silicon compounds is preferably 100 to 30,000.
• -C 3 H 6- indicates a propylene group
• R 13 indicates an alkyl group having 1 to 6 carbon atoms, and a indicates 1 to 250.
• -C 3 H 6- indicates a propylene group
• R 13 indicates an alkyl group having 1 to 6 carbon atoms, and a indicates 1 to 250.
• -C 3 H 6- indicates a propylene group.
• alkyl vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tertiary pentyl vinyl ether, n-hexyl vinyl ether, and iso.
• alkyl allyl ethers include ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, isobutyl allyl ether, n-propyl allyl ether, allylglycidyl ether, 3-allyloxy-1,2-propanediol, and glycerol- ⁇ -.
• alkyl allyl ethers include ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, isobutyl allyl ether, n-propyl allyl ether, allylglycidyl ether, 3-allyloxy-1,2-propanediol, and glycerol- ⁇ -.
• alkyl allyl ethers include ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, isobut
• acrylic acid ester examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, and isopentyl acrylate.
• methacrylic acid ester examples include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, and n-nonyl methacrylate.
• vinyl ester examples include vinyl acetate, vinyl n-butyrate, vinyl isobutyrate, vinyl propionate, vinyl caproate, vinyl caprylate, vinyl caproate, vinyl laurate, vinyl myristate, vinyl partimate, and the like.
• carboxylic acid vinyl esters such as vinyl stearate.
• the fluorine-containing copolymer of the present invention can form a coating film having excellent long-term water and oil repellency, repeated decontamination, chemical resistance, and weather resistance.
• Other copolymerizable monomer units may be contained within a range not exceeding 20 mol% depending on the purpose of use and the like.
• Examples of the other copolymerizable monomers include olefins such as ethylene and propylene, haloolefins such as vinyl chloride and vinylidene chloride, and halogenated vinyl ethers such as 2- (perfluorohexyl) ethyl vinyl ether, 2.
• Halogenated methacrylic acid esters such as- (perfluorobutyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, halogens such as 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorohexyl) ethyl acrylate
• Examples thereof include methacrylic acid esters.
• the polymerization unit fluoroolefin is less than 5 mol% in the fluorine-containing copolymer, sufficient stain resistance cannot be obtained when it is used as a paint base, which is not preferable.
• it is more than 85 mol%, the solubility in various solvents is lowered, which is not preferable. It is preferably 30 to 80 mol%.
• the proportion of the organic silicon compound selected from the general formulas (1), (2), (3), (4), (5) and (6) is less than 0.001 mol%, Sufficient water and oil repellency for a long period of time cannot be obtained, which is not preferable. Further, when it is more than 50 mol%, sufficient chemical resistance and weather resistance cannot be obtained, which is not preferable.
• the proportion of the organic silicon compound is preferably 0.005 to 30 mol%.
• the fluorine-containing copolymer of the present invention can be produced by copolymerizing a predetermined ratio of monomer mixture by a solution polymerization method using a polymerization initiator.
• polymerization initiator used in the solution polymerization method examples include peroxyester-type peroxides such as t-butylperoxyisobutyrate and t-butylperoxyacetate, diisopropylperoxydicarbonate, and dinormalpropylperoxydi. Dialkylperoxydicarbonate such as carbonate, benzoyl peroxide, azobisisobutyronitrile and the like are used.
• the amount of the polymerization initiator used is appropriately selected depending on the type, copolymerization reaction conditions, etc., but is usually 0.005 to 5% by weight, preferably 0.005 to 5% by weight, based on the total amount of the polymerization units (monomers) used. It is selected in the range of 0.1 to 2% by weight.
• Examples of a particularly preferable solvent for obtaining the fluorine-containing copolymer of the present invention by the solution polymerization method include ethyl acetate, butyl acetate, xylene, toluene, methyl ethyl ketone and the like.
• the reaction temperature in the copolymerization reaction is usually selected in the range of 0 ° C. to 100 ° C., preferably 10 ° C. to 90 ° C.
• the reaction pressure is not particularly limited, but is usually selected in the range of 0.1 to 10 MPa, preferably 0.1 to 5 MPa. Further, the copolymerization reaction can be carried out by adding an appropriate chain transfer agent.
• the fluorine-containing copolymer of the present invention contains a hydroxyl group as a curing site, it can be cured at room temperature using polyhydric isocyanates.
• polyhydric isocyanates include non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, their adducts, and polyvalent isocyanates having isocyanurates, among which isocyanurates are included. Polyvalent isocyanates are particularly effective.
• curing at room temperature using isocyanates curing can be accelerated by adding a known catalyst such as dibutyltin dilaurate.
• a melamine curing agent examples include butylated melamine, methylated melamine, epoxy-modified melamine, and the like, and those having various degrees of modification are appropriately used depending on the intended use, and the degree of self-condensation can also be appropriately selected.
• the urea resin curing agent examples include methylated urea resin and butylated urea resin
• examples of the polybasic acid curing agent include long-chain aliphatic dicarboxylic acids, aromatic polyvalent carboxylic acids, and acid anhydrides thereof. Things etc. can be mentioned.
• blocked polyvalent isocyanates can also be suitably used as a curing agent. Further, when using a melamine curing agent or a urea resin curing agent, curing can be promoted by adding an acidic catalyst.
• a curing agent used in ordinary curable epoxy paints such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.
• Aliphatic amines or modified products thereof aromatic amines such as metaphenylenediamine, pp'-diaminodiphenylmethane, diaminophenylsulfone, etc. or modified products thereof, phthalic anhydride, maleic anhydride, oxalic acid anhydride, hexa.
• examples thereof include polyvalent carboxylic acids such as hydrophthalic acid and pimelli acid, or anhydrides thereof.
• solvents can be used in the production of the fluorine resin paint or varnish containing the fluorine-containing copolymer of the present invention as the main component, or the curable fluorine resin paint or varnish, and for example, aromatic carbonization such as xylene and toluene can be used.
• aromatic carbonization such as xylene and toluene
• examples include hydrogens, acetate esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as ethyl cellosolve, and various commercially available thinners, such as ethyl acetate, butyl acetate and xylene.
• Toluene is particularly preferable. Further, it is possible to add an acrylic resin or an epoxy resin as needed. It is preferable to adjust the fluorine-containing copolymer so as to be contained in the coating material in an amount of 5 to 80% by weight, particularly 20 to 60% by weight.
• an amine compound is used as the stabilizer.
• the amine compound include organic amines such as a primary amine, a secondary amine, and a tertiary amine.
• a trialkylamine is preferable, and in particular, a trialkylamine having a lower alkyl group having 1 to 4 carbon atoms, for example, trimethylamine, triethylamine, tributylamine and the like can be mentioned.
• triethylamine and tributylamine are particularly preferable because of their performance as stabilizers, the degree of coloring, and availability.
• the reaction solution after polymerization contains a fluorine-containing copolymer and a solvent as main components, and a predetermined amount of amine compound is contained in this reaction solution. Can be added to obtain the fluorine-containing copolymer composition of the present invention.
• the amount of the amine compound added is preferably 0.005 to 10% by weight, more preferably 0.05 to 10% by weight, and more preferably 0.05 to 10% by weight, based on the total weight of the fluorine-containing copolymer of the present invention. It is more preferably 5% by weight. That is, the amount of the amine compound added is preferably 0.005 to 10 parts by weight, more preferably 0.05 to 10 parts by weight, per 100 parts by weight of the fluorine-containing copolymer. It is more preferable to include it in a ratio of 0.05 to 5 parts by weight. If the amount of the amine compound is too small, it tends to be difficult to prevent gelation for a long period of time. On the other hand, if the amount of the amine compound is too large, the stabilizer is wasted in order to obtain the same stabilizing effect, and the degree of coloring and the like tends to be non-negligible.
• the fluorine-containing copolymer composition of the present invention is excellent in long-term storage stability, and substantially no increase in viscosity or change in hue occurs even after storage for 3 months. Therefore, it is suitable for paints and varnishes.
• the paint or varnish prepared from the fluorine-containing copolymer composition of the present invention includes a gravure coater, a spin coater, a dip coating, a roll coater, a reverse roll coater, a comma coater, and a doctor knife coater. , Bar coater, kiss roll coater, curtain flow coater, roller coating, spray coating, electrostatic spray coating, rotary screen printing, inkjet coating, brush coating, etc.
• Exterior applications include vehicle exterior films such as automobile exterior coatings, automobile exterior coating films, automobile coating protective films, automobile window films, and automobile marking films. Specific examples thereof include automobile exterior and exterior parts such as automobile bodies, bumpers, spoilers, doorknobs, headlamps, blinkers, side mirrors, radiator grilles, and wheels. Examples thereof include motorcycle exteriors and exterior parts such as motorcycle bodies, handles, saddles, and gasoline tanks. Other examples include exteriors, exterior films, and exterior parts of vehicles such as trains. Further, window films, glass surface coatings, marking films, protective films, coatings and the like in vehicles such as automobiles, motorcycles and trains can be mentioned. In addition, examples of interior applications in vehicles such as automobiles include automobile interior seats, steering wheels, meter panels, control panels, dashboards, door interiors, and paints, protective films, design films, and the like in these applications. ..
• release films include, for example, release films, mobile phones, smartphones, personal computers, televisions, portable terminals (including game machines), electronic devices such as printers, televisions, air conditioners, microwave ovens, refrigerators, washing machines, and air purifiers.
• Home appliances such as machines, vacuum cleaners and ventilation fans, toys, shelves, bookshelves, beds, desks, chairs, sofas and other interiors, ventilation fans, range hoods, kitchen panels, stainless sinks, bathtubs, toilets, etc.
• paints, protective films, and design films in the above applications include paints, protective films, and design films in the above applications.
• window films, glass surface coats, outdoor marking films, protective films for various articles, coatings for building materials, etc. in buildings and the like can be mentioned.
• Example 1 After degassing into an autoclave (pressure: 10 MPa) with an internal volume of 1 L and a stainless steel stirrer, vinylidene fluoride (hereinafter abbreviated as VDF) 4.7 g, tetrafluoroethylene (hereinafter abbreviated as TFE) 29.6 g, the following formula : 11.4 g of organosilicon compound represented by, hydroxybutyl vinyl ether (hereinafter abbreviated as HBVE) 42.7 g, cyclohexyl vinyl ether (hereinafter abbreviated as CHVE) 46.7 g, methyl methacrylate (hereinafter abbreviated as MMA) 136.0 g, acetic acid 400 g of butyl, 50 g of methyl ethyl ketone and 5 g of t-butyl peroxypivalate were added, and
• the polymer yield (fluorine-containing copolymer yield) was 236 g, and the monoma reaction rate was 87%. 0.71 g of triisobutylamine was added to the reaction solution containing the obtained copolymer, butyl acetate and methyl ethyl ketone to obtain the fluorine-containing copolymer composition of the present invention.
• the hydroxyl value of the separately isolated copolymer measured by the acetylation method with acetic anhydride was 88 mgKOH / g resin
• the fluorine content by the combustion method was 8.0 wt%
• the number average molecular weight measured by GPC was 2. 0 ⁇ l0 it was 4.
• the characteristics of the obtained fluorine-containing copolymer composition were investigated by the following method. The results are shown in [Table 1].
• Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.] is added to the obtained fluorine-containing copolymer composition so that the hydroxyl group / NCO group of the polymer (fluorine-containing copolymer) becomes 1 / 1.1, and acetic acid is added. Dilute with butyl so that the solid content concentration becomes 29%, adjust the coating agent, apply it on the adjusted glass plate with a # 40 bar coater, heat-treat at 80 ° C. for 24 hours, and apply a thickness of 25 ⁇ m. A membrane was prepared and evaluated.
• the yellowness (YI) of the coating film was measured with a handy type spectrocolor difference meter NR 555 (manufactured by Nippon Denshoku Industries Co., Ltd.).
• turbidity (HAZE) The turbidity (HAZE) of the coating film was measured by a haze meter HM-150L2 (manufactured by Murakami Color Technology Laboratory Co., Ltd.).
• Examples 2 to 10, Comparative Examples 1 to 4 Copolymers and copolymer compositions were produced using the monomers shown in [Table 1] according to the operation of Example 1 above, and their properties were examined in the same manner. The results are shown in [Table 1]. Comparative Examples 1 to 4 are comparative examples outside the scope of the present invention. Further, in Table 1, the amount of the amine compound is shown in parts by weight when the polymer yield (fluorine-containing copolymer yield) in the reaction solution is 100 parts by weight.
• Fluoroolefin VDF Vinylidene fluoride TFE: Tetrafluoroethylene
• Structural formula of organosilicon compound (3) Hydroxy group (OH group) -containing DEGMVE: Diethylene glycol monovinyl ether HBVE: Hydroxybutyl vinyl ether (4) Hydroxy group (OH group) -free CHVE: Cyclohexyl vinyl ether n-BVE: n-Butyl vinyl ether MMA: Methyl methacrylate
• the fluorine-containing copolymer composition of the present invention containing an amine compound in the range of 0.005 parts by weight to 10 parts by weight per 100 parts by weight of the fluorine-containing copolymer has a Gardner color even after being stored at 50 ° C. for 14 days. It was found that the number was as low as 1 to 3, the yellowness (YI) of the coating film was 8.32 or less, the turbidity was 41.9 or less, and almost no discoloration or the like occurred.
• the monomer mixture of Comparative Example 1 using 4 mol% of fluoroolefin did not undergo a polymerization reaction, and a fluorine-containing copolymer could not be obtained.
• the fluorine-containing copolymer composition of Comparative Example 2 using 90 mol% of fluoroolefin was not evaluated thereafter because it was a cloudy and highly viscous liquid.

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• 2021
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