JPH10183049A - Film-forming composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film-forming composition improved in water/oil repellency and long-term adhesion by mixing a specified fluororesin with a repellent and a surface roughness modifier. SOLUTION: An acrylic monomer is subjected to seed polymerization at 20-120 deg.C, desirably 30-70 deg.C for 5-100hr under a pressure of 1.0-50fkg/cm<2> at gauge in an aqueous medium in the presence of fluororesin particles having a mean particle diameter of 40-190nm and a fluoro reactive emulsifier to obtain a base resin comprising a fluororesin comprising a fluoro resin and an acrylic resin and having a mean particle diameter of 50-300nm. 100 pts.wt. base resin is mixed with 0.1-20 pts.wt. at least one repellent selected among fluorosilicone repellents and hydrocarbon repellents and 20-300 pts.wt. surface roughness modifier selected among fluoroolefin polymers, graphite fluoride, silicon dioxide compounds, graphite and potassium titillate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming composition having excellent water and oil repellency and adhesion with time, and a snow and ice preventing paint using the same.

[0002]

2. Description of the Related Art For a composition used for various purposes by exhibiting water and oil repellency by being coated on a base material such as metal or plastic to form a coating film, for example, it is necessary to prevent snow and icing in cold regions. Various studies have been conducted because they can be applied to paints and the like.

JP-A-58-65779 discloses an anti-icing composition comprising a specific organopolysiloxane resin and a specific alkali metal compound.
Japanese Patent No. 6888 discloses an anti-icing composition comprising a specific organopolysiloxane resin, a specific alkali metal compound, and liquid or solid paraffin.
No. 69 discloses a composition for preventing icing comprising a specific organopolysiloxane resin, a specific alkali metal compound and a carboxyl group-containing hydrophobic silicon compound. A coating composition comprising a water-soluble silicone rubber, a specific water-repellent compound, and an organic water-soluble compound has the effect of preventing snow and icing, as disclosed in
JP-A-84069 discloses that a paint containing a specific organopolysiloxane copolymer and a hydroxyl group-containing resin has an anti-icing effect.

Japanese Patent Application Laid-Open No. 6-122838 discloses a fluorinated tetrafluoroethylene powder having a specific molecular weight, an acrylic silicone resin, a polyester resin, an epoxy resin,
A technique for obtaining a water-repellent powder coating by mixing a specific amount of an acrylic resin, a urethane resin, and a fluororesin is disclosed in
No. 3,331,114 discloses an icing film forming composition containing a hydrophobic treatment filler and a binder. Further, WO95 / 18188 discloses that a coating composition containing a specific amount of a compound containing a polyfluorinated carbon chain and a silicone oil can form a coating film having excellent water and oil repellency and stain resistance. It is disclosed.

However, in these prior arts, even if they have sufficient water and oil repellency, the dispersibility and reproducibility of the composition or the like at the time of coating are still insufficient, so However, it was not possible to eliminate the disadvantage that the coating film was peeled off or the coating film was cracked.
In particular, when these compositions are used to prevent snow and icing, in cold regions, on galvanized iron sheets on house roofs;
Because it is applied to the surface of painted objects such as roofs of vehicles such as ships, buses and passenger cars, it does not have the dispersibility and reproducibility at the time of painting. Adhesion was impaired, and peeling of the coating film and cracking of the coating film were likely to occur.

In Japanese Patent Application Laid-Open Nos. 4-189879 and 61-12760, when an acrylic resin is added to a fluorine-based copolymer, the dispersibility of each component in the composition is improved and the adhesion is improved. It is described that the property can be improved,
There is no disclosure of a technique for utilizing this to prevent snow and icing, and it has been difficult to obtain the effect of preventing snow and icing by improving water and oil repellency from this technique. .

[0007]

SUMMARY OF THE INVENTION In view of the above situation, the present invention provides a film-forming composition which has a sufficient effect of preventing snow and icing, and which does not change with time and can be maintained for a long period of time. It is another object of the present invention to provide a snow- and ice-prevention paint using the same.

[0008]

The present invention is a film forming composition comprising a main resin mixed with a repellent and a surface roughness regulator, wherein the main resin comprises a fluorine resin and an acrylic resin. It is a fluorine-containing resin. Hereinafter, the present invention will be described in detail.

The main resin used in the present invention is a fluorine-containing resin composed of a fluorine-based resin and an acrylic resin. In the present specification, the fluorine-containing resin is a fluorine-containing resin (1) obtained from a fluorine-containing resin aqueous dispersion and an acrylic resin, and an organic solvent-soluble resin obtained by mixing an organic solvent-soluble fluorine-containing resin with an acrylic resin. It can be broadly classified into three types: a fluorine-containing resin (2), and a fluorine-containing resin (3) obtained by mixing an acrylic resin with a copolymer of a fluoroolefin and a specific vinyl monomer. Hereinafter, the above three fluorine-containing resins will be described.

A fluorine-containing resin obtained from an aqueous dispersion of a fluorine-containing resin and an acrylic resin (1) The first of the above-mentioned fluorine-containing resins is a fluorine-containing resin obtained from an aqueous dispersion of a fluorine-containing resin and an acrylic resin (1) It is. The fluorine-containing resin (1) can be roughly classified into the following four. Fluorine-containing resin obtained from a fluororesin aqueous dispersion obtained by seed polymerization of an acrylic resin (1-
1). A fluorine-containing resin (1-2) obtained by mixing an acrylic resin with the fluorine-containing resin (1-1). A fluorine-containing resin (1-3) obtained by mixing an acrylic resin with another aqueous dispersion of a fluorine-containing resin. A fluorine-containing resin (1-4) obtained by mixing an acrylic resin with a fluorine-containing resin aqueous dispersion. Among the fluorine-containing resins (1), first,
The fluorine-containing resin (1-1) will be described. The fluorine-containing resin (1-1) is a fluorine-containing resin obtained from a fluorine-containing resin aqueous dispersion obtained by seed polymerization of an acrylic resin. The fluorine-containing resin aqueous dispersion is obtained by forming a fluorine-containing composite resin in an aqueous medium with an acrylic monomer in the presence of the fluorine-containing resin particles. The aqueous medium is not particularly limited, and examples thereof include those obtained by adding an additive or a solvent described in detail below to water.

The fluorine-containing resin constituting the above-mentioned fluorine-containing resin particles is a copolymer of fluoroolefin. The fluoroolefin copolymer is dispersed in the form of particles in an aqueous medium, and is polymerized by so-called seed polymerization when a fluorine-based composite resin is formed from the acrylic monomer. In the present specification, “seed polymerization” means a reaction of polymerizing with another monomer in an aqueous medium in which resin particles exist. Accordingly, the fluorine-based composite resin refers to a seed polymer after the seed polymerization, and the resin particles refer to seed particles in the seed polymerization.

The fluoroolefin includes vinylidene fluoride (VdF), tetrafluoroethylene (TFE), and chlorotrifluoroethylene (CTF).
E), hexafluoropropylene (HFP) and the like. Examples of the fluoroolefin copolymer include VdF / TFE copolymer, VdF / CTFE copolymer, VdF / HFP copolymer, TFE / CTFE copolymer, TFE / HFP copolymer, and CTFE / HFP copolymer. Merged, VdF / TFE / CTFE copolymer, VdF / T
FE / HFP copolymer, TFE / CTFE / HFP copolymer, VdF / CTFE / HFP copolymer, VdF / T
FE / CTFE / HFP copolymer and the like can be mentioned.

The fluoroolefin copolymer constituting the seed particles is preferably a VdF-based copolymer, and more preferably a polymer containing 70 mol% or more of VdF. When VdF is 70 mol% or more, the compatibility between the seed particles and the polymer composed of the acrylic monomer is improved.

The average particle diameter of the seed particles is closely related to the average particle diameter of the fluorine-based composite resin after the seed polymerization, and the average particle diameter of the fluorine-based composite resin after the seed polymerization is set to 50 to 300 nm. Therefore, the thickness is preferably set to 40 to 290 nm.

The copolymer constituting the seed particles can be obtained by a usual emulsion polymerization method. For example, 0.01 to 1.0% by weight, based on water, of a fluorine-based reactive emulsifier having a hydrophilic site, and 0 to 1.0% by weight of a fluorine-based emulsifier.
It can be prepared by emulsion polymerization of a monomer mixture containing a fluoroolefin in the coexistence of each of the above components.

[0016] Further, based on water, 1.0% by weight or less, preferably 0.5% by weight or less, more preferably 0.2% by weight
0.001 to 0.1% by weight, preferably 0.01 to 0.05% by weight, of the nonionic non-fluorine-based interface with respect to the fluorine-based surfactant (the lower limit is usually 0.01% by weight) and water. It can be prepared by emulsion polymerization of a monomer mixture containing a fluoroolefin in the presence of an activator. The aqueous dispersion obtained by these methods can stably contain seed particles having an average particle diameter of 0.2 μm or less at a high concentration of 30 to 50% by weight.

Examples of the fluorine-based reactive emulsifier having a hydrophilic site include CF ₂ 2CF— (CF ₂ CF
X) _n Y ( _where X is F or CF ₃ , Y is SO
₃ M, COOM (M is a hydrogen atom, amine, ammonium or alkali metal), n represents an integer. ), CF ₂
ＣＦCF—O (CFX) _n (where X, Y and n are the same as above), CH ₂ ＣＦCF—CF ₂ —O (CF (CF ₃ ) C
_{F 2 O) n -CF (CF} 3) Y ( wherein, Y, n, the _{same.), CF 2 = CF-} CF 2 -O (CF (C
F ₃ ) CF ₂ O) _n -CF (CF ₃ ) Y (where Y, n
Is the same as above. And the like, having the structure represented by formula (1), but from the viewpoint of solubility in water and surface activity,
n is preferably in the range of 0 to 3. More specifically, CF ₂ = CF—CF ₂ —O (CF (CF ₃ ) CF ₂
O) _n -CF (CF ₃₎ the structure of COOH, n is 0-2
Is used.

The polymerization temperature is from 20 to 120 ° C., preferably from 30 to 70 ° C. When the polymerization temperature is lower than 20 ° C., the stability of the produced latex generally becomes low, and the polymerization temperature becomes lower than 12 ° C.
If it is higher than 0 ° C., the polymerization rate tends to stall due to chain transfer. Polymerization depends on the type of polymer, but usually,
1.0 to 50 kgf / cm ² (gauge pressure)
Heating is performed for ~ 100 hours.

Examples of the fluorine-based emulsifier used for the emulsion polymerization of the seed particles include one or a mixture of two or more compounds having a fluorine atom in the structure and having surface activity. For example, X (CF ₂ ) _n CO
An acid represented by OH (n is an integer of 6 to 20, X represents F or a hydrogen atom) and an alkali metal salt, an ammonium salt, an amine salt or a quaternary ammonium salt thereof; Y (CH
₂ CF ₂ ) _m COOH (m is an integer of 6 to 13, Y is
Represents an F or chlorine atom. And the alkali metal salts, ammonium salts, amine salts and quaternary ammonium salts thereof. More specifically, ammonium salts of perfluorooctanoic acid, ammonium salts of perfluorononanoic acid and the like can be mentioned. In addition, a known fluorine-based surfactant can be used.

In the emulsion polymerization for obtaining seed particles, a small amount of a nonionic non-fluorinated surfactant can be used in the presence of a fluorine-based surfactant, and specific examples thereof include polyoxyethylene alkyl ethers. , Polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerin esters and derivatives thereof.

More specifically, examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether and the like. Polyoxyethylene alkyl phenyl ethers include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether and the like, and polyoxyethylene alkyl esters include monolaurate polyethylene glycol, Examples thereof include polyethylene glycol oleate and polyethylene glycol monostearate. Examples of the sorbitan alkyl esters include monolaurin. Examples include polyoxyethylene sorbitan, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and the like.Examples of glycerin esters include glyceryl monomyristate and glyceryl monostearate. And glyceryl monooleate.

Examples of these derivatives include polyoxyethylene alkylamine, polyoxyethylene alkylphenyl-formaldehyde condensate, and polyoxyethylene alkyl ether phosphate.
Particularly preferred are polyoxyethylene alkyl ethers and polyoxyethylene alkyl esters having an HLB value of 10 to 18, specifically, polyoxyethylene lauryl ether (EO: 5 to 5).
20. EO represents the number of ethylene oxide units. ),
Polyethylene glycol monostearate (EO: 6 ~
10).

The acrylic monomer according to the present invention is not particularly limited. For example, the alkyl group has 1 to 1 carbon atoms.
Examples thereof include an alkyl acrylate of 18; an alkyl methacrylate having an alkyl group of 1 to 18 carbon atoms; and a monomer having an ethylenically unsaturated bond copolymerizable therewith.

The alkyl acrylate having 1 to 18 carbon atoms in the alkyl group includes, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate,
I-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, n-hexyl acrylate, t-butyl cyclohexyl acrylate, stearyl acrylate And lauryl acrylate.

The alkyl methacrylate having 1 to 18 carbon atoms in the alkyl group includes, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-methacrylic acid.
Butyl, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, t-butylcyclohexyl methacrylate, stearyl methacrylate, lauryl methacrylate, and the like. .

For the purpose of improving solvent resistance and water resistance, polyfunctional monomers such as ethylene glycol dimethacrylate and propylene glycol dimethacrylate can be copolymerized. Examples of the monomer having an ethylenically unsaturated bond copolymerizable with the acrylate and the methacrylate include the following (I) and (II).

(I) Monomers having a reactive functional group, for example, ethylenically unsaturated carboxylic acids such as maleic acid, itaconic anhydride, succinic anhydride, crotonic acid; acrylamide, methacrylamide, N-methyl Amide compounds such as acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, N-methylolmethacrylamide, N-methylmethacrylamide, N-butoxymethylmethacrylamide; hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate , Hydroxyl-containing monomers such as hydroxypropyl methacrylate; epoxy-containing monomers such as glycidyl acrylate and glycidyl methacrylate; γ-trimethoxysilane methacrylate, γ-triethoxysilane methacrylate and the like And aldehyde group-containing monomers such as acrolein; caprolactone-modified hydroxy acrylate and caprolactone-modified hydroxy methacrylate.

(II) Other vinyl compounds, for example, α-olefins such as ethylene, propylene and isobutylene; ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether Vinyl ethers such as polyoxyethylene vinyl ether; alkenyls such as polyoxyethylene allyl ether, ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol, allyl ether; vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, benzoic acid Vinyl esters such as vinyl, VEOVA9, VEOVA10 (manufactured by Shell); itaconic anhydride, succinic anhydride,
Ethylenically unsaturated carboxylic acids such as crotonic acid; aromatic vinyl compounds such as styrene, α-methylstyrene and p-tert-butylstyrene; acrylonitrile and the like.

As the monomer having an ethylenically unsaturated bond copolymerizable with the acrylate or methacrylate, a compound containing in its molecule a low molecular weight polymer or oligomer containing a hydrophilic site may be used. it can. The above-mentioned hydrophilic site means a site having a hydrophilic group or a site having a hydrophilic bond, and a site comprising a combination thereof. The hydrophilic group may be any of ionic, non-ionic, amphoteric and combinations thereof, but is preferably a non-ionic or anionic hydrophilic group. Further, a known reactive emulsifier may be used.

Examples of the acrylic ester, the monomer having an ethylenically unsaturated bond copolymerizable with the methacrylic ester, and the reactive emulsifier include polyethylene glycol methacrylate, polypropylene glycol methacrylate, methoxypolyethylene glycol methacrylate, and polyethylene. Glycol acrylate,
Polypropylene glycol acrylate, methoxy polyethylene glycol acrylate, polyethylene glycol allyl ether, methoxy polyethylene glycol allyl ether, polyethylene glycol polypropylene glycol monomethacrylate, polyethylene glycol polytetramethylene glycol monomethacrylate, polyoxyethylene alkyl allyl phenyl ether, polyoxyethylene alkyl allyl phenyl Ether sulfate, styrene sulfonate, allyl alkyl sulfonate, polyethylene glycol methacrylate sulfate, alkyl allyl sulfosuccinate, bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate, polyoxyethylene alkyl phenyl ether acrylic Acid Ether, methacryloyloxy polyoxyalkylene sulfates, methacryloyloxy alkylene sulfates, polyoxyethylene vinyl ethers include polyoxyethylene vinyl esters, and the like.

In the present invention, when the acrylic monomer is subjected to seed polymerization in the presence of fluorine-containing resin particles, the acrylic monomer first swells into the fluorine-containing resin, and at this time, the acrylic monomer is swelled. An aqueous dispersion of the fluorinated copolymer in which the monomer is uniformly dissolved is obtained. Thereafter, by adding a polymerization initiator, the acrylic monomer is polymerized to form compatible particles with molecular chains entangled. When the acrylic monomer is polyfunctional, an interpenetrating network (IPN) can be formed. As the polyfunctional acrylic monomer, for example,
Monoglycol dimethacrylate, diglycol dimethacrylate and the like can be mentioned.

The above-mentioned seed polymerization of the acrylic monomer is carried out by a known method, for example, a method in which the whole amount of the acrylic monomer is charged into the reaction system in the presence of the fluorine-containing resin particles, Can be carried out by a method in which a part of the above is charged and then the remainder is continuously or dividedly charged, or a method in which the entire amount of the acrylic monomer is continuously charged. Also,
The polymerization conditions for the seed polymerization are the same as those for ordinary emulsion polymerization.For example, in an aqueous medium containing fluororesin particles, a surfactant, a polymerization initiator, a chain transfer agent, and in some cases, a chelating agent, Add pH adjuster and solvent
Polymerization can be carried out by performing the reaction at a temperature of 0 to 90 ° C for 0.5 to 6 hours.

As the surfactant, anionic, nonionic or anionic-nonionic combinations can be used, and in some cases, amphoteric surfactants can also be used. Examples of the anionic surfactant include higher alcohol sulfates, alkyl sulfonate sodium salts, alkylbenzene sulfonate sodium salts, dialkyl succinate sodium sulfonates, and alkyl diphenyl ether disulfonate sodium salts such as hydrocarbon-based anionic surfactants. In addition to the surfactant, a fluorine-containing anionic surfactant such as a fluoroalkyl carboxylate, a fluoroalkyl sulfonate, a fluoroalkyl sulfate, and the like can be given.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, sorbitan alkyl esters, and glycerin. Esters and their derivatives can be mentioned. Examples of the amphoteric surfactant include lauryl betaine.

As the above-mentioned surfactant, a so-called reactive emulsifier which can be copolymerized with an acrylic monomer can be used. Further, such a reactive emulsifier and the above-mentioned emulsifier can be used in combination. it can. The amount of the surfactant used is usually, per 100 parts by weight of the acrylic monomer,
It is 0.05 to 5.0 parts by weight.

The polymerization initiator used in the seed polymerization is not particularly limited as long as it generates a radical capable of being subjected to a free radical reaction in an aqueous medium at a temperature between 20 ° C. and 90 ° C. It is also possible to use in combination with a reducing agent. Examples of such a polymerization initiator include water-soluble polymerization initiators such as persulfate and hydrogen peroxide, and reducing agents such as sodium pyrobisulfite, sodium hydrogen sulfite, sodium L-ascorbate and Rongalite. it can. As an oil-soluble polymerization initiator, diisopropyl peroxydicarbonate (IP
P), benzoyl peroxide, dibutyl peroxide, azobisisobutyronitrile (AIBN) and the like. The amount of the polymerization initiator is usually 0.05 to 2.0 parts by weight per 100 parts by weight of the acrylic monomer.

As the chain transfer agent used in the seed polymerization, for example, halogenated hydrocarbons such as chloroform and carbon tetrachloride; n-dodecyl mercaptan, tert-
Mercaptans such as dodecyl mercaptan and n-octyl mercaptan can be exemplified. The amount of the chain transfer agent to be used is generally 0 to 5.0 parts by weight per 100 parts by weight of the acrylic monomer.

The above-mentioned solvent is used within a range that does not impair workability, disaster prevention safety, environmental safety, and manufacturing safety, for example, in a range of 20% by weight or less. For example, methyl ethyl ketone, acetone, trichlorotrifluoroethane, Methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, dioxane, butyl carbitol acetate, texanol, ethyl acetate,
Butyl acetate and the like can be mentioned. The addition of such a solvent may improve the swellability of the acrylic monomer in the fluororesin particles.

The particle diameter of the fluororesin particles of the present invention in the aqueous dispersion is preferably from 50 to 300 nm. More preferably, it is 50 to 200 nm. The particle size is 50n
When the concentration is less than 30%, which is a practical range, the viscosity of the fluororesin aqueous dispersion significantly increases,
It interferes with the work of coating. When the particle diameter exceeds 300 nm, the sedimentation stability of the obtained fluororesin aqueous dispersion becomes poor, and the resin composition having the same composition causes an increase in the minimum film forming temperature of the fluororesin aqueous dispersion. It will be. The fluorine-containing resin (1-
In 1), the total amount of the seed-polymerized acrylic resin is based on 100 parts by weight of the resin constituting the seed particles.
Usually, it is 10 to 400 parts by weight, preferably 5 to 9 parts by weight.
5 parts by weight.

The description of the fluorine-containing resin (1-1) has been completed.
2) a fluorine-containing resin (1-3) obtained by mixing an acrylic resin with another fluorine-containing resin aqueous dispersion, and
The fluorine-containing resin (1-4) obtained by mixing the acrylic resin with the fluorine-containing resin aqueous dispersion will be described. Hereinafter, first, other fluororesin aqueous dispersions will be described. The other fluorine-containing resin aqueous dispersion constituting the fluorine-containing resin (1-3) has a basic structure in which fluorine-containing resin particles are dispersed in an aqueous medium. The fluororesin constituting the fluororesin particles is a fluororesin made of a copolymer of a fluoroolefin and a monomer copolymerizable therewith. The fluoroolefin is not particularly limited, and examples thereof include vinyl fluoride, vinylidene fluoride (VdF), and tetrafluoroethylene (T
FE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), fluoroolefins having about 2 to 4 carbon atoms such as trifluoroethylene, and the like.

Examples of the monomer copolymerizable with the fluoroolefin include olefins such as ethylene, propylene and isobutylene; ethyl vinyl ether (EV)
E), vinyl ethers such as cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, and polyoxyethylene vinyl ether; polyoxyethylene allyl ether;
Alkenyls such as ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol, allyl ether; vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, VEOVA9 (manufactured by Shell), VEOVA10 (manufactured by Shell), etc. And ethylenically unsaturated carboxylic acids such as itaconic anhydride, succinic anhydride and crotonic acid.

The copolymer of the above-mentioned fluoroolefin and a monomer copolymerizable therewith is not particularly limited, and examples thereof include a CTFE / vinyl ether copolymer, a CTFE / vinyl ester copolymer, and a TFE / vinyl ether copolymer. Coalesce, TFE / vinyl ester copolymer, TFE / ethylene copolymer, TFE / propylene copolymer, CTFE /
Ethylene copolymer, CTFE / propylene copolymer, C
TFE / ethylene / vinyl ether copolymer, CTFE
/ Ethylene / vinyl ester copolymers, and those obtained by modifying those copolymers with a small amount of copolymerizable monomers.

The aqueous fluororesin dispersion is, for example,
After polymerizing the fluorine-containing resin constituting the fluorine-containing resin particles in a solvent or the like, in the presence of an emulsifier, dispersed in water,
A phase inversion method in which the solvent is distilled off, a method in which the emulsion polymerization of the fluorine-containing resin constituting the fluorine-containing resin particles is performed in an aqueous medium, and the like can be given. Preferred is a method in which emulsion polymerization is carried out in an aqueous medium.
The emulsion polymerization can be carried out by the same method as the emulsion polymerization usually performed, for example, in a closed container, in an aqueous medium, a surfactant, a polymerization initiator, a chain transfer agent, in some cases, a chelating agent, In the presence of a pH adjuster and a solvent, a fluoroolefin, a monomer such as a monomer copolymerizable with the fluoroolefin, is heated at a temperature of 10 to 90 ° C for 0.5 to 40.
It can be obtained by reacting for a time.

As the above-mentioned surfactant, an anionic, nonionic or anionic-nonionic combination can be used, and in some cases, an amphoteric surfactant can also be used. Examples of the anionic surfactant include higher alcohol sulfates, alkyl sulfonate sodium salts, alkylbenzene sulfonate sodium salts, dialkyl succinate sodium sulfonates, and alkyl diphenyl ether disulfonate sodium salts such as hydrocarbon-based anionic surfactants. In addition to the surfactant, a fluorine-containing anionic surfactant such as a fluoroalkyl carboxylate, a fluoroalkyl sulfonate, a fluoroalkyl sulfate, and the like can be given.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, sorbitan alkyl esters, and glycerin. Esters and their derivatives can be mentioned. Examples of the amphoteric surfactant include lauryl betaine. Further, a so-called reactive emulsifier can be used as the surfactant, and further, such a reactive emulsifier and the above-mentioned emulsifier can be used in combination.

The polymerization initiator used in the emulsion polymerization is not particularly limited as long as it generates a radical capable of being subjected to a free radical reaction in an aqueous medium at a temperature of 10 to 90 ° C., and in some cases, It is also possible to use in combination with a reducing agent. Examples of such a polymerization initiator include water-soluble polymerization initiators such as persulfate and hydrogen peroxide, and reducing agents such as sodium pyrobisulfite, sodium hydrogen sulfite, sodium L-ascorbate and Rongalite. it can. As the oil-soluble polymerization initiator,
Diisopropyl peroxydicarbonate (IPP),
Examples include benzoyl peroxide, dibutyl peroxide, azobisisobutyronitrile (AIBN), and the like.

Examples of the chain transfer agent used in the above emulsion polymerization include halogenated hydrocarbons such as chloroform and carbon tetrachloride; mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan and n-octyl mercaptan. Can be mentioned.

The above-mentioned solvent is used within a range that does not impair workability, disaster prevention safety, environmental safety, and production safety, for example, in a range of 20% by weight or less. For example, methyl ethyl ketone, acetone, trichlorotrifluoroethane, Methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, dioxane, butyl carbitol acetate, texanol, ethyl acetate,
Butyl acetate and the like can be mentioned.

The description of the other fluororesin aqueous dispersion has been completed. The fluorine-containing resin (1-3) of the fluorine-containing resin (1) is obtained by mixing an acrylic resin with the above-mentioned other fluorine-containing resin aqueous dispersion. Further, the fluorine-containing resin (1-2) of the fluorine-containing resin (1)
Is obtained by mixing an acrylic resin with the fluorine-containing resin (1-1) which has already been described. Further, the fluorine-containing resin (1-4) obtained by mixing the acrylic resin with the aqueous fluorine-containing resin dispersion is the same as the “seed particles” described in detail in the description of the fluorine-containing resin (1-1), except that the aqueous medium is an aqueous medium. It has a basic structure dispersed therein, but is not an acrylic resin subjected to seed polymerization. The “seed particles” are made of a copolymer of fluoroolefin, as described in detail above. Examples of the fluoroolefin include vinylidene fluoride (VdF), tetrafluoroethylene (TFE), and chlorotrifluoroethylene. (CTF
E), hexafluoropropylene (HFP) and the like. Examples of the fluoroolefin copolymer include VdF / TFE copolymer, VdF / CTFE copolymer, VdF / HFP copolymer, and TFE / CTFE. Copolymer, TFE / HFP copolymer, CTFE / HFP copolymer, VdF / TFE / CTFE copolymer, VdF / TF
E / HFP copolymer, TFE / CTFE / HFP copolymer, VdF / CTFE / HFP copolymer, VdF / TF
E / CTFE / HFP copolymer and the like,
A detailed description of these has already been given.

The acrylic resin is not particularly limited as long as it is a polymer whose main chain is constituted by a hydrocarbon chain derived from acrylic acid and / or methacrylic acid. And a copolymer of an acrylic monomer and another monomer having an ethylenically unsaturated double bond copolymerizable therewith. The acrylic monomer is not particularly limited as long as it contains acrylic acid and / or methacrylic acid (hereinafter also referred to as “(meth) acrylic acid”). For example, acrylic acid, alkyl acrylate, Examples thereof include methacrylic acid and alkyl methacrylate. The alkyl (meth) acrylate is not particularly limited. For example, the alkyl acrylate has 1 to 18 carbon atoms, and the alkyl group has 1 to 1 carbon atoms.
18 alkyl methacrylate and the like.

The alkyl acrylate having 1 to 18 carbon atoms in the alkyl group includes, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate,
I-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, n-hexyl acrylate, t-butyl cyclohexyl acrylate, stearyl acrylate And lauryl acrylate.

Examples of the alkyl methacrylate having 1 to 18 carbon atoms in the alkyl group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, and n-methacrylic acid.
Butyl, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, t-butylcyclohexyl methacrylate, stearyl methacrylate, lauryl methacrylate, and the like. . For the purpose of improving solvent resistance and water resistance, a polyfunctional monomer such as ethylene glycol dimethacrylate or propylene glycol dimethacrylate may be copolymerized with the acrylic monomer. Examples of the monomer having an ethylenically unsaturated bond copolymerizable with the acrylate and the methacrylate include the following (I) and (I)
I) and the like.

(I) Monomers having a reactive functional group, for example, ethylenically unsaturated carboxylic acids such as maleic acid, itaconic anhydride, succinic anhydride, crotonic acid; acrylamide, methacrylamide, N-methyl Amide compounds such as acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, N-methylolmethacrylamide, N-methylmethacrylamide, N-butoxymethylmethacrylamide; hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate , Hydroxyl-containing monomers such as hydroxypropyl methacrylate; epoxy-containing monomers such as glycidyl acrylate and glycidyl methacrylate; γ-trimethoxysilane methacrylate, γ-triethoxysilane methacrylate and the like And aldehyde group-containing monomers such as acrolein; caprolactone-modified hydroxy acrylate and caprolactone-modified hydroxy methacrylate.

(II) Other vinyl compounds, for example, α-olefins such as ethylene, propylene and isobutylene; ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether Vinyl ethers such as polyoxyethylene vinyl ether; alkenyls such as polyoxyethylene allyl ether, ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol, allyl ether; vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, benzoic acid Vinyl esters such as vinyl, VEOVA9, VEOVA10 (manufactured by Shell); itaconic anhydride, succinic anhydride,
Ethylenically unsaturated carboxylic acids such as crotonic acid; aromatic vinyl compounds such as styrene, α-methylstyrene and p-tert-butylstyrene; acrylonitrile and the like.

As the monomer having an ethylenically unsaturated bond copolymerizable with the above-mentioned acrylate or methacrylate, a compound containing in its molecule a low molecular weight polymer or oligomer containing a hydrophilic site may be used. it can. The above-mentioned hydrophilic site means a site having a hydrophilic group or a site having a hydrophilic bond, and a site comprising a combination thereof. The hydrophilic group may be any of ionic, non-ionic, amphoteric and combinations thereof, but is preferably a non-ionic or anionic hydrophilic group. Further, a known reactive emulsifier may be used.

Examples of the acrylic acid ester, a monomer having an ethylenically unsaturated bond copolymerizable with the methacrylic acid ester, and the reactive emulsifier include, for example, polyethylene glycol methacrylate, polypropylene glycol methacrylate, methoxypolyethylene glycol methacrylate, and polyethylene. Glycol acrylate,
Polypropylene glycol acrylate, methoxy polyethylene glycol acrylate, polyethylene glycol allyl ether, methoxy polyethylene glycol allyl ether, polyethylene glycol polypropylene glycol monomethacrylate, polyethylene glycol polytetramethylene glycol monomethacrylate, polyoxyethylene alkyl allyl phenyl ether, polyoxyethylene alkyl allyl phenyl Ether sulfate, styrene sulfonate, allyl alkyl sulfonate, polyethylene glycol methacrylate sulfate, alkyl allyl sulfosuccinate, bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate, polyoxyethylene alkyl phenyl ether acrylic Acid Ether, methacryloyloxy polyoxyalkylene sulfates, methacryloyloxy alkylene sulfates, polyoxyethylene vinyl ethers include polyoxyethylene vinyl esters, and the like.

In order to obtain the acrylic resin of the present invention, a homopolymer of the acrylic monomer and a copolymer of the acrylic monomer and another copolymerizable monomer are prepared. The polymerization method is not particularly limited, and conventionally known methods, for example, emulsion polymerization, suspension polymerization, bulk polymerization and the like can be appropriately selected and used. Also, the molecular weight of the polymer after polymerization can be appropriately selected in consideration of its use.

A polymerization vessel used for polymerization;
As the polymerization method, polymerization initiator, polymerization inhibitor, other auxiliaries, emulsification aids in emulsion polymerization, surfactants, and other additives, conventionally known ones can be appropriately selected and used. In the selection, any conventionally known acrylic resin can be used as long as the obtained acrylic resin is appropriate.

The fluorine-containing resin (1-2), the fluorine-containing resin (1-3) and the fluorine-containing resin (1-
The mixing amount of the acrylic resin to be mixed to constitute 4) is preferably from 5 to 80% by weight, particularly preferably from 10 to 7% by weight.
0% by weight. If the mixing amount of the acrylic resin is too low,
The object of the present invention cannot be achieved because the dispersibility and adhesion of the entire composition are reduced, and when the mixing amount is too large, the weather resistance is deteriorated.

The fluorine-containing resin (1-2), the fluorine-containing resin (1-3) or the fluorine-containing resin (1-
The mixing ratio in the case where 4) and the acrylic resin are mixed in the aqueous medium is not particularly limited, and the solid content concentration of both resins is generally about 5 to 90% by weight, preferably 20 to 8% by weight.
It is preferable to mix them so as to be 0% by weight. The mixing method is not particularly limited, and a generally known method can be used.

A curing agent may be added to the fluorine-containing resin (1) of the present invention, if desired, for the purpose of further improving the durability and solvent resistance of the coating film formed by the coating composition. As described above, the acrylic resin contained in the fluorine-containing resin (1) may have a functional group. In such a case, the fluorine-containing resin (1) reacts with the curing agent. Having a functional group. The curing agent is not particularly limited, and examples thereof include an isocyanate-based curing agent and a melamine-based curing agent.

Organic solvent-soluble fluorine-containing resin obtained by mixing an organic solvent-soluble fluorine-containing resin with an acrylic resin (2) The second type of the fluorine-containing resin according to the present invention is a mixture of an organic solvent-soluble fluorine-containing resin and an acrylic resin. And a fluorine-containing resin (2) soluble in an organic solvent. As the organic solvent-soluble fluorine-containing resin, preferably, for example, a fluoroolefin copolymer and the like can be mentioned. Examples of the fluoroolefin include VdF, TFE and CTFE. The fluoroolefin copolymer includes VdF / TFE copolymer, VdF /
CTFE copolymer, TFE / CTFE copolymer, VdF
/ TFE / CTFE copolymer and the like.

Examples of the above-mentioned organic solvent-soluble fluorine-containing resin include, in addition to those described above, homopolymers of fluoroolefins, copolymers of fluoroolefins other than those described above, and copolymers of fluoroolefins with other monomers. Can be mentioned. These are not particularly limited, and include, for example, a homopolymer of VdF, a homopolymer of trifluoroethylene (TrFE), a homopolymer of TFE,
TFE homopolymer, HFP homopolymer, VdF / T
rFE copolymer, VdF / vinyl fluoride (VF) copolymer, VdF / HFP copolymer, TFE / TrFE copolymer, TFE / VF copolymer, TFE / HFP copolymer, CTFE / TrFE copolymer Coalescence, CTFE / VF copolymer, CTFE / HFP copolymer, VdF / TFE / T
rFE copolymer, VdF / TFE / VF copolymer, Vd
F / TFE / HFP copolymer, VdF / CTFE / Tr
FE copolymer, VdF / CTFE / VF copolymer, Vd
F / CTFE / HFP copolymer, TFE / CTFE / T
rFE copolymer, TFE / CTFE / VF copolymer, T
FE / CTFE / HFP copolymer and the like can be mentioned.

Among them, a VdF-based copolymer containing VdF is preferred. Further, in order to increase the possibility of using an organic solvent, one containing 50 to 90 mol% of VdF, 5 to 30 mol% of TFE, 5 to 30 mol% of CTFE, and VdF
dF50-90 mol%, TFE5-30 mol%, HFP
Those containing 5 to 30 mol% are more preferred.

The above-mentioned organic solvent-soluble fluororesin can be prepared by polymerizing the above-mentioned monomer by a usual polymerization method. As such a polymerization method, for example, a fluorine-containing resin (1-1) obtained from a fluorine-containing resin aqueous dispersion obtained by seed-polymerizing the acrylic resin described above.
And the method described in detail in the section of the method for polymerizing the fluorine-containing resin constituting the seed particles in the section.

The organic solvent is not particularly limited, but from the viewpoint of solubility, ketones or esters having a boiling point of about 60 to 250 ° C. are particularly preferable. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Examples thereof include cyclohexanone, ethyl acetate, n-butyl acetate, and methyl cellosolve acetate. These can be used alone or in combination of two or more. In addition to the above, examples of the organic solvent include tetrahydrofuran (THF), dimethylformamide (D
MF) and the like. Further, aromatic organic compounds such as toluene and xylene, alcohols, and the like may be added. These organic solvents can dissolve the above-mentioned organic solvent-soluble fluororesin well to obtain a composition in a wide concentration range from low to high, and have excellent gloss and weather resistance as a film-forming composition. It will be.

The acrylic resin to be mixed with the organic solvent-soluble fluorine-containing resin is not particularly limited, and examples thereof include the same acrylic resins as those described in detail in the section of the fluorine-containing resin (1). The mixing amount of the acrylic resin mixed with the organic solvent-soluble fluororesin is 5 to 5.
80% by weight is preferable, and particularly preferably, 10 to 70% by weight.
It is. If the mixing amount of the acrylic resin is too low, the dispersibility and adhesiveness of the entire composition are reduced, and the object of the present invention cannot be achieved. If the mixing amount is too large, the weather resistance deteriorates.

The mixing ratio when the above-mentioned organic solvent-soluble fluororesin and the above-mentioned acrylic resin are mixed in the above-mentioned organic solvent is not particularly limited. It is preferable to mix so that the content is preferably 20 to 80% by weight. The mixing method is not particularly limited, and a generally known method can be used.

The above organic solvent-soluble fluorine-containing resin (2)
For the purpose of further improving the durability and solvent resistance of the coating film formed by the film-forming composition, a curing agent may be added thereto, if desired. As described above, the acrylic resin contained in the organic solvent-soluble fluorine-containing resin (2) may have a functional group. In such a case, the organic solvent-soluble fluorine-containing resin (2) is cured. It has a functional group that reacts with the agent. The curing agent is not particularly limited, and examples thereof include an isocyanate-based curing agent and a melamine-based curing agent.

Fluorine-containing resin (3) prepared by mixing an acrylic resin with a copolymer of a fluoroolefin and a specific vinyl monomer (3) The third fluorine-containing resin is a fluorine-containing resin (3). The fluoroolefin constituting the copolymer of the above fluoroolefin and a specific vinyl monomer has a formula: CF ₂ 2CFX (where X represents a hydrogen atom, a fluorine atom, a chlorine atom or a trifluoromethyl group) )). Preferred among such fluoroolefins are TF
E, CTFE, TrFE, and HFP, but the durable water repellent of the present invention is free of chlorine and can form a more durable and tough coating film.
TFE is preferred from the viewpoint that the fluorine content of the durable water repellent of the present invention is improved and the water repellency is improved.

The specific vinyl monomer copolymerized with the fluoroolefin is (i) a β-methyl-β-alkyl-substituted α-olefin, (ii) a vinyl group-containing ether,
And (iii) a vinyl group-containing ester, and any one of (i), (ii) and (iii) is copolymerized with the fluoroolefin to form the fluororesin (3). However, it is also possible to use two or more of these.
These are preferably carboxyl group-containing vinyl monomers, or hydroxyl groups, epoxy groups, or vinyl monomers having a curing reactive site such as a silyl group.
If they have neither a carboxyl group nor a curing reactive site, they have a carboxyl group-containing vinyl monomer separately from these vinyl monomers; It is preferable to list a vinyl monomer as a specific vinyl monomer copolymerized with the above-mentioned fluoroolefin.

The (i) β-methyl-β-alkyl-substituted α-olefin has the formula: CH ₂ ＣＲCR ⁰ (CH ₃ ) (wherein R ⁰ represents an alkyl group having 1 to 8 carbon atoms) .)
It is represented by Such is not particularly limited,
For example, isobutylene, 2-methyl-1-butene, 2-
Methyl-1-pentene, 2-methyl-1-hexene and the like can be mentioned, and among them, isobutylene is preferable. The above (i) β-methyl-β-alkyl-substituted-α-
The content ratio of the olefin in the copolymer of the fluoroolefin and the specific vinyl monomer is preferably from 5 to 45% by weight. If it is less than 5% by weight, the weather resistance of the durable water repellent of the present invention will be poor, and if it exceeds 45% by weight, it will be difficult to prepare the copolymer.

The (ii) vinyl group-containing ether is
Alkyl vinyl ether or alkyl allyl represented by the formula: CH ₂ ＣＨCHR (wherein R represents OR ¹¹ or CH ₂ OR ¹¹ (R ¹¹ represents an alkyl group having 1 to 8 carbon atoms)) Ethers having a hydroxyl group as hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether (in this case, R ¹¹ is an alkyl group having a hydroxyl group), the hydroxyl group is used as a reaction site with a curing agent described later. Will work, which is preferable. The (ii) vinyl group-containing ether is not particularly restricted but includes, for example, ethyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy -2-
Methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether And the like. Among them, 4-hydroxybutyl vinyl ether is preferred.

The content of the vinyl group-containing ether (ii) in the copolymer of the fluoroolefin and the specific vinyl monomer is preferably from 1 to 45% by weight. 1
If it is less than 45% by weight, the curability of the durable water repellent of the present invention will be inferior. If it exceeds 45% by weight, gelation will easily occur and storage stability will be poor, and the resulting coating film will become brittle. More preferably 1 to 30% by weight, even more preferably,
5 to 15% by weight.

The (iii) vinyl group-containing ester is
CHR ²¹ ＣＨCHR ³¹ (wherein, R ²¹ represents a hydrogen atom or COOR ⁴¹ ; R ³¹
Represents COOR ⁴¹ or OCOR ⁴¹ . R ⁴¹ may be substituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. Represents a phenyl group. When R ³¹ is OCOR ⁴¹ , R ²¹ is a hydrogen atom. ). More specifically, a vinyl carboxylate represented by the formula; CH ₂ ＣＨCH (OCOR ⁴¹ ); a maleic acid diester or a fumaric acid diester represented by the formula: (R ⁴¹ OOC) CH ＝ CH (COOR ⁴¹ ); .

The vinyl carboxylate is not particularly restricted but includes, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate,
Vinyl stearate, vinyl benzoate, pt-butyl vinyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate, vinyl hexafluoropropionate,
Examples thereof include vinyl trichloroacetate. The maleic acid diester or fumaric acid diester is not particularly limited and includes, for example, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, diphenyl maleate, dibenzyl maleate, ditrityl maleate, ditrifluoro maleate. Methyl, ditrifluoroethyl maleate, dihexafluoropropyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate,
Examples thereof include diphenyl fumarate, dibenzyl fumarate, ditrityl fumarate, ditrifluoromethyl fumarate, ditrifluoroethyl fumarate, and dihexafluoropropyl fumarate. Of these, vinyl pivalate is preferred.

The content of the vinyl group-containing ester (iii) in the copolymer of the fluoroolefin and the specific vinyl monomer is preferably from 1 to 45% by weight.
If the amount is less than 1% by weight, the solubility and the compatibility are inferior, and the glass transition temperature is lowered. If the amount exceeds 45% by weight, the weather resistance is deteriorated. More preferably, it is 5 to 40% by weight, and further preferably, 10 to 30% by weight.

The carboxyl group-containing vinyl monomer described above as a specific vinyl monomer other than the above (i), (ii) and (iii) can be used for dispersing and curing the fluororesin (3) of the present invention. Improves reactivity, adhesion of the durable water repellent of the present invention to a substrate, and the like. Examples of the carboxyl group-containing vinyl monomer include those derived from crotonic acid, maleic acid, acrylic acid, methacrylic acid, itaconic acid, vinyl acetic acid, and the like. The ratio of the carboxyl group-containing vinyl monomer to the total vinyl monomer is 0.1%.
It is preferably from 0.01 to 10 mol%. If the amount is too small, the compatibility with the curing agent decreases, and if the amount is too large, the water resistance decreases.

As the vinyl monomer having a curing reaction site already described as a specific vinyl monomer other than the above (i), (ii) and (iii), the curing reaction site may be a hydroxyl group, an epoxy group or a silyl group. Is the base. Examples of the vinyl monomer whose curing reaction site is a hydroxyl group include the hydroxyalkyl vinyl ethers and hydroxyalkyl vinyl esters already described in the above section (ii). Examples of other vinyl monomers having a curing reaction site include, for example, JP-A-2-232250.
JP-A-2-232251, an epoxy group-containing vinyl monomer disclosed in JP-A-61-2417.
And a silyl group-containing vinyl monomer described in JP-A No. 13 and the like. Examples of the epoxy group-containing vinyl monomer include epoxy vinyl and epoxy vinyl ether represented by the following general formula.

[0080]

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Specific examples thereof include the following.

[0082]

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Specific examples of the above silyl group-containing vinyl monomer include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyldiethoxysilane, Vinyltris (β-methoxy) silane, trimethoxysilylethylvinylether, triethoxysilylethylvinylether, trimethoxysilylbutylvinylether, trimethoxysilylethylvinylether, trimethoxysilylpropylvinylether, triethoxysilylpropylvinylether, vinyltriisopropenyloxysilane , Vinylmethyldiisopropenyloxysilane, triisopropenyloxysilylethyl vinyl ether,
Triisopropenyloxysilylpropyl vinyl ether, triisopropenyloxysilylbutyl vinyl ether, vinyl tris (dimethyliminooxy) silane,
Vinyltris (methylethyliminooxy) silane, vinylmethylbis (methyldimethyliminooxy) silane, vinyldimethyl (dimethyliminooxy) silane,
Tris (dimethyliminooxy) silylethyl vinyl ether, methylbis (dimethyliminooxy) silylethyl vinyl ether, tris (dimethyliminooxy)
Silyl butyl vinyl ether, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ-
(Meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropyltriisopropenyloxysilane, γ- (meth) acryloyloxypropyltris (dimethyliminooxy) silane, γ- (meth) acryloyloxypropyltris ( Dimethyliminooxy) silane, allyltrimethoxysilane and the like.

The ratio of the above-mentioned vinyl monomer having a curing reaction site to all the vinyl monomers is not particularly limited.
~ 15 mol% is preferred. If the amount is too small, the curability becomes insufficient, and if the amount is too large, gelation easily occurs and storage stability deteriorates.

A copolymer of the above-mentioned fluoroolefin and a specific vinyl monomer can be prepared by polymerizing the above-mentioned monomer by a usual polymerization method. As such a polymerization method, for example, the method described in detail in the section of the polymerization method of the fluorine-containing resin constituting the seed particles in the section of the fluorine-containing resin aqueous dispersion (1-1) in which the acrylic resin is seed-polymerized. And the like.

The organic solvent is not particularly limited, but from the viewpoint of solubility, ketones or esters having a boiling point of about 60 to 250 ° C. are particularly preferable. For example, acetone, methyl ethyl ketone, methyl i-butyl ketone,
Examples thereof include cyclohexanone, ethyl acetate, n-butyl acetate, and methyl cellosolve acetate. These can be used alone or in combination of two or more. In addition to the above, examples of the organic solvent include tetrahydrofuran (THF), dimethylformamide (D
MF) and the like. Further, aromatic organic compounds such as toluene and xylene, alcohols, and the like may be added. These organic solvents can dissolve the above-mentioned organic solvent-soluble fluororesin well to obtain a composition in a wide concentration range from low to high, and have excellent gloss and weather resistance as a film-forming composition. It will be.

The acrylic resin to be mixed with the copolymer of the fluoroolefin and the specific vinyl monomer includes:
There is no particular limitation, for example, the above-mentioned fluorine-containing resin (1)
And the same as the acrylic resin described in detail in the section. The mixing amount of the acrylic resin mixed with the copolymer of the fluoroolefin and the specific vinyl monomer is preferably 5 to 80% by weight, particularly preferably 10 to 7% by weight.
0% by weight. If the mixing amount of the acrylic resin is too low,
The object of the present invention cannot be achieved because the dispersibility and adhesion of the entire composition are reduced, and when the mixing amount is too large, the weather resistance is deteriorated.

The mixing ratio when the copolymer of the fluoroolefin and the specific vinyl monomer and the acrylic resin are mixed with the organic solvent is not particularly limited. It is preferable to mix them so as to be about 90 to 90% by weight, preferably 20 to 80% by weight. The mixing method is not particularly limited, and a generally known method can be used.

The fluorine-containing resin (3) obtained by mixing the above-mentioned copolymer of a fluoroolefin and a specific vinyl monomer with an acrylic resin has the durability and the solvent resistance of the coating film formed by the coating composition. For the purpose of further improving the properties, a curing agent may be added, if desired. As detailed above,
The copolymer of the fluoroolefin and the specific vinyl monomer in the fluorine-containing resin (3) has (ii) a vinyl group-containing ether as a component thereof, and the copolymer always contains a hydroxyl group. It has a functional group that reacts with the curing agent. The curing agent is not particularly limited, and examples thereof include an isocyanate-based curing agent and a melamine-based curing agent.

The film-forming composition of the present invention is obtained by mixing the above-mentioned main resin with a repellent and a surface roughness regulator. The repellent is described in detail below.

The repellent is not particularly limited as long as it has a water / oil repellent effect. Preferably, at least one of a fluorine-based repellent, a silicone-based repellent, and a hydrocarbon-based repellent is used. Select The fluorine-based repellent and silicone-based repellent are not particularly limited, but are preferably selected from the following.

(I) Fluorine-based surfactant (II) Fluorine-based oil (III) Polymer having perfluoroalkyl group (IV) Fluorosilicone oil (V) Silicone oil Are described in International Publication WO 95/18188.

(I) Fluorinated Surfactant The fluorinated surfactant used in the present invention is a surfactant having a perfluoroalkyl group or a surfactant having a perfluoroalkylene group. Surfactants, cationic fluorine-based surfactants, amphoteric fluorine-based surfactants, and nonionic fluorine-based surfactants. More specifically, Unidyne DS-101 (manufactured by Daikin Industries, Ltd.), Unidyne DS
-202 (manufactured by Daikin Industries, Ltd.), Unidyne DS-30
1 (manufactured by Daikin Industries, Ltd.) and Unidyne DS-406 (manufactured by Daikin Industries, Ltd.).

(II) Fluorinated Oil As the fluorinated oil used in the present invention, a polymer of perfluoropolyether or chlorotrifluoroethylene, or other specific fluorinated hydrocarbon compounds can be exemplified. More specifically, Demnum S-20 (manufactured by Daikin Industries, Ltd.) and Daifoil # 20 (manufactured by Daikin Industries, Ltd.) can be exemplified.

(III) Polymer Having a Perfluoroalkyl Group The polymer having a perfluoroalkyl group used in the present invention is specifically a polymer of a perfluoroalkyl group-containing ethylenically unsaturated monomer. Alternatively, the main component is a copolymer of a perfluoroalkyl group-containing ethylenically unsaturated monomer and a monomer copolymerizable therewith. More specifically, Unidyne TG652 (made by Daikin Industries), Unidyne TG664 (made by Daikin Industries), Unidyne TG410 (made by Daikin Industries) and the like can be mentioned.

(IV) Fluorosilicone Oil The fluorosilicone oil used in the present invention contains a fluoroalkyl group on the side chain or terminal of polysiloxane. More specifically, FS-1265 (manufactured by Dow Corning Toray Silicone Co., Ltd.), X-22-8
19 (manufactured by Shin-Etsu Chemical Co., Ltd.) and FL100 (manufactured by Shin-Etsu Chemical Co., Ltd.).

(V) Silicone Oil The silicone oil used in the present invention is 25 ° C.
And a silicone oil having a reactive group in a side chain or a terminal. More specifically, dimethyl silicone oil, methyl chloride silicone oil, methyl phenyl silicone oil, organically modified silicone oil and the like can be mentioned, for example, PRX413 (manufactured by Dow Corning Toray Silicone Co., Ltd.), SF8417 (same as above), SF8418
(Same as above), BY16-855B (same as above), SF8427
(Same as above), SF8428 (Same as above), X-22-161C (Shin-Etsu Chemical Co., Ltd.), KF-857 (Same as above), KP-358
(The same), KP-359 (the same) and the like.

Examples of the hydrocarbon-based repellent used in the present invention include waxes, oils and fats, and waxes. More specifically, for example, Quinproof W-10 (a white emulsion manufactured by Kotani Chemical Co., Ltd.) Quinproof W-3 (Kotani Chemical Co., white paste type repellent), Quinproof WE (Kotani Chemical Co., white paste type repellent), WAX-P (Kotani Chemical Co., white liquid) WAX-S (manufactured by Kotani Chemical Co., Ltd., white liquid type saturated higher fatty acid-based emulsion repellent), WAX-C (manufactured by Kotani Chemical Co., light brown liquid type high boiling wax-based emulsion repellent), raster ( Examples thereof include an oil / fat-derived water-soluble oil repellent manufactured by Kotani Chemical Co., Ltd., ISTPE (a self-emulsifying polyethylene emulsion-based repellent manufactured by Kotani Chemical Co., Ltd.), and natural wax.

The repellent is preferably mixed in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the solid content of the main resin.
If it is less than 0.1, sufficient water / oil repellency cannot be obtained, and if it exceeds 20 parts by weight, the compatibility will be poor.
More preferably, it is 0.5 to 10 parts by weight. The film-forming composition of the present invention is obtained by mixing a repellent and a surface roughness adjuster with the above main resin. The surface roughness adjuster will be described in detail below.

The surface roughness adjusting agent is not particularly limited as long as it can adjust the surface roughness when the main resin forms a coating film to improve the effect of preventing snow and ice formation. However, preferred examples include fluoroolefin polymers, fluorinated graphite, silicon dioxide compounds, graphite and potassium titanate. The above-mentioned fluoroolefin polymer, in order to fulfill the function as a surface roughness regulator, is different from the fluoroolefin polymer constituting the main resin, and can be dissolved in an aqueous medium or an organic solvent which is a solvent of the main resin. And has the property of not dissolving when heated to form a coating film.

The fluoroolefin polymer includes:
For example, polyflon TFE (manufactured by Daikin Industries, Ltd.) which is PTFE having a heat resistance of 260 ° C., Rubron (manufactured by Daikin Industries, Ltd.) which is a low molecular weight PTFE having a heat resistance of 260 ° C., TFE having a heat resistance of 260 ° C. / Neoflon PFA which is a perfluorovinyl ether copolymer
(Manufactured by Daikin Industries, Ltd.), TF having heat resistance of 200 ° C.
NEOFLON FEP (manufactured by Daikin Industries, Ltd.) as an E / HFP copolymer, TFE / ethylene copolymer NEOFRON ETFE (manufactured by Daikin Industries) having a heat resistance of 150 ° C., and PVdF having a heat resistance of 150 ° C. Certain NEOFLON VDF (manufactured by Daikin Industries, Ltd.) and NEOFLON CTFE (manufactured by Daikin Industries, Ltd.), which is a CTFE having a heat resistance of 150 ° C., can be exemplified.

The above-mentioned surface roughness adjuster was prepared by adding
It is preferable to mix 20 to 300 parts by weight with respect to 0 parts by weight. If the amount is less than 20 parts by weight, the surface roughness becomes insufficient, and a sufficient effect of preventing snow and icing cannot be obtained. If the amount exceeds 300 parts by weight, the coating film forming property of the composition becomes insufficient. It becomes extremely brittle. More preferably, 50 to
200 parts by weight.

In preparing the film-forming composition of the present invention, in addition to the above, it is possible to further incorporate additives as appropriate. Such additives are not particularly limited,
For example, pigments, viscosity modifiers, leveling agents, ultraviolet absorbers, anti-skin agents, dispersants, defoamers, known additives and the like commonly used in paints such as curing accelerators, and the like, The amounts of these additives are not particularly limited, and ordinary amounts can be employed.

In preparing the film-forming composition of the present invention, it is important to adjust the contact angle with respect to water. The method for measuring the contact angle with water will be described in detail in the following Examples.
For example, when the contact angle of water of the main resin of the present invention is 70 ° or more, when the film-forming composition of the present invention is formed by adding a repellent and a surface roughness regulator to the main resin of the present invention. It has been found that the effect of preventing snow and icing is further improved. Further, when the contact angle with water of the composition when the repellent was added to the main resin of the present invention was 90 ° or more, a surface roughness regulator was further added to constitute the film-forming composition of the present invention. It has been found that the effect of preventing snow and icing at the time is even better. Still further, when the contact angle with water of the film-forming composition of the present invention obtained by adding the repellent and the surface roughness adjusting agent to the main resin of the present invention is 150 ° or more, the film-forming composition of the present invention is constituted. It has been found that the effect of preventing snow and icing in the event of snowfall is extremely excellent.

The film-forming composition of the present invention is a novel composition which has not been described in the literature in view of its constitution. Can be applied as anti-icing paint. There is no particular limitation on the application location of such a snow and icing prevention paint, for example, a roof of a building such as a house, a building, or a gymnasium;
Roofs of vehicles such as passenger cars, buses and ships can be mentioned. The method for applying the snow / ice accretion preventive paint of the present invention is not particularly limited. A coating film may be formed. These are mainly cold regions such as Hokkaido and the Tohoku region, Northern Europe,
It is suitable for use in cold regions such as North America.

The mechanism by which the film-forming composition and the snow- and ice-preventing paint of the present invention exhibit an extremely excellent effect of preventing snow and icing is not always clear, but the conventional snow- and ice-preventing paint is simply water- and water-repellent. Because oil properties and surface roughness were taken into account and the continuity of the effect was not considered, no consideration was given to degradation phenomena in which the coating film peels off due to use over time, peels off the coating film, and cracks the coating film. However, the film-forming composition of the present invention is provided with selectivity in the dispersibility of the surface roughness regulator contained therein, thereby improving the adhesion to the base metal or plastic and improving the peeling and the like. This is because cracks are no longer generated, and the acrylic resin contained in the film-forming composition of the present invention does not decrease the effect of preventing snow and icing over time to give reproducibility during coating. It is assumed that It can be.

[0107]

The present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.

Preparation of Main Resin 1500 g of water and 3 g of Unidyne DS-101 (manufactured by Daikin Industries, Ltd.) were placed in an autoclave of 3 L of main resin A, and the mixture was degassed and purged with nitrogen.
3/14/13 (mol%) mixed monomer was charged, and 39
The pressure was increased to 20 kg / cm ² G at ℃. Under stirring, 3.5 g of diisopropyl peroxycarbonate was added to initiate polymerization. Polymerization was carried out for 8 hours while continuously supplying the mixed monomer so that the polymerization pressure became 20 kg / cm ² G. The obtained dispersion was freeze-thinned, washed with water to remove the emulsifier, and dried at 80 ° C. under reduced pressure to obtain 270.
g of the copolymer was obtained. As a result of elemental analysis, this copolymer was found to have VdF / TFE / CTFE of 74/14 /
12, melting point (Tm): 108 ° C., [η] = 0.69
0 (DMF, 35 ° C.).

Main resin B In a 100 mL stainless steel autoclave, 250 g of butyl acetate, 32.4 g of vinyl pivalate (VPi) and 29.4 g of hydroxybutyl vinyl ether (HBVE) were used.
g, 36.9 g of vinyl benzoate (VBz), and 2,
2'-azobis (2,4-dimethylvaleronitrile)
After charging 6.0 g, the mixture was cooled to 0 ° C with ice, and then degassed under reduced pressure. 28.3 g of isobutylene (IB) and TF
9. E122 g was charged and heated to 50 ° C. with stirring.
Reaction was performed for 0 hours, and the reactor internal pressure was 17.5 kg / cm ² G
The reaction was stopped at the time when the pressure decreased from 9.5 kg / cm ² G to 9.5 kg / cm ² G (polymerization yield: 60.4% by weight). When the obtained fluorinated copolymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR and elemental analysis, 44 mol% of TFE, 34 mol% of IB,
It is a copolymer composed of 15 mol% of VPi, 9 mol% of HBVE and 1 mol% of VBz. The number average molecular weight (Mn) measured by GPC is 3.4 × 10 ⁴ , and the glass transition temperature (Tg) measured by DSC is: 24.5 ° C.

In a pressure-resistant reaction vessel equipped with a stirrer having a capacity of 1 L in the main resin C , deionized water 50
0 mL and 5.0 g of reactive emulsifier were charged, nitrogen gas injection and degassing were repeated to remove dissolved air, and then Vd
F73 mol%, TFE14 mol%, CTFE13 mol%
At 60 ° C. and the internal pressure of the vessel is 10 kgf /
Press-fit until cm ² . Thereafter, 0.2 g of ammonium persulfate was charged, and the internal pressure of the container was reduced to 10 kgf / cm ^2.
After the above-mentioned mixed monomer was continuously supplied so as to be constant and polymerization was carried out for 20 hours, the inside of the vessel was returned to normal temperature and normal pressure, and the polymerization was terminated to obtain an aqueous copolymer dispersion. As a result of elemental analysis, VdF / TFE / CTFE = 74/14/1
It was found that 2 (mol%) of the copolymer was obtained.

Acrylic resin As the acrylic resin, methyl methacrylate / ethyl methacrylate / n-butyl methacrylate = 63/30/7
(Mol%) was used. However, in the case of Examples 11 and 12, methyl methacrylate /
Ethyl methacrylate / isobutyl methacrylate / 2-hydroxyethyl methacrylate = 25/6/55/14
(Mol%), and furthermore, duranate THA100 (manufactured by Asahi Kasei Corporation) as a curing agent, and a molar ratio of isocyanate groups of the curing agent to hydroxyl groups contained in the main resin B and the acrylic resin is 1: 1: The one added in such an amount as to be 1 was used.

The repellent “Demnum” represents a perfluoropolyether oil (manufactured by Daikin Industries, Ltd.). "TG-652" represents Unidyne TG-652 (manufactured by Daikin Industries, Ltd.), which is a perfluoroalkyl group-containing acrylate repellent. "TG-4
"10" represents Unidyne TG-410 (same as above). "R
f-silane ”is KB which is a perfluoroalkylsilane
M7803 (manufactured by Shin-Etsu Silicone Co., Ltd.). "KP-3
"59" represents KP-359 (manufactured by Shin-Etsu Silicone Co., Ltd.) which is a silicone oil. The surface roughness adjuster “FEP” represents NEOFLON FEP NP-12X (manufactured by Daikin Industries, Ltd.), which is a TFE / HFP copolymer.
“Sirophobic 704” indicates silophobic 704 (manufactured by Fuji Silycin Chemical Co., Ltd.), which is colloidal silica.

The main resins, acrylic resins, repellents, and surface roughness modifiers shown in Tables 1, 2, and 3 are expressed in parts by weight (provided that the main resins and acrylic resins are shown in Tables 1, 2, and 3). Are parts by weight of the solid content). Butyl acetate was used as a diluting solvent for the main resin A and the main resin B and the acrylic resin. The main resin C and the acrylic resin were diluted with tap water, and diethyl adipate was used as a film-forming aid in an amount of 15% by weight based on the total weight of the resin. Adecanol UH-4 was used as a thickener.
20 was added in an amount of 0.4% by weight based on the total amount of the resin. Spray painting was carried out by WIDER88 manufactured by Iwata Coating Machine Industry Co., Ltd. or hand painting was carried out using a brush. As the target substrate A, JIS H 4000 (A1050P), AM7
12 treated aluminum substrate (manufactured by Nippon Test Panel Co., Ltd.)
Was used. As the target substrate B, Acridic A-801 (manufactured by Dainippon Ink and Chemicals, Inc.)
/ Duranate THA100 (made by Asahi Kasei Corporation) (OH
/ NCO = 1/1). Dilution viscosity at spray coating 4 Ford Cup 13 seconds / 20
° C and the dilution viscosity No. at the time of brush painting. 4 Ford cup 40 seconds / 20 ° C.

Using the film-forming composition prepared as described above, an object coated on a target substrate was subjected to a thermal-cooling cycle test. The test was repeated several times. Thereafter, the performance was evaluated by the following evaluation method. Tables 1 and 2 show the results.
And Table 3.

In Iwate Prefecture in the Tohoku region, January 1
An exposure test was performed for a total of 30 days from 6 to 14 February, and evaluated according to the following evaluation criteria. The results are shown in Tables 1, 2 and 3. ○: Snow area was less than 1/5 △: Snow area was 1/5 to 3/5 ×: Snow area was more than 3/5 After exposing the ice, 5 ℃ × 5
After cooling for 20 minutes at −20 ° C. × 60 minutes, the coated plate was inclined at 30 ° in an environment of 5 ° C., and the falling time (seconds) of ice on the surface was measured. The results are shown in Tables 1, 2 and 3.

Evaluation of Adhesion The adhesion was evaluated at a clearance of 1 mm in accordance with JIS K 5400, cross cut method. Measurement of contact angle with water The measurement was performed by the droplet method. A CA-DT type measuring device manufactured by Kyowa Interface Science Co., Ltd. was used. Measurement of icing power The substrate was allowed to stand on a stainless steel flat plate, and a coating film to be inspected was formed on the surface thereof. A cloth soaked in distilled water was placed on the substrate on which the coating film was formed, and distilled water was further dropped from the cloth with a dropper. This was cooled at −20 ° C. × 24 hours, and the distilled water was frozen. Thereafter, while pulling the edge of the cloth with a tension gauge, the tension (g / cm ² ) when the cloth was peeled off from the coating film was measured.

[0117]

[Table 1]

[0118]

[Table 2]

[0119]

[Table 3]

[0120]

Since the film-forming composition of the present invention has the above-mentioned constitution, it has a sufficient snow- and ice-preventing effect, and it can be maintained for a long time without changing over time. Because it can be used, it is extremely useful as a snow and icing prevention paint.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Katsuhiko Imoto, Inventor 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Keiko Kunimasa 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries Inside Yodogawa Works (72) Inventor Akira Senda 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works

Claims (5)

[Claims] 1. A film-forming composition comprising a main resin mixed with a repellent and a surface roughness adjuster, wherein the main resin is a fluorine-containing resin comprising a fluorine-based resin and an acrylic resin. A film-forming composition having excellent anti-icing and anti-icing properties. 2. The repellent is added to 100 parts by weight of the main resin.
The film-forming composition according to claim 1, wherein 1 to 20 parts by weight and 20 to 300 parts by weight of a surface roughness regulator are mixed. 3. The film-forming composition according to claim 1, wherein the repellent is at least one of a fluorine-based repellent, a silicone-based repellent, and a hydrocarbon-based repellent. 4. The surface roughness regulator is a fluoroolefin polymer, fluorinated graphite, a silicon dioxide compound, graphite or potassium titanate.
A film-forming composition as described in the above. 5. An anti-icing / icing coating comprising the coating composition according to claim 1, 2, 3 or 4.