KR100700903B1 - Crosslinkable aqueous fluoropolymer based dispersions - Google Patents

Abstract

The present invention relates to vinylidene fluoride polymer-based acrylic modified fluoropolymers in which the acrylic phase can crosslink. The final cured product provides better solvent extraction resistance on the fluoropolymer.

Acrylic modified fluoropolymers, vinylidene fluoride polymers, hexafluoropropylene, solvent extraction resistance, latex, curable compositions, crosslinks

Description

Crosslinkable aqueous fluoropolymer based dispersions

This application claims priority to US Provisional Application No. 60 / 143,663, filed July 14, 1999.

The present invention relates to residues derived from monomers copolymerizable with fluoropolymers, more particularly vinylidene fluoride (VDF) -based fluoropolymers, more particularly polyvinylidene fluoride (PVDF) -based polymers, even more particularly VDF. PVDF homopolymers and PVDF based polymers, in particular residues derived from hexafluoropropylene (HEP) or PVDF / HFP copolymers, more particularly PVDF based polymer particles, in particular PVDF homopolymers and / or PVDF / HFP Copolymer particles are used as seeds for polymerizing acrylic polymers from acrylic monomers and monomers capable of copolymerizing with acrylic monomers to form polymers referred to as "AMF polymers", more particularly crosslinking Other functionality of the acrylic moiety of the other AMF polymer in the presence or absence of a separate crosslinking aid to form AMF polymers comprising functional groups of acrylic moieties capable of reacting with groups, methods of making and uses of the polymers thereof, compositions comprising uncrosslinked polymers and compositions and products comprising crosslinked polymers .

Vehicles that have been commercially successful for many years, such as paints, films, and the like to form VDF homo- and copolymeric coatings for substrates, have incorporated acrylic polymer fractions contained for use in attaching coatings to substrates and wetting and bonding pigments. It is based.

VDF polymers or copolymers and acrylic polymers are prepared separately by known techniques or by simply mixing the pigments with any other components to form the composition used to form the coating.

Recently, for PVDF homopolymers and copolymer coatings, attempts have been made to prepare AMF polymers on the basis of various advantages that can be realized in the above method.

It is also well known in the literature that thermoset acrylics increase solvent and wear resistance as well as physical and mechanical properties for acrylic polymers as compared to corresponding non-thermoset acrylics. Thermosetting can be accomplished in a number of ways, such as Diels Alder addition, self-oxidation, free radical coupling, condensation and transesterification. Phase separation of the immiscible polymer can also be reduced through internal crosslinking.

U. S. Patent No. 5,349, 003 describes an aqueous dispersion of vinylidene fluoride-based polymers used as seeds in the synthesis of acrylic polymers for preparing aqueous dispersions of AMF polymers.

PVDF polymers are homopolymers or ethylenically unsaturated compounds containing other fluorides such as trifluorochloroethylene (CTFE), tetrafluoroethylene (TFE), HFP, vinyl fluoride (VF), hexafluoroisobutyl Ethylene perfluoroacrylic acid], ethylenically unsaturated compounds containing no fluorine (e.g. cyclohexylvinyl ether, hydroxyethylvinyl ether) or diene compounds containing no fluorine (e.g. butadiene, isoprene and chloroprene) with VDF It may be a copolymer. Preference is given to VDF homopolymers, VDF / TFE copolymers and VDF / TFE / HFP copolymers.

Many acrylic type monomers and monomers copolymerizable with acrylic type monomers are described for polymerization in the presence of fluoropolymer seeds. Possible monomers include those having a plurality of functional groups capable of crosslinking with similar groups in other polymeric molecules by reaction with groups or monomeric crosslinkers which can react with other polymeric molecules. This material was not actually manufactured. It has been suggested from the actual produced molecules that there is no difference in the properties for such crosslinkable AMF molecules, and it is excellent to be found by the inventors to include acrylic monomers containing crosslinkable functional groups in the preparation of AMF. It is not shown to provide AMF polymers with application properties.

Japanese Patent Application Laid-Open No. 4 (1992) -325509 mentions that AMF polymers containing carboxyl functional groups in the acrylic moiety provide improved water dispersibility in alkaline solutions. The fluoropolymer seed may be a poly (vinylidene-fluoride) homopolymer or copolymer. For crosslinked AMF polymers, the advantages of the advantageous application properties found by the inventors have not been proposed.

U.S. Patent 5,646,201 describes copolymerized AMF polymers of vinylidene fluoride and chlorotrifluoroethylene for use in waterborne paints. The third comonomer may be present in the VDF based copolymer. CTFE must be present to obtain the gloss and flexibility required for paint coatings. The acrylic phase may comprise monomeric residues comprising crosslinkable functional groups. Such AMF was not actually produced, and the benefits found by the inventors for the crosslinked AMF composition have not been described or suggested.

Japanese Patent Application Laid-Open No. 8 (1996) -170045 discloses that the fluoropolymer seed may be a vinylidene fluoride-hexafluoropropylene copolymerization system, and the acrylic phase may include a monomer having a crosslinkable functional group. Aqueous coatings for AMF polymer-based inorganic binding materials are described. Crosslinkable AMF polymers were not actually produced and the benefits found by the inventors for the crosslinked coatings were not proposed.

Japanese Patent Application Laid-Open No. 8 (1996) -259773 is similar to the last document described above, but in order to improve the adhesion of the coating film, it is necessary to incorporate a monomer having a cyclohexyl group on the acrylic. In other words, crosslinkers on acrylic have not been described or suggested and no hint is made of the unique properties of the crosslinked films found by the inventors.

Japanese Patent Laid-Open No. 9 (1997) -165490 describes crosslinked AMF-based coatings in which crosslinking is carried out by reaction of polyfunctional hydrazines with reactive carbonyl groups on acrylics. The document clearly mentions that chlorotrifluoroethylene and vinylidene fluoride should be the predominant monomers on the fluoropolymer, a practical example of which is only described for the AMF polymer type. The advantages found by the inventors with respect to the compositions claimed by them are not proposed.

WO 96 / 06887A1 describes a stable aqueous dispersion of AMF polymers based on vinylidene fluoride monomers, reactive emulsifiers and vinylidene fluoride copolymers as seeds.

Aqueous dispersions of both polymer types are described as very stable. Crosslinking of the coatings from both polymer types was not discussed, nor were the properties found by the inventors of such crosslinked coatings.

The present invention is directed to a first composition embodiment, comprising a vinylidene fluoride polymer-based acrylic modified fluoropolymer selected from vinylidene fluoride homopolymer and vinylidene fluoride-hexafluoropropylene copolymer group.
Crosslinking the acrylic moiety provides a vinylidene fluoride polymer based acrylic modified fluoropolymer comprising monomer residues having functional groups to which the acrylic part of the polymer can react and wherein the functional groups do not comprise carboxylic acid groups alone. do.

An effective embodiment of the first composition of the invention is a white or light solid with physical and chemical properties that facilitate the identification of the molecular structure imparted herein.

The above chemical and physical properties, together with standard analytical techniques and synthesis methods, such as kinetic analysis, infrared and nuclear magnetic resonance spectroscopy, and differential scanning calorimetry, further confirm the above structures for the first composition embodiments of the present invention. do.

An effective embodiment of the first composition embodiment of the present invention is included in solvent-based or water-based paints and varnish vehicles as pigment binders in powder coating formulations for forming crosslinked coatings and films that are excellent in luster and weathering, solvents, abrasion, and the like. It has unique use characteristics that make it suitable for use. The crosslinked coating can withstand solvent attack on the acrylic phase as well as surprisingly solvent attack on the fluoropolymer phase.

In an aspect of the second composition, the present invention provides a polyvinylidene fluoride polymer-based acrylic modified fluoropolymer selected from the group consisting of polyvinylidene fluoride homopolymer and polyvinylidene fluoride hexafluoropropylene copolymer and at least one A curable composition comprising a crosslinking catalyst, wherein the acrylic phase contains a monomer moiety having a functional group that reacts to allow the acrylic phase to crosslink, and wherein the acrylic moiety is not comprised solely of carboxylic acid groups.

An effective embodiment of the second composition aspect of the present invention has inherent use properties that result in improved resistance to extraction by solvents on fluoropolymers to form cured films and coatings that have improved weather resistance, abrasion resistance and chemical resistance in use.

In an aspect of the third composition, the present invention includes a polyvinylidene fluoride polymer-based acrylic modified fluoropolymer selected from the group consisting of polyvinylidene fluoride homopolymer and polyvinylidene fluoride-hexafluoropropylene copolymer. A cured composition produced from a curable composition is provided, wherein the composition has a functional group that enables the acrylic phase to crosslink and contains a monomer moiety that crosslinks reacts.

The blind embodiment of the third composition aspect of the present invention has inherent physical properties of hardness, gloss and wear resistance. They also have good weather resistance and solvent resistance, and the fluoropolymer portion of the third composition embodiment of the present invention extracts fluoropolymer residues from acrylic modified fluoropolymer coatings, films and the like when the acrylic portion is not crosslinked. High resistance to extraction by solvents known to be known.

Thus, an effective embodiment of the third composition embodiment has inherent use properties to form coatings and films having gloss, hardness, wear resistance, weather resistance and good solvent resistance.

In a fourth composition embodiment, the present invention provides a three-dimensional object having a coating on at least one surface comprising the third composition of the invention.

In a fifth composition, the present invention relates to a copolymer of vinylidene fluoride and a mixture of two or more of chlorotrifluoroethylene, vinyl fluoride, tetrafluoroethylene and chlorotrifluoroethylene, vinyl fluoride and tetrafluoroethylene Based on vinylidene fluoride copolymers selected from the group consisting of, copolymers of vinylidene fluoride and chlorotrifluoroethylene, vinyl fluoride and / or tetrafluoroethylene, hexafluoropropylene may be included as comonomers And the acrylic portion of the polymer contains monomer residues having functional groups that can be reacted to crosslink the acrylic portion, and the functional group does not comprise a carboxylic acid group.

An effective aspect of the fifth composition aspect of the present invention provides the same unexpected results for solvent attack on the fluoropolymer while having the same inherent and use properties as the effective aspect of the first composition of the invention.

The preparation and use methods of aspects of the present invention will now be described with reference to specific embodiments thereof. In other words, ASTM D using a 15: 1 L / D capillary with a vinylidene fluoride content of 85.8% by weight, a hexafluoropropylene content of 14.2% by weight, and a melt viscosity at 232 ° C. of 23kp (conical inlet angle of 120 °) ^. 3835) 100s- ¹ Phosphorus vinylidene fluoride-hexafluoropropylene copolymer seed (vinylidene fluoride-hexafluoropropylene copolymer) is present in a weight ratio of 70:30 relative to the total acrylic solids. Describes an acrylic modified fluoropolymer prepared by using as a seed latex upon polymerization of a mixture of acrylic monomers comprising methyl methacrylate, ethyl acrylate and glycidyl methacrylate in a weight ratio of 18: 9: 5. something to do.

Vinylidene fluoride, hexafluoropropylene copolymer latexes used as starting materials in the practice of the present invention may be prepared by methods similar to those of US Pat. No. 3,178,399. Synthesis is controlled so that the final particle size is less than 350 nm on average by known techniques using suitable amounts of surfactant and / or water to monomer to provide particles in latex with an average size of less than 250 nm, preferably less than 150 nm. .

The vinylidene fluoride-hexafluoropropylene copolymer latex can be free radical initiator such as ammonium persulfate, and sodium lauryl sulfate, methyl methacrylate (18 parts by weight), ethyl acrylate (9 parts by weight) and glycidyl meta Mixed with a surfactant such as a portion of a mixture of acrylates (5 parts by weight), the preparation is carried out in a suitable size reaction vessel equipped with a suitable stirring device, a feed inlet for the addition of reactants, a suitable reflux concentrator and an inlet for an inert blanking gas. After filling, isooctylmecaptopropionate (about 1 part by weight) is added and stirred at a speed that is sufficient but not enough to cause condensation of the latex emulsion, conveniently at a speed of about 90 rpm. The reactor and its contents are purged with an inert gas, conveniently argon, for a time sufficient to remove air, conveniently for about 30 minutes, during the soaking / purging period. At the end of purging, the temperature of the reactor and its contents rises to about 70 ° C. and the reaction time is measured from the start of the heating period. The reaction is continued for a period of time, conveniently for about 1 hour, and then with the aid of a wash pump, at a rate sufficient to maintain the remaining monomer mixture but not exceeding the heat exchange capacity of the reflux concentrator. Take it and supply it. After all monomer mixtures have been added, the reaction is continued with stirring while maintaining the reaction at 70 ° C. for an additional time, conveniently about 120 minutes, to consume the unreacted monomers. The reactor is then cooled to ambient temperature, about 20 ° C. and the latex contained in the reactor is discharge filtered through a loose cotton cloth.

The preferred pH of the filtered latex is then adjusted to any desired convenient value (eg to pH 8 using ammonia water) using a known pH adjusting agent. If desired, the resin can be separated by condensing the latex, separating it from the remaining liquid and then washing the resulting solid with water. After drying, the solid is generally in finely divided form.

One skilled in the art, in addition to certain vinylidene fluoride-hexafluoropropylene polymer latexes specifically exemplified as starting materials, the present invention provides other known vinylidene fluoride hexafluoropropylene copolymers as equivalents thereof. US Pat. No. 5,093,427 and PCT Application WO 98/38242] and vinylidene fluoride homopolymers (US Pat. Nos. 3,475,396 and 3,857,827), which can be substituted as seed polymers in the reactions described above. I will understand.

The present invention also includes vinyl fluoride polymers of the type described in PCT applications WO 98/46657 and WO 98/46658 as suitable seed polymers.

Those skilled in the art, in addition to the specifically exemplified ethyl acrylate, methyl methacrylate and glycidyl methacrylate, are known ethylenically unsaturated monomers known to be copolymerizable to any known acrylic monomer and acrylic monomer, It will also be appreciated that as long as it contains a functional group capable of initiating the crosslinking reaction, it can be substituted. Suitable acrylic, methacrylic and other copolymerizable monomers can be selected from the following, provided that the majority of the monomers should be selected from acrylic esters and methacrylic esters and that at least one of the remaining selected monomers can be crosslinked. : Ethyl acrylate, methyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, ethyl methacrylate (EMA), methyl methacrylate, butyl methacrylate, propyl methacrylate Isobutyl methacrylate, amyl methacrylate, 2-ethyl hexyl methacrylate; Among the above groups, ethyl acrylate, methyl acrylate, butyl acrylate and methyl methacrylate are preferred; α, β-unsaturated carboxylic acid (acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid), vinyl ester compound, amide compound (acrylamide, methacrylamide, N-alkyl methacrylamide, N- dialkyl methacryl) Amides, N-dialkyl acrylamides), hydroxyl group-containing ethylenically unsaturated monomers (e.g., hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, Diethylene glycol ethyl ether acrylate), silanol-containing monomers (e.g. γ trimethoxysilane methacrylate, γ triethoxysilane methacrylate), aldehyde functional group-containing monomers such as acrolein, acrylonitrile methacryl Alkenyl cyanide, such as ronitrile.

Conjugated dienes (e.g. 1,3-butadiene, isoprene, fluoro alkyl acrylates, fluoroalkyl methacrylates), aromatic alkenyl compounds (e.g. styrene, α-methylstyrene, styrene halides) and divinyl hydrocarbon compounds ( Some nonfunctional monomers, such as divinyl benzene) may also be incorporated.

If desired, small amounts of copolymerizable low molecular weight polymers or oligomers known as reactive emulsifiers may also be included. Monomers containing one or more ethylenically unsaturated functional groups can be used to form crosslinked modified fluororesin particles. Preferably they will be used in an amount of less than 5% by weight of the monomer mixture. Typical examples of suitable monomers of this type are ethylene glycol dimethacrylate and diethylene glycol dimethacrylate.

The acrylate and / or methacrylate monomers that do not contain functional groups capable of crosslinking reaction after polymerization should preferably be at least 70% by weight of the total monomer mixture, more preferably greater than 90% by weight. At lower rates, miscibility with the fluoropolymer seeds may be reduced and the transparency of the final coating or other molding may be poor. Similarly, one of ordinary skill in the art will be able to control the relative amounts of acrylic and methacrylic esters in the monomer mixture by a series of bench scale tests, based on the known properties provided for each type of monomer, to each monomer. It will be possible to achieve a desirable balance between the properties provided by.

The total amount of copolymerizable monomers containing functional groups capable of crosslinking reaction may be used in an amount of about 0.01 to 10 parts by weight, preferably about 0.01 to about 5 parts by weight based on 100 parts by weight of the total monomers.

The total amount of monomer mixture used may be about 10 to about 200 parts by weight, preferably about 20 to about 80 parts by weight, based on 100 parts by weight of the fluoropolymer seed.

Although the amount of the monomer mixture may be used more or less than a predetermined range, properties such as adhesion to the substrate, wettability of the pigment and weather resistance may be affected and become poor.

As mentioned above, the seed polymerization can be carried out under the same conditions as are commonly used in conventional emulsion polymerization of acrylics and similar monomers. Surfactants, polymerization initiators, chain transfer agents and pH adjusting agents and optional solvents and chelating agents are mixed with the seed latex, followed by purification to remove molecular oxygen, followed by about 20 to about 90 at atmospheric pressure under an inert atmosphere. The reaction is carried out for 0.5 to 6 hours at a temperature of about 40 to about 80 ℃.

The reaction itself can be carried out according to the type of reaction according to any of the standard techniques known in the art, using the fluoropolymer as the seed, for example in batch polymerization the entire monomer mixture is fluoro at the beginning of the reaction. To the polymer dispersion, in the semi-continuous polymerization part of the monomer mixture is added at the beginning of the reaction and then the remainder is fed continuously or batchwise during the reaction, in the continuous polymerization the monomer mixture is fed or reacted continuously. It is supplied batchwise throughout the process.                     

In addition, the emulsion polymerization may be carried out in one or more steps. Where a multistage approach is employed, each step contains the same monomers, surfactants, polymerization initiators, chain transfer agents, pH adjusters, optional solvents and optional chelating agents as already mentioned in the one-step process, or one or more components Depending on the desired shape of the final particles of the latex formed during this reaction, the state can be altered based on principles known in the art. The final latex particles may consist of single, double or more phases with various geometries in addition to the innermost fluoropolymer phase, such as homogeneous particles, core-shells, incomplete cores of such phase geometries. Same as shell, inverted core-shell, half moon, strawberry, internally penetrating mesh. Such geometric shapes and shapes are well known in the art for making them. While certain geometric shapes and / or shapes are not considered important factors to limit the invention, the preferred shape is the homogeneous particle form.

It is not clear how the fluoropolymer phase and the acrylic and any other monomer phases are arranged in the final particles, but it is believed that the monomer mixture is almost absorbed or absorbed by the fluoropolymer particles and polymerized while swelling the particles.

As emulsifiers, anionic emulsifiers, nonionic emulsifiers or mixtures thereof can be used. In some cases, amphoteric or cationic surfactants can be used. As the anionic surfactant, for example, sodium salts of sulfuric acid esters of higher alcohols, sodium alkyl benzene sulfonates, sodium salts of dialkyl succinate succinic acid and sodium salts of alkyldiphenylether sulfonic acids can be used. Among them, sodium alkyl benzene sulfonate, sodium lauryl sulfate, polyoxyethylene alkyl (or alkyl phenyl) ether sulfonate and the like are preferred. As the nonionic emulsifier, for example, polyoxyethylene alkyl ether and polyoxyethylene alkyl aryl ether can be used. Polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, etc. are preferable. Amphoteric emulsifier lauryl betaine and the like are suitable. As the cationic surfactant, for example, alkyl ferridinium chloride, alkyl ammonium chloride or the like can be used. In addition, emulsifiers copolymerizable with monomers such as sodium styrene sulfonate, sodium alkyl aryl sulfonate and the like can be used.

The amount of surfactant or emulsifier used is generally from about 0.05 to about 5 parts by weight per 100 parts by weight of the total amount of vinylidene fluoride polymer particles and monomer mixture.

As polymerization initiator, optionally known water and oil-soluble free radical sources for initiating ethylene polymerization can be used.

As the water-soluble initiator, for example, water-soluble persulfonate and hydrogen peroxide can be used. In some cases, the polymerization initiator can be used in admixture with a reducing agent. Suitable reducing agents can be used, for example, sodium pyrosulfite, sodium pyrosulfite, sodium hydrogen sulfite, sodium thiosulfate, L-ascorbic acid and salts thereof and sodium formaldehyde sulfoxylate. Oil soluble initiators that can be dissolved in the monomer mixture or solvent include organic peroxides and azo initiators. Typical examples of such compounds are 2,2'-azobisisobutyronitrile, 1,1'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- 2,4-dimethylvaleronitrile, 1,1'-azobis-cyclohexane-1-carbonitrile, benzoyl peroxide, dibutyl peroxide, cumene hydroperoxide, isopropyl benzene hydroperoxide, p-methane hydride Monomer content of loperoxide, tertiary butylperoxy- (2-ethyl hexanoate), succinic peroxide, and generally diacyl peroxide, peroxy dicarbonate, and generally peroxymonocarbonate and generally residue It is a peroxy ester containing t-amyl peroxy ester found to be used, ensuring low. T-amyl hydroperoxide is also useful. Initiator mixtures may also be used. Preferred initiators are cumene hydroperoxide, isopropyl benzene hydroperoxide, ammonium persulfate, p-methane hydroperoxide, 2,2'-azobisisobutylonitrile, benzoyl peroxide, tertiary butyl hydroperoxide, 3 , 5,5-trimethylhexanol peroxide and tert butyl peroxy- (2-ethyl hexanoate). The amount of polymerization initiator used is about 0.1 to 3 parts by weight of the monomer mixture.

It is envisaged to use known chain transfer agents. Such materials include, for example, halogenated hydrocarbons (e.g. carbon tetrachloride, chloroform, bromo form, etc.), mercaptans (e.g. n-decyl mercaptan, tertiary dodecyl mercaptan, n-octyl mercaptan, etc.) Acidogens such as dimethylxanthogen disulfide, diisopropyl xanthogen disulfide and the like and terpenes such as dipentene, terpinolene and the like. The amount of chain transfer agent is preferably about 0 to about 10 parts by weight of the monomer mixture.

Chelating agents include, for example, glycine, alanine and ethylene diamine tetraacetic acid and pH adjusting agents include, for example, sodium carbonate, potassium carbonate and sodium bicarbonate. The amount of chelating agent and pH adjusting agent used is about 0 to about 0.1 parts by weight and about 0 to about 3 parts by weight of the weight of the monomer mixture, respectively.

A small amount of solvent can be added during the reaction to aid in swelling and seed the polymer. Typically, for example, such solvents are methyl ethyl ketone, acetone, trichlorofluoroethane, methyl isobutyl ketone, dimethyl sulfoxide, toluene, dibutyl phthalate in amounts that do not compromise fire risk and environmental and manufacturing safety. , Methyl pyrrolidone, ethyl acetate, and the like. The amount of solvent used is about 0 to about 20 parts by weight of the monomer mixture.

The final acrylic modified fluoropolymer particle size has been found to affect the properties of the latex resulting from the synthesis reaction and the coating made from the particles. Small particle size is desirable to obtain good film formation and good coated glass. The particle size should range from about 50 to 400 nm, with 50 to 200 nm being preferred. If the average particle diameter is less than 50 nm, the resulting aqueous dispersion has a high boiling point, so that a dispersion with a high solid content cannot be obtained, and condensation occurs when stronger shear conditions are applied. If the particle size is 400 nm or more, latex with poor storage stability is produced.

The average particle size of the acrylic modified fluoropolymer of the present invention can be controlled by appropriately selecting the size of the vinylidene fluoride polymer particles.

The z-average particle diameter of the polymer particles can be measured using a capillary hydrodynamic fractionation (CHDF) device.

If desired, additional amounts of surfactant and / or pH adjusting agent may be added to the final latex to improve its storage stability and / or reactivity.

The acrylic modified fluoropolymer resins obtained in the present invention can be prepared by self-condensation of their functional groups or by catalysts and / or crosslinkers (e.g. divalent or higher polyisocyanates, polyaziridines, polycarbodiimides, poly Known low molecular weight crosslinkers, alicyclic epoxy molecules, organosilanes, such as oxazolines, dialdehydes such as glyoxal, difunctional and trifunctional acetoacetates, malonates, acetals, thiols and acrylates For example, epoxysilanes and amino silanes, carbamates, diamines and triamines, as well as melamine resins, epoxy resins, etc.), inorganic chelating agents such as certain zinc and zirconium salts, titanium, glycouril and other aminoplasts. It can be crosslinked through the reaction. In some cases, functional groups from other polymeric components, such as surfactants, initiators, seed particles, may be involved in the crosslinking reaction. When two or more functional groups are involved in the crosslinking process, examples of complementary reaction groups include hydroxyl-isocyanate, acid-epoxy, amine-epoxy, hydroxyl-melamine, acetoacetate-acid. Other complementary functional groups are well known in the art and are considered equivalent by the present invention.

In order to form a good film from the acrylic modified fluoropolymer of the present invention, it is preferred that the minimum film forming temperature of the dispersion be maintained in the range of about 0 to about 70 ° C. This can be controlled by the glass transition temperature (Tg) of the polymer, since the minimum film formation temperature is closely related to Tg. The Tg of the final acrylic modified fluoropolymer can be obtained by appropriately selecting seed fluoropolymer particles having an appropriate Tg and monomer mixtures which provide a known Tg for the acrylic phase according to the principles generally used in miscible resin systems. Can be determined [see literature; Emulsion Polymerization and Emulsion Polymers ", Chapters 9 and 18, P. Lovell and M. Elasser (authors), J. Wiley, Ed. 1997].

Formulated baking paints or dry paints, cationic electrodeposition paints, fiber treatments, paper processing agents, floor coatings, carpet backings, water and oil repellents, non-adhesive treatments and protective surface coatings using acrylic modified fluoropolymers. Can be mad.

The acrylic modified fluoropolymer dispersions formed by the methods of the present method can be used as such or formulated as dyes of the aqueous emulsion type by addition of such typical dye additives such as dyes, dispersions, thickeners, antifoams, cryoprotectants and film formers. Can be mad. Those skilled in the art will be able to easily adjust the proportion of these additives to optimize the desired properties of the dye and films formed therefrom.

One or more water soluble resins (e.g., N-methyl melamine resins, alkylated methyl melamine resins, acrylic resins, urethane resins, epoxy resins, polyester resins, nylon resins, urea resins, alkyl resins, maleated oils, etc.) and / or moisture Acidic resins such as (meth) acrylic resins, vinyl acetate resins, ethylene vinyl acetate resins, urethane resins, and the like may be added when formulating paints and other coating materials from the acrylic modified fluoropolymers of the present invention. Those skilled in the art will also be able to optimize the number and relative proportions of these additives to obtain the desired properties of the product, such as the final film and the film obtained therefrom which form the mixture.

The acrylic modified fluoropolymer resin can also be separated from the latex formulated by known means, optionally by known methods, and formulated with such molding films as solvent dispersions, solvent solutions, aqueous dispersions or powder paints. have.

Those skilled in the art can crosslink the resins according to the invention from the above, either through self-condensation (self-reaction) or by using internal crosslinkers with or without a catalyst. It will also be apparent that crosslinking can occur by reaction of two different functional groups in the same molecule or in different molecules. The catalyst acts in a conventional manner to promote curing or to lower the required curing temperature.

One skilled in the art also knows that certain properties of the cured resins according to the present invention can be used in the manufacture of such resins, such as the chemical and physical stability of the crosslinks, the crosslink density, the nature and amount of the crosslinker, and the location of the crosslinking groups within the polymer molecules. It will be appreciated that many of the factors that control within the scope of the description will be affected.

Those skilled in the art will also readily appreciate that different crosslinkable systems can be prepared by changing the monomers and processing conditions in well known fashion. Examples of these include homogeneous systems in which the crosslinkable groups are statistically distributed, interfacial systems in which the crosslinking groups are mainly present on the surface of the polymer particles, systems in which the uncrosslinked particles are embedded in the matrix of the crosslinked polymer, and There is a system in which crosslinked particles are embedded in a matrix of uncrosslinked polymers.

The following examples further illustrate the best methods contemplated by the inventors in carrying out the invention and should not be construed as limiting or limiting examples thereof.

General protocol

In all experiments, seed latex, monomer [manufactured by Aldrich Chemical Co.], (sigma-Aldrich) initiator [manufactured by Alrich and Dupont], chain transfer agent [manufactured by Evans Evans Chemetic] and surfactant (Aldrich) are used as received without further purification.

Prefill , purge -ammonium persulfate (1.40 g), sodium lauryl sulfate (1.5 g) and seed latex (33.4 weight% solids, 85.8 weight% VF ₂ , 14.2 weight% HFP, melt viscosity 23 kp, 600 g) Prefill with kettle with high purity argon and monomer inlet and mechanical stirrer. In a separation vessel, a monomer mixture of methyl methacrylate (34.6 g), ethyl acrylate (14.8 g) and isooctyl mercaptopropionate (IOMP) (0.66 g) is prepared.

Immersion step —After flushing and purging the reactor and its initial contents for 30 minutes, an initial charge of monomer mixture (12.80 g) is introduced into the reactor. The mixture is then stirred for 60 minutes under argon at ambient pressure and temperature (90 rpm).

Reaction step —After the immersion step, the reactor and its contents are heated to 70 ° C. The time t ₀ is determined as the start of the heating step. After 60 minutes (t ₆₀ ), the remaining monomer mixture is introduced using a syringe (feed 37.26 g over 55 minutes). The monomer dosing rate is controlled using a syringe pump. When all monomer mixtures are added, residual monomers are consumed by maintaining a reaction temperature of 70 ° C. and a stirring rate of 90 rpm for an additional 120 minutes. The reaction mixture is then cooled to ambient temperature, discharged and the latex produced by the reaction is filtered through a loose cotton cloth. The pH of the filtered latex is then adjusted to 8 using aqueous ammonia. The polymer resin is then recovered as fines by condensation of the latex and the solid recovered is washed with water and dried. The final solids content of the latex before solid recovery is 38% by weight.

Throughout the following table, the amounts of monomer (s) and seed particles are given in parts by weight.

Nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), infrared spectroscopy (IR), mechanical mechanical analysis (DMA), and other measurement results are reported in the standard literature. By technology.

The solid concentration is dried overnight at 100 ° C. in an oven and then measured at 15-20 inch Hg (50.8-67.7 kPa) under vacuum at 100 ° C. for 1 hour. Solids content is expressed as% of weight of residue relative to weight of aqueous dispersion before drying. Glass transition temperature (Tg) is measured using a Perkin Elmer apparatus.

As shown in the table, the strains in stress and fracture values in the calculation are the average of five or more measurements measured using an Instron device.                     

Plaques 15 mm thick are molded from acrylic modified fluoropolymers (recovered from aqueous latex by coagulation using a freeze-thaw method). The plaques are baked for 2 to 5 minutes at 360 to 450 ° F. (182 to 234 ° C.) depending on the type of seed particles used. For acrylic modified fluoropolymers made from certain types of fluoropolymer seeds, the baking conditions are the same regardless of the composition of the acrylic monomer mixture. The tensile bars that meet the ASTM standards are then cut from the plaques.

Storage and loss modulus is measured with a controlled stress flow meter (DSR-200) using a 25 mm parallel plate arrangement. Plaques are prepared as described above, and samples 25 mm in diameter are cut. It is measured in a dynamic manner at 200 ° C. under a nitrogen atmosphere.

Solvent Tolerance: The fragments are cut from the plaques prepared as described above and immersed in the solvent at the specified time and temperature. The remaining material is removed and then washed with distilled water and dried to constant weight in 15-20 inch Hg (50.8-67.7 kPa) under vacuum at 120 ° C. for several hours.

Coating Evaluation: 15 g of modified fluoropolymer powder, 20 g of isophorone and 8 g of toluene are thoroughly mixed. As a representative pigmented paint formulation, 8 g of TiO ₂ is added to the mixture before mixing. The "as prepared" formulation is covered in aluminum Q-panel 0.6 mm thick. The panels are baked for 2 to 5 minutes at 360 to 540 ° F. (182 to 282 ° C.) depending on the seed particles used for the modified fluoropolymer synthesis. For modified fluoropolymers made using the same seed particles, the same baking conditions apply.

The coated surface of the aluminum Q-panel is cut in cross sections to form 100 squares of 2 mm x 2 mm each. The cut section is subjected to a peel test using a reduced pressure tape. The predetermined value is the number of squares remaining after the test. Pencil hardness is measured by ASTM D3363.

Impact test: 50in direct and reversible impact test. Apply in accordance with NCCA II-6, Method A with a lbs. (6.78J) load. 50-in cross-hatch direct and reversible impact tests. Perform in accordance with NCCA II-16 with a lbs. (5.65J) load. The same cross-hatch direct and reversible impact test is applied after the Q-panel is immersed in the boiling water for 10 minutes. The results for all tests are as follows.

Gloss: Films are cast on a Leneta type 2A brightness chart using a 0.127 m stretch applicator at 250 μm spacing. Film gloss is measured using a Hunter Lab Progloss PG-2 gloss meter.

Methyl ethyl ketone (MEK) resistance: Rub the coated surface of the aluminum panel with a hammer coated with a loose cotton cloth instantaneously impregnated with MEK until the coating has dissolved and reaches the aluminum surface. The predetermined number is the double frictional number required to reach the aluminum surface. If the aluminum surface is not reached, the predetermined value is the maximum number of double frictions performed earlier with a larger ">" mark.

In all tables, the amounts of monomers and seed particles are given in parts by weight, unless otherwise specified.

In the following table, the fluoropolymer seeds used as starting materials are identified as follows.

Fluoropolymer A: Vinylidene fluoride alone having a melt viscosity of 13.5-16.0 kp (ASTM D 3835 under the conditions specified above) and a particle size of about 100-350 nm, prepared as described in US Pat. No. 4,569,978. polymer.

Fluoropolymer B: about 90% by weight vinylidene fluoride content, about 10% by weight hexafluoropropylene content, synthesized as described in US Pat. No. 4,569,978, with a melt viscosity of about 23 kp (above) Copolymer under ASTM D 3835 and specified particle size of about 230 nm.

Fluoropolymer C: A vinylidene fluoride content of about 88% by weight, a hexafluoropropylene content of about 12% by weight, and a melt viscosity of about 23 kp (above), prepared as described in US Pat. No. 4,569,978. Copolymers having a particle size of about 20 nm under specified conditions.

Fluoropolymer D is a polyvinylidene fluoride homopolymer synthesized according to US Pat. No. 4,549,978 with a melt viscosity of 17 to 23 kp (ASTM D 3835 under the conditions specified above) and a particle size of about 90 nm.

Fluoropolymer E has a hexafluoropropylene content of about 11% by weight, a melt viscosity of about 23 kp (ASTM D 3835 under the conditions specified above) and a vinylidene fluoride-hexafluorine having a particle size of about 100 mm to about 110 mm. It is a low propylene copolymer.

In all cases, acrylic polymerization is initiated using the identified seed polymers and is carried out using monomers specified in total amounts relative to the amount of seed polymer and in proportions specified with one another.

In all tables, the amounts of monomer (s) and seed particles are given in parts by weight, unless otherwise specified.

Comparative Example

Modified fluoropolymers containing no functional groups capable of crosslinking reactions

Seed polymerization is carried out according to the procedure as described above.

In Table 1, reference polymers are prepared from homopolymer seeds (fluoropolymer A), methyl methacrylate and ethyl acrylate monomers in the ratios shown.

In Table 2, reference polymers are prepared using methyl methacrylate and ethyl acrylate monomers in the amounts specified in the table from the fluoropolymer seeds identified during each run. In Table 2, azo initiator VAZO 67 (Aldrich) is substituted with ammonium persulfate, which is used in other runs in Example 11.

Table 1 illustrates adjusting Tg by changing the VF seed / acrylic monomer ratio and / or the methyl methacrylate-ethyl acrylate ratio. Table 2 suggests that the Tg range and thus the minimum film formation temperature of the polymer can be greatly broadened by changing the seed particle composition.

Synthesis of Modified Fluoropolymer Dispersions Conduct number FP ^* solid / acrylic monomer ratio (weight) MMA / EA Ratio (wt%) Solid content (% by weight) Dn (Nm) Tg (℃)  One  70/30  80/20  46  371  60.3  2  70/30  70/30  45  341  51.2  3  70/30  60/40  46  338  40  4  70/30  50/50  46  360  -  5  80/20  70/30  42  315  50.1  6  70/30  70/30  51  350  -  7  60/40  70/30  49  -  54.6  8  54/46  70/30  41  360  -   Seed latex: fluoropolymer A aqueous dispersion. Monomer mixture: methyl methacrylate (MMA) and ethyl acrylate (EA). Dn: modified fluoropolymer particle size. Tg: glass transition temperature. * In this and subsequent tables, FP used as an abbreviation refers to a fluoropolymer.

Synthesis of Modified Fluoropolymer Dispersions Conduct number Fluoropolymer FP Solid / Acrylic Monomer Specific Weight% MMA / EA Specific Weight% Solid content weight% Dn (nm) Tg (℃)  One  B  70/30  70/30  48  -  -  2  B  61/39  70/30  42  373  14  3  B  68/32  72/28  48  345  -  4  B  69/31  73/27  48  342  -  5  B  71/29  72/28  46  -  -  6  B  94/6  67/33  43  300  -  7  B  81/19  69/31  48  333  -  8  B  81/19  69/31  48  334  -  9  B  81/19  69/31  46  330  -  10  B  80/20  70/30  46  346  -  11  B  81/19  70/30  47  -  -  12  C  80/20  70/30  32  240  14  13  C  70/30  75/25  45  -  -   Seed latex: fluoropolymer B latex or fluoropolymer C aqueous dispersion. Monomer mixture: methyl methacrylate (MMA) and ethyl acrylate (EA). Dn: modified fluoropolymer particle size. Tg: glass transition temperature.

Example 1

Modified fluoropolymers with functional groups

Seed Particles = VF ₂  Homopolymer

Table 3 sets forth the properties of polymers containing a plurality of functional groups, synthesized at the ratios indicated from the monomers presented using fluoropolymer A as the seed polymer.

The data demonstrate that the storage coefficient, G ¹ (10 ² Pa), stress in calculation, and strain at break can be adjusted by suitably selecting the properties and amounts of functional monomers used. For example, in Experiments 1-3, the amount of glycidyl methacrylate (GMA) was varied from 0.3 parts by weight to 5 parts by weight in the acrylic monomer mixture. From the changes in storage coefficients, stresses in calculation and strain values at break, it is evident that the final cured material will become harder depending on the GMA content. In the absence of any functional monomers, the final material of Example 13 is poorer in mechanical and physical properties.

From the data set forth in Table 4, the solvent resistance of the modified fluoropolymers can be significantly increased compared to the case where they do not contain any at all by incorporating a polymer containing a crosslinkable functional group into the acrylic monomer mixture. Is obvious. For example, when extracted using triethylphosphate (TEP), the modified fluoropolymer resin containing 5% by weight HEMA or GMA is maintained at 72% of its initial weight while at the same time crosslinking functional groups The sample containing no at all dissolves completely. This not only makes the crosslinked acrylic phase insoluble, but also demonstrates that the fluoropolymer phase is partially or substantially completely prevented from dissolution.

Table 5 shows that when applied as an organic solvent carrier coating, modified fluoropolymers having crosslinkable functional groups in the composition are excellent in hardness. Examples 13, 1 and 3 of Table 5 also illustrate that the coating's resistance to methylethyl ketone (MEK) can be adjusted by varying the amount of crosslinkable functional monomer. Table 5 suggests that coating properties can be significantly improved with suitable amounts of crosslinkable functional monomers and proportions thereof.

Synthesis of Modified Fluoropolymer Dispersions group One 2 3 4 5 6 7 8 9 10 11 12 13 MMA 10 21 20 18 21 18 21 20 18 21 18 21 21 EA 9 9 8.5 7 9 7 9 8 7 9 7 9 9 AA - - - - 5 0.3 IA - - - - 2 HEMA - - - 5 0.3 GMA 5 0.3 1.5 - EMA - - - - 5 0.3 TMPA - - - - 5 0.3 Solid content 47 44 46 47 18 43 47 40 42 46 46 44 50 DN (nm) ¹ 340 346 350 289 - - 315 350 285 - 284 340 Tg (℃) ² - 30.8 - - 23 - 26 - - 33 - - 37 Calculation stress (psi) *** 2950 5730 5900 4360 4570 3030 5650 7220 4920 *** 4600 2770 % Strain in calculation *** 429 296 83 433 152 407 274 123 363 *** 260 425 G '(10 ² Pa) > 800 100 200 > 800 200 > 500 150 40 - 150 - > 600 40 40   Seed latex: Aqueous dispersion of fluoropolymer A of 70 parts by weight of solid. The monomer mixture composition is expressed in parts by weight per 100 parts by weight of the total acrylic-modified fluoropolymer particles. Notes: 1. Dn: modified fluoropolymer particle size; 2. Tg: glass transition temperature. *** Destroyed during test.

Synthesis of Modified Fluoropolymer Dispersions  Example 20 21 22 23 24 25 26  MMA 21 20.8 19 19 21 19 20  EA 9 8.5 9 8.5 8 8.5 9  IBMA 2.5  MAA One  HEMA  1.7  GMA 2.5  AEA 2 One  DGEA 2 One  Solid weight% 48 48 49 46 48 48 48 Dn ¹ (nm) 95 105 102 110 95 95 120 G '(10 ² Pa) 20 200 20 100 100 > 800   Seed Latex: Aqueous dispersion of fluoropolymer A small particles. The monomer mixture composition is expressed in parts by weight per 100 parts by weight of the total acrylic-modified fluoropolymer particles. Notes: 1. Dn: Modified fluoropolymer particle size.

Solvent resistance                          Example number Functional monomer (% by weight) 13 10 6 7 8 5 3 2 One 15 12 18 19 4 HEMA 0.3 5 GMA 1.5 0.3 5 0.5 IBMA 5 NMA 5 0.3 2.5 AA 0.3 0.2 One 2 IA 2 TMPA 0.3 THF, 80 ° C, 2 hours 65 67 - 68 68 70 - 80 - 77 100 - - - NMP, 60 ° C, 2 hours 0 - 50 - - - 0 0 - - 95 - - - TEP, 100 ° C, 2 hours 0 - - 0 - - 0 - 72 - - 34 65 72   Seed latex: Aqueous dispersion of fluoropolymer A. Monomer composition: parts by weight per 100 parts by weight of the total monomer mixture. The dry matter remaining after the test is expressed in parts by weight per 100 parts by weight of the initial material.

 Film measurement                   Example number  Monomer 13 One 14 3 8 9 16  MMA 21 18 21 20 20 18 20  EA 9 9 8.3 8.5 8 7 9  AA - 0.2 5 0.4  IA - 2  HEMA - 0.6  GMA 5 0.5 1.5  AOPD  Solid (wt%) 50 47 48 46 40 42 50 Dn (nm) ³ 350 340 320 350 350 285 334  Pencil hardness H-F 3H-2H 3H-2H 3H-2H 3H-2H 3H-2H 2H-H  Adhesive 100 100 100 100 100 100 100 Impact test ¹ P P P P P P P MEK ² 400 > 1600 300 620 200 405 400 Seed latex: Aqueous dispersion of fluoropolymer A. Monomer composition: parts by weight per 100 parts by weight of the total monomer mixture. Note: 1. Impact resistance: P passed the test; F fails the test. 2. MEK: Number is the number of double frictions. 3. Dn: modified fluoropolymer particle size

Example 2

Seed polymerization processes similar to those described above are carried out using fluoropolymers B and C as indicated in Tables 6 and 7.

Table 6 illustrates an example of the use of functional monomers. From the changes in the storage coefficient, the stress at calculation and the strain at break, it is clear that the final aerated natural properties are increased. These results show that the final properties can be adjusted by appropriately selecting the nature and amount of the functional monomers used. In the absence of crosslinking, the material is inferior in hardness and tensile strength. In Example 5, where the crosslinkable monomer is not included in the acrylic monomer mixture, the mechanical properties are inferior to those in which the crosslinkable monomer is included (see Examples 4, 7, 9 and 11).

Table 7 also describes the effect of crosslinking on the acrylic phase on the solubility of the fluoropolymer in contrast to when crosslinking was not possible. These results show that the insoluble portion is larger than the portion due to the acrylic present initially, so that the fluoropolymer portion is prevented from solubilization.

Synthesis of Modified Fluoropolymer Dispersions Example One 2 3 4 5 6 7 8 9 10 11 Fluoropolymer B B B C C C C C C C C Fluoropolymer Weight% 68 68 68 70 70 69.7 69 70 70 71 71 MMA 21 20 21 20 22 19.5 17 18 18.5 20 18.5 EA 9 9 10 9.8 8 10 10 10.5 7 7.7 8 AA One MAA One 2 0.5 One HEMA 2.5 0.8 GMA 3 1.5 AEA 2 1.5 IBMA 2 TMPA 0.2 Solid weight% 47 48 42 42 45 41 43 - 44 40 44 Tg ¹ (℃) 9 8 - - 8 6 - - 14 - 12 Dn ² (nm) 340 362 - - - 270 - - 260 - 290 Calculation stress (PSI) 3670 3360 - 2380 2800 3000 1800 - - 3200 3550 Stress at Break (%) 192 202 - 232 450 480 430 - - 430 60 G '(10 ² Pa) > 800 400 - > 800 100 100 300 150 250 200 500   Seed Latex: Fluoropolymer B or C aqueous dispersion. The monomer mixture composition is expressed in parts by weight per 100 parts by weight of the total monomer mixture. Notes: 1. Tg: glass transition temperature 2. Dn: modified fluoropolymer particle size

Solvent resistance Example Monomers containing functional groups % By weight of functional groups contained on the final modified fluoropolymer particles Residual material after treatment (% by weight) 5 None None 0 10 MAA / HEMA 0.5 / 0.8 0 12 MAA / HEMA 0.3 / 1 0 9 MAA / HEMA 2 / 2.5 0 4 TMSPA 0.2 68 11 MAA / GMA 1 / 1.5 45 6 MAA One 0 8 AEA 1.5 22   Seed latex: fluoropolymer B aqueous dispersion. Monomer composition: parts by weight per 100 parts by weight of the total monomer mixture. The residual dry matter after the test is given in parts by weight per 100 parts by weight of starting material. The material is treated for 2 hours at room temperature in triethyl phosphate.

Example 3

Seed polymerization is carried out using fluoropolymers D and E as seeds according to the above-mentioned methods. The coating formulation is then prepared from the seed polymer thus formed.

Table 8 shows the fluoropolymer seeds used, the amounts, parts by weight, and the units of acrylic (and other copolymerizable monomers applicable) used in the seed polymerization reaction and the total weight percent solids in the resulting seed polymer latex and particles in the latex. Approximate particle size of. In the formulations summarized in the table, the ratio of fluoropolymer to acrylic is 70 to 30 parts by weight, and the acrylic monomer ratio is expressed as parts by weight relative to the total polymer solid phase.

Seed polymer number Starting fluoropolymer Methyl methacrylate Ethyl acrylate Methacrylic acid Other monomers Total solids (% by weight) Particle size (nm) III-A D 19 8 3 - 50 120 III-B D 18 8 One Hydroxyethyl methacrylate 3 51 120 III-C D 19 8 One Hydroxyethyl methacrylate 3 51 120 III-D D 15 7 2 Hydroxyethyl methacrylate 3 50 120 III-E E 20 8 - Glycidyl Methacrylate 2 51 140-150 III-F E 20 8 - Acetoacetoxy ethyl methacrylate 2 46 140-150 III-G E 20 8 - Isobutyl methacrylamide 2 53 140-15

Table 9 lists coating formulations made from the seed polymers of Table 8. In Tables 9 and 10, the amounts of ammonia listed are 7% by weight of ammonia solution in water, TEXANOL ™ is an alcoholic ester coalescent from Eastman Chemical, and ARCOSOLVE. ™ DPM is a binder from Arco Chemical, provided the content of Formulation III-2 shown is 50:50 weight of the premix in water and TRITON ™ X-405 is Union Carbide Surfactant from, the tabled content is 35% by weight solution in water, the indicated p-toluenesulfonic acid content is 10% by weight in water, BYK 346 is a wetting agent from BYK Chemical Company, TMP- Tris-Aziridine is a crosslinker from Aldrich Chemical Co. (CAS 64265-57-2), the content shown in the table is 50% by weight in propylene glycol meth ether ether acetate and UCARINK ) ™ Crosslinker XL -2-SE is a carbodiimide crosslinker from Union Carbide, ACRYLSOL ™ QR-1279W and RM-825 are binding extenders from Rohm and Hass Company and are listed in the table. The content is 5% by weight solid in water mixture.

Base coating formulation Coating formulation Seed polymer latex Latex amount information (parts by weight) Other ingredients (parts by weight) III-1 III-A 100 Ammonia (1.50) Texanol (5.00) III-2 III-C 134.8 Texanol (6.72) Arcosolve-DPM (10.10) III-3 III-C 100 Triton X-405 (6.00) Arcosolve DPM (20.00) III-4 III-R 120 Premix of Triton X-40D (5.00) Acrylsol RM-1279M (12.00) with ethylene glycol monobutyl ether (12.00) III-5 III-F 200 Arcosolve DPM (40.00) III-6 III-P 100 Triton X-405 (6.00) Arcosolve DPM (20.00) III-7 III-F 100 Arcosolve DPM (20.00) Acrylsol RM 825 (1.89) BYX 346 (0.10) Ammonia (0.10) Glycerol [40% by weight] (0.60) in water (0.60) III-8 III-C 170.01 Ammonia (pH 3.36 to 8.3) Acrylsol RM 825 (1.89) Ethylene glycol monobutyl ether (8.56) BYX 346 (0.10) III-9 III-B 169.95 Ammonia (pH 2.0 to 7.9) Acrylsol RM 825 (1.90) Ethylene glycol monobutyl ether (8.49) and water (8.80) III-10 III-D 100 Triton X-405 (2.00) Arcosolve DPM (20.00) III-11 III-B 140 Arcosolve DPM (29.02) Acrylic Sol RM-825 (2.42) BYX 346 (0.10) III-12 III-E 100 Arcosolve DPM (20.06) Acrylic Sol RM-825 (2.19) BYX 346 (0.07) III-13 III-A 100 Arcosolve DPM (2.66) Acrylic Sol RM-825 (2.42) BYX 346 (0.07)

In Table 10, the coating formulation shows that the cure / crosslinking adjuvant is added to the formulation in Table 9.

In Table 10, the developing curing agent (DPC-750) is a developing diamine curing agent from a shell resin; The amount of adipic dihydrazide is 5% by weight in water solution; Bayhydur is a polyisocyanate curing agent from Bayerdur ^R XP7063, Bayer Corporation and Cymel 303 is a melamine crosslinker from Cytec Ind.

Formulation Number Starting formulation number Volume (parts by weight) Other Added Ingredients (parts by weight) III-14 III-1 25.00 Yucca Link Crosslink XL-29SB (3.36) III-15 III-1 50.00 TPM-trisaziriden (2.50) III-16 III-3 70.00 p-toluenesulfonic acid (10% by weight in water) (1.00) BKK-346 (0.05) acrylic sol RM-825 (5.00) III-17 III-4 35.00 Development hardener DPC-750 (0.20) III-18 III-5 19.53 Adipic Dihydrazine (1.11) III-19 III-8 70.00 Beydur (1.11) III-20 III-9 70.05 Beydur (1.26) III-21 III-10 80.0 Simel 303 (5.00) BYK 346 (0.07) acrylic brush RM-825 (1.60) III-22 III-3 40.60 III-11 (13.25) III-23 III-12 75.00 III-13 (26.00)

The formulations of Tables 9 and 10 are applied to glass (for free film irradiation) and aluminum chromate panels with a dry film thickness of 20 to 25 μm using a draw applicator. For crosslinked or catalyzed systems, after addition of the crosslinker or catalyst, stretching is performed within a few hours. The panels are dried at room temperature (or optionally further cured at higher temperatures for a short time). Physical properties are measured after two weeks or more.

The results are shown in Table 11.

1 hour solvent soak ^** Free film tensile test Formulation III AMF Sensory Group * Crosslinker or catalyst Curing condition (AD = air drying) MEK Swelling Ratio / Soluble Fraction THF Swelling Ratio / Soluble Fraction % Strain at break Toughness, psi ^*** Pencil hardness on AL 1 14 15 Acid 3% maa 3% maa None (control) ciarbodiimide asyridine AD AD AD d 1.7 / 9 1.2 / 6 d 4.0 / 8 1.1 / 6 F HB H  2 2 3 16 16 Acrylamide 2% iBMA 2% iBMA 2% iBMA 2% iBMA 2% iBMA  None None None pTSA Catalyst pTSA Catalyst  10 minutes at AD 200 ° C 30 minutes at AD 100 ° C  5.9 / 6.7 6.5 / 65 d 5.6 / 7.4 4.6 / 28  7.0 / 6.1 7.6 / 62 d 7.0 / 64 5.3 / 17  43 249 17 8 14  812 8182 533 Low 314  B 2H HB 4B 2H  4 17 Epoxy 2% GMA 2% GMA  None (Control) Diamine  AD AD  d 2.4 / 31  d 5.6 / 32  5 48  108 926   5 16 6 7 7 Acetoacetate 2S AAEM 2% AAEM 2% AAEM 2% AAEM 2% AAEM   None (Control) Dihydrazide None (Control) Aldehyde Aldehyde   AD AD AD AD 30 min at 100 ° C   d 2.9 / 32 d nm / 32 6.6 / 53   d 4.9 / 31 d nm / 20 6.4 / 42   46 91 17 11 22   1261 3100 341 332 683

 8 19 9 20 21 21 Hydroxy 1% MAA / 2% HEMA 1% MAA / 2% HEMA 1% MAA / 3% HEMA 1% MAA / 3% HEMA 2% MAA / 6% HEMA 2% MAA / 6% HEMA  None (Control) Isocyanate None (Control) Isocyanate Melamine Melamine  54 C 54 C 54 C 64 C AD 30 min at 100 ° C  d 3.7 / 20 d 2.3 / 2 2.0 / 7 2.3 / 0  d 4.2 / 21 d 3.1 / 5 3.6 / 10 2.3 / 2  d 4.2 / 21 d 3.1 / 5 3.6 / 10 2.3 / 2  F 2H HB 2H 2H 2H  22 22 23 Mixed hydroxy + acrylamide hydroxy + acrylamide epoxy + acid  None None None  30 minutes at 100 ℃ 30 minutes at 100 ℃   d = dissolved nm = not measured * expressed as weight percent functional monomer in AMF solids ** swell: weight after 1 hour solvent soaking / weight of soluble fraction before soaking: weight after drying / weight before soaking. Lower values indicate higher crosslinking. *** Toughness: Area under the shear force-shear curve. Pencil Hardness Grade: 2H> H> F> HB> B> 2B> 3B> 4B> 5B

The present invention provides vinylidene fluoride polymer based acrylic modified fluoropolymers, wherein the acrylic phase can crosslink, and the final cured product provides better solvent extraction resistance on the fluoropolymer.

Claims (18)

An acrylic modified fluoropolymer based on latex particles of a vinylidene fluoride polymer selected from the group consisting of vinylidene fluoride homopolymer and vinylidene fluoride-hexafluoropropylene copolymer, The acrylic moiety contains monomer moieties having functional groups capable of crosslinking reactions, the functional groups do not comprise carboxylic acid groups alone, and the fluoropolymer moiety is known such as triethylphosphate and N-methylpyrrolidone. An acrylic modified fluoropolymer based on latex particles of a vinylidene fluoride polymer, characterized in that solubilization is prevented by a fluoropolymer solvent. The acrylic modified fluoropolymer of claim 1 which is a vinylidene fluoride homopolymer. The acrylic modified fluoropolymer of claim 1 wherein the vinylidene fluoride polymer is a vinylidene fluoride-hexafluoropropylene copolymer. The acrylic modified fluoropolymer of claim 3 wherein the acrylic moiety is prepared by polymerizing methyl methacrylate, ethyl acrylate and glycidyl methacrylate in the presence of vinylidene fluoride-hexafluoropropylene copolymer seeds. . Latex containing an acrylic modified fluoropolymer according to claim 1. A curable composition comprising an acrylic modified fluoropolymer according to claim 1 and at least one crosslinkable catalyst. A curable curable composition comprising an acrylic modified fluoropolymer based on latex particles of a vinylidene fluoride polymer selected from the group consisting of vinylidene fluoride homopolymer and vinylidene fluoride-hexafluoropropylene copolymer As a cured composition produced from The acrylic phase of the acrylic modified fluoropolymer contains monomeric residues having crosslinkable functional groups, and a portion of the fluoropolymer is inhibited in solubilization by known fluoropolymer solvents such as triethylphosphate and N-methylpyrrolidone. And a cured composition resulting from the curable curable composition. delete On the basis of latex particles of vinylidene fluoride polymers selected from the group consisting of vinylidene fluoride and chlorotrifluoroethylene, vinyl fluoride, tetrafluoroethylene and these comonomer mixtures and these copolymer mixtures As one acrylic modified fluoropolymer, Acrylic modified based on latex particles of vinylidene fluoride polymer, characterized in that the acrylic moiety contains monomer moieties having functional groups capable of crosslinking reaction, and the functional groups do not contain carboxylic acid groups alone. Fluoropolymers. 10. The acrylic modified fluoropolymer of claim 9 wherein one of the vinylidene fluoride copolymers may comprise hexafluoropropylene as comonomer. Latex containing an acrylic modified fluoropolymer according to claim 9. Latex containing an acrylic modified fluoropolymer according to claim 10. A curable composition comprising an acrylic modified fluoropolymer according to claim 9 and at least one crosslinkable catalyst. A curable composition comprising an acrylic modified fluoropolymer according to claim 10 and at least one crosslinkable catalyst. On the basis of latex particles of vinylidene fluoride polymers selected from the group consisting of vinylidene fluoride and chlorotrifluoroethylene, vinyl fluoride, tetrafluoroethylene and these comonomer mixtures and these copolymer mixtures A cured composition resulting from a curable curable composition comprising an acrylic modified fluoropolymer, A cured composition resulting from a curable curable composition, wherein the acrylic modified copolymer contains monomeric residues having functional groups capable of crosslinking reactions, and wherein the functional groups do not comprise carboxylic acid groups alone. The cured composition of claim 15, wherein the vinylidene fluoride copolymer can further contain hexafluoropropylene as comonomer. delete delete