JP2767819B2 - Non-aqueous dispersion type resin composition - Google Patents

Description

The present invention relates to a non-aqueous dispersion type resin composition useful for paints, sealing agents, films, and the like. An olefin and a vinyl monomer containing a hydroxyl group and, if necessary, another copolymerizable monomer, a fluoroolefin copolymer [I] obtained from the monomer mixture
A non-aqueous polymer dispersion obtained by non-aqueous dispersion polymerization in the presence of a dispersion stabilizer comprising a fluoroolefin copolymer [II] that can be dissolved or swelled in an organic solvent in which And a non-aqueous dispersion type resin composition characterized by comprising as an essential component.

(Conventional technology and its problems) In recent years, room temperature-curable fluoroolefin copolymers that form solution-type and ultra-high weather resistant coatings have been developed and are mainly used for coatings. ing.

However, the solvent used in such a solvent-type fluoroolefin copolymer usually comprises an organic solvent having high photochemical reactivity such as aromatic hydrocarbon, and the solvent-type fluoroolefin copolymer is applied as a paint. In such a case, an organic solvent having high photochemical reactivity is discharged into the atmosphere, causing air pollution. Furthermore, the above-mentioned organic solvent generally has high polymer solubility, and when a paint composed of a solution-type fluoroolefin copolymer is applied to an undercoated paint, the undercoat film swells. Cause "chummy" and "swelling".

In addition, the solution-type fluoroolefin copolymer has a viscosity characteristic that the viscosity increases as the molecular weight increases as in the case of a normal solution-type resin. In the case of applying a coating composed of coalesced paints, a large amount of solvent is required to lower the viscosity to a level at which the coating can be performed.

(Problems to be Solved by the Invention) The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, in an organic solvent which does not dissolve the generated hydroxyl group-containing fluoroolefin copolymer [I]. A monomer comprising, as an essential component, a fluoroolefin and a hydroxyl-containing vinyl monomer in the presence of a dispersion stabilizer comprising a fluoroolefin copolymer [II] which can be dissolved or swelled in the organic solvent. A non-aqueous dispersion type resin composition comprising a non-aqueous polymer dispersion obtained by subjecting a mixture to non-aqueous dispersion polymerization as an essential component solves the above-described problems, and
It has been found that an excellent and durable coating film is formed, and the present invention has been completed.

[Configuration of the invention]

(Means for Solving the Problems) To summarize the present invention, the present invention uses a fluoroolefin and a vinyl-based monomer containing a hydroxyl group as essential monomer components, and further includes another monomer if necessary. A monomer mixture containing a polymerizable monomer is dissolved in an organic solvent which does not dissolve the fluoroolefin copolymer [I] obtained from the monomer mixture. A non-aqueous polymer dispersion obtained by non-aqueous dispersion polymerization in the presence of a dispersion stabilizer composed of an olefin copolymer [II] (hereinafter abbreviated as a dispersion stabilizer) is contained as an essential component. And a non-aqueous dispersion type resin composition.

 Hereinafter, the configuration of the present invention will be described in detail.

As the fluoroolefin component of the fluoroolefin copolymer [I], which is a dispersion in the present invention, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, bromotrifluoroethylene,
Representative examples include chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, and (per) fluoroalkyltrifluorovinyl ether (provided that the (per) fluoroalkyl group has 1 to 18 carbon atoms).

Next, the hydroxyl group-containing vinyl monomers used in the present invention include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 3-hydroxybutyl vinyl ether. 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 3-hydroxypropyl allyl ether, 4-hydroxybutyl allyl ether, 2-hydroxyethyl (meta ) Acrylate and 1-hydroxymethyl-4-vinyloxymethylcyclohexane are typical.

When preparing the hydroxyl group-containing fluoroolefin copolymer [I] according to the present invention, in addition to the essential monomer components,
Other monomers that can be copolymerized with these essential monomer components can be used as needed. Such other copolymerizable monomers [hereinafter, abbreviated as copolymerizable monomers (1). ] As methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether,
Alkyl vinyl ethers such as ethylhexyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether; aralkyl vinyl ethers such as benzyl vinyl ether or phenethyl vinyl ether; 2,2,3,3-tetrafluoropropyl vinyl ether; , 2,3,3,4,4,5,5-
Octafluoropentyl vinyl ether, 2,2,3,3,4,4,
5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl vinyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether, perfluorohexyl vinyl ether (Per) fluoroalkyl vinyl ethers such as vinyl acetate;
Vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl p-tert-butyl benzoate, vinyl salicylate, cyclohexane carboxylate Representative examples thereof include carboxylic acid vinyl esters such as vinyl acid; and ethylene, vinyl chloride, vinylidene chloride, (meth) acrylonitrile, and various (meth) acrylic esters described below. Then, among the copolymerizable monomers (1), alkyl vinyl ethers, cycloalkyl vinyl ethers,
Aliphatic vinyl esters of monocarboxylic acids having an alkyl group of C ₁ -C _17, vinyl benzoate, p-tert-butylbenzoic acid vinyl, may be used in combination with at least one member selected from the group consisting of cyclohexanecarboxylic acid vinyl Particularly preferred.

With respect to the fluoroolefin copolymer [I] obtained from each of the monomer components described above, a fluoroolefin containing a hydroxyl group from the viewpoint of the yield of the copolymer, insolubility in various organic solvents and weather resistance as described below, and the like. The proportion of each monomer component forming the copolymer [I] is 15 to 70% by weight of a fluoroolefin, and 1 to 40% of hydroxyl group-containing vinyl monomers.
Wt%, other co-additive monomers (1) 0-84 wt%,
More preferably, it is controlled to 20 to 60% by weight of a fluoroolefin, 3 to 25% by weight of a hydroxyl group-containing vinyl monomer, and 10 to 77% by weight of another copolymerizable monomer (1).

Further, the copolymerization amount of the hydroxyl group-containing vinyl monomer and the copolymerizable monomer (1) is determined based on the amount of the hydroxyl group-containing fluoroolefin copolymer [I] with respect to various organic solvents described below. Is appropriately determined within the range of each ratio of the hydroxyl group-containing vinyl monomer and the other copolymerizable monomer (1) to such an extent that does not dissolve.

Next, the organic solvent used in the present invention is non-polar or has relatively low dissolving power and does not dissolve the fluoroolefin copolymer [I], but can dissolve or swell the dispersion stabilizer. Any can be used.

Specific examples of such an organic solvent include hexane,
Aliphatic hydrocarbons such as heptane or octane; having a boiling point of 30 to 30 such as petroleum benzene, petroleum ether, ligroin, mineral spirits, petroleum naphtha or kerosene
Hydrocarbon mixtures at 300 ° C .; cyclohexane,
Examples include alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane, and these may be used alone or as a mixture. Further, to the extent that the fluoroolefin copolymer [I] is not dissolved, for example, an aromatic hydrocarbon solvent, an alcohol solvent, an ester solvent, a ketone solvent or an ether solvent can be used in combination.

Next, the dispersion stabilizer used in the present invention is one that can be dissolved or swelled in the organic solvent as described above, and has an affinity for the fluoroolefin copolymer [I] and polymer fine particles generated during polymerization. It can be stably dispersed.

Specific examples of such a dispersion stabilizer include the following.

-1: vinyl esters of the above-mentioned fluoroolefins and aliphatic monocarboxylic acids having an alkyl group of C _{4 to} C ₁₇ , vinyl cyclohexanecarboxylate, alkyl vinyl ethers having an alkyl group of C _{2 to} C ₁₈ , and cycloalkyl Copolymers containing at least one selected from the group consisting of alkyl vinyl ethers as a main component and, if necessary, copolymerizing other vinyl monomers copolymerizable therewith; such copolymers; Other possible vinyl monomers [hereinafter abbreviated as vinyl monomers (2)]. Specific examples of the dispersion stabilizer include the monomers (1) copolymerizable with the essential monomer components constituting the fluoroolefin copolymer [I]. All monomers except the monomers constituting the main component group of -1; vinyl monomers having a hydroxyl group as described above; monovinyl succinate, monovinyl adipic ester,
Monomers having a carboxyl group such as sebacic acid monovinyl ester, (meth) acrylic acid or crotonic acid; amino group, carboxylic anhydride group, epoxy group, isocyanate group, amide group, aziridinyl group, hydrolyzable silyl group, Examples include vinyl monomers having a reactive functional group such as a silyloxycarbonyl group and a silyloxy group.

-1: An unsaturated bond-containing polyolefin polymer such as polybutadiene or polyisoprene is copolymerized with at least one selected from the group consisting of fluoroolefins and the other vinyl monomers (2). -2 and -2: unsaturated copolymers as described above with respect to the carboxyl group of the copolymer having a carboxyl group, among the dispersion stabilizers of -1 and -1 described above. Each unsaturated bond-containing copolymer obtained by subjecting a bond-containing epoxy compound to an addition reaction.

-3, -3: among the above-mentioned dispersion stabilizers of -1 and -1, respectively, maleic anhydride, itaconic anhydride or trimellitic anhydride monovinyl ester with respect to the hydroxyl group of the copolymer having a hydroxyl group. Unsaturated bond-containing copolymers obtained by subjecting monomers containing a carboxylic acid anhydride group to an addition reaction; -4, -5: Unsaturated bond-containing copolymers of -2 and -3 described above. Each graft copolymer obtained by copolymerizing a carboxylic acid vinyl ester having an alkyl group of C _{1 to} C ₃ into the union is mentioned, and in addition to the above-mentioned carboxyl group and hydroxyl group as the graft point, It is also possible to use a reactive functional group such as described above, and an addition reaction of an unsaturated bond-containing monomer having a reactive functional group capable of reacting with the reactive functional group with respect to the reactive functional group as the graft point. Sesame It can also be prepared the unsaturated bond-containing copolymer by.

Further, for each of the above-mentioned dispersion stabilizers having an unsaturated bond, a monomer mixture forming a fluoroolefin copolymer [I] as a dispersion in the composition of the present invention is crafted. The obtained graft copolymer can also be used.

Among the various dispersion stabilizers as described above, as a measure of the solubility of the dispersion stabilizers except the graft copolymer,
From the viewpoint of dispersion stability or polymerization stability of the non-aqueous polymer dispersion which is an essential component in the composition of the present invention, heptane tolerance (25 ° C.) is 200% or more [heptane is dropped to a predetermined resin solid content. The value obtained by dividing the amount of heptane (ml) required for the resin solution to become cloudy by the amount of resin (g) and further multiplying by 100. And more preferably 300% or more.

As the fluoroolefin-based polymer [II] used as the dispersion stabilizer in the present invention, from the viewpoints of the solubility in an organic solvent and the weather resistance described above, a monomer mainly forming the fluoroolefin-based polymer [II] may be used. The ratio of the components is 10 to 70% by weight of a fluoroolefin, 30 to 90% by weight of the fluoroolefin and another copolymerizable monomer (1) and / or another vinyl monomer (2), More preferably, it is controlled to 15 to 60% by weight of a fluoroolefin, and 40 to 85% by weight of the fluoroolefin and another copolymerizable monomer (1) and / or another vinyl monomer (2). You. Further, in order to impart a graft point to the dispersion stabilizer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer or a monomer having a reactive functional group as described above is dispersed in the above-mentioned various organic solvents. The copolymerization can be performed to such an extent that the solubility of the stabilizer is not reduced.

Further, the amount of the dispersion stabilizer used as a solid content,
It is preferably in the range of 2 to 400 parts by weight, more preferably 5 to 300 parts by weight, per 100 parts by weight of the total amount of the monomers forming the hydroxyl group-containing fluoroolefin copolymer [I].

In preparing the non-aqueous polymer dispersion according to the present invention, a known and commonly used radical polymerization initiator is used as a polymerization initiator to be used. Representative examples of such a polymerization initiator include azobisisobutyronitrile, Azo compounds such as azobisisovaleronitrile; tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-
Butylperoxy-2-ethylhexanoate, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, etc. Of peroxide.

The amount of the radical polymerization initiator used is appropriately determined depending on the type of the polymerization initiator, the polymerization temperature, the molecular weight of the copolymer, and the like, but generally, 0.01 to 10 of the total amount of the monomers to be copolymerized.
% By weight.

In the polymerization, the molecular weight can be adjusted by using a chain transfer agent such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol or α-methylstyrene dimer.

In order to prepare a non-aqueous polymer dispersion from each of the monomer components by a non-aqueous dispersion polymerization method, the monomers and the polymerization initiator are continuously fed into a reactor charged with a solvent and a dispersion stabilizer, respectively. Solvent added to or dispersed in,
Dispersion stabilizer, the remaining monomers and the polymerization initiator are continuously or separately added to a reactor charged with a part of the monomers and a part of the polymerization initiator, a solvent and Monomers, a polymerization initiator and the remaining dispersion stabilizer are added to a reactor charged with a part of the dispersion stabilizer continuously or separately, respectively. A method such as adding the monomers, the polymerization initiator and the dispersion stabilizer continuously or dividedly can be applied.

In the preparation of the non-aqueous polymer dispersion described above, the reaction temperature and the reaction pressure are appropriately selected depending on the type of the polymerization initiator and the polymerization solvent, the molecular weight of the objective copolymer, but the reaction temperature is 0 to 140 ° C., preferably 40 to 100 ° C. is employed, and the reaction pressure is usually 100 kg / cm ² or less.

Next, the curing agent having reactivity with the hydroxyl group of the fluoroolefin copolymer [I] used in the present invention will be described.

As the curing agent component, any of conventionally known curing agents can be used, and specifically, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylcyclohexane- Diisocyanates such as 2,4- (or 2,6-) diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate) or 1,3-di (isocyanatomethyl) cyclohexane; triisocyanates such as 4-isocyanatomethyloctamethylene diisocyanate Isocyanates: the diisocyanates and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or hydroxyl-containing polyether A polyisocyanate resin obtained by reacting a polyhydroxy compound such as ter; a polyisocyanate resin having a burette bond obtained by reacting the diisocyanate with water or an isocyanate obtained by cyclopolymerizing the diisocyanate Polyisocyanate resins having a nullate ring;
Amino resins such as methyl etherified methylol melamine, n-butyl etherified methylol melamine, n-butyl etherified benzoguanamine; the above polyisocyanates or polyisocyanate resins having an active hydrogen such as alcohol, phenol, methyl ethyl ketoxime or ε-caprolactam A blocked isocyanate obtained by blocking with a compound; a polyvalent metal alkoxide such as tetrabutoxytitanium, tributoxyaluminum or tetrabutoxyzirconium; and reacting the polyvalent metal alkoxide with a chelating agent such as acetylacetone or ethyl acetoacetate. The resulting polyvalent metal chelate compound includes a polycarboxylic anhydride such as trimellitic anhydride or pyromellitic anhydride.

When such a curing agent is blended, the amount of the curing agent is suitably in the range of 1 to 100 parts by weight of the solid content of the curing agent component based on 100 parts by weight of the solid content of the non-aqueous polymer dispersion.

The thus obtained non-aqueous dispersion type resin composition of the present invention can be used as such, or as a curing agent, a pigment, or a filler as described above, which can react with a hydroxyl group in the fluoroolefin copolymer [I], which is an essential component of the composition. It can be used for paints, sealing agents, films, etc. by blending agents, curing catalysts and the like.

〔Example〕

Next, the present invention will be described more specifically with reference examples, examples and comparative examples, but the present invention is not limited to these examples. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 sufficiently substituted 1 stainless steel autoclave of ethyl vinyl ether 50 parts by nitrogen (Preparation of dispersion stabilizer), "Beoba 9" (Netherlands Shell Co., vinyl fatty acid having branched alkyl group comprising C ₈ Ester) 300 parts, mineral spirit 300
Part, tert-butyl peroxypivalate 5 parts and tert
-Butyl peroxy-2-ethylhexanoate (5 parts) was charged. Then, 150 parts of liquefied and collected hexafluoropropylene was injected, and the mixture was reacted at 60 ° C. for 15 hours with stirring, then heated to 85 ° C. and reacted for 4 hours. The nonvolatile content (NV) was 59.8%, (G.Vis.) A resin solution having ST, heptane tolerance (HT) 2,000% or more and Gardner color (GC) 1 or less was obtained. Hereinafter, this is abbreviated as dispersant (a-1).

Reference Example 2 (same as above) n-butyl vinyl ether was placed in the same reactor as in Reference Example 1.
50 parts, 4-hydroxybutyl vinyl ether 10 parts, vinyl laurate 290 parts, "LAWS" (manufactured by Shell, The Netherlands, white spirit containing 29.5% by volume of an aromatic component)
300 parts, 50 parts of toluene, 5 parts of tert-butyl peroxypivalate and 2.5 parts of tert-butyl peroxy-2-ethylhexanoate were charged. Then, after injecting 150 parts of liquefied and collected chlorotrifluoroethylene, the reaction was carried out in the same manner as in Reference Example 1 to obtain NV 55.8%, G.Vis.
A resin solution having an HT of 1800%, a GC of 1 or less, and a hydroxyl value (OHV) of 5.4 was obtained. Hereinafter, this is abbreviated as dispersant (a-2).

Reference Example 3 (same as above) In the same reactor as in Reference Example 1, 232 parts of "Vova 9", 8 parts of monovinyl adipate, "ISOPAR E"
(A mixture of fatty acids and hydrocarbons manufactured by Exxon, USA; bp = 115
-142 ° C) 300 parts, toluene 50 parts, tert-butylperoxypivalate 4 parts and tert-butylperoxy-2-
4 parts of ethyl hexanoate were charged. Then, after injecting 160 parts of liquefied and collected hexafluoropropylene,
The same reaction as in Reference Example 1 was carried out, and NV50.7%, G.Vis.M
A resin solution having -N, HT1800%, GC1 or less, and an acid value (AN) of 3.3 was obtained. Hereinafter, this is abbreviated as dispersant (a-3).

Next, 500 parts of the dispersant (a-3) thus obtained and a carboxyl group in the dispersant (a-3) were placed in one reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube. Glycidyl methacrylate 4.2
Part, 2-methylimidazole 0.5 part and hydroquinone
0.5 part was charged and the temperature was raised to 130 ° C. with stirring, followed by a reaction at the same temperature for 6 hours to add glycidyl methacrylate to the dispersant (a-3), and the reaction was carried out by pursuit of AN. . Thus, NV51.1%,
A resin solution containing G.Vis.N, HT1600%, GC9, and AN1 or less was obtained. Hereinafter, this is abbreviated as dispersant (b-1).

Further, 400 parts of the dispersant (b-1) thus obtained was charged into a similar reactor, and the mixture was heated to 65 ° C. while stirring under a nitrogen atmosphere. Then, 50 parts of vinyl acetate and vinyl propionate were added at the same temperature. A mixture of 50 parts, 70 parts of toluene, 10 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 7.5 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise over 3 hours, After completion of the dropwise addition, the mixture was reacted at the same temperature for 5 hours, then heated to 90 ° C. and reacted for 3 hours to convert vinyl acetate and vinyl propionate into a dispersant (b).
-1), NV51.0%, G.Vis.MN,
A resin solution of HT1000% and GC10 was obtained. Hereinafter, this is abbreviated as dispersant (c-1).

Reference Examples 4 to 6 (Preparation Agent for Non-Aqueous Polymer Dispersion) In a stainless steel autoclave sufficiently substituted with nitrogen, a part of the solvent and the dispersion stabilizer as shown in Table 1 were charged and stirred for 60 minutes. C., and then the monomers, the polymerization initiator and the mixture of the remaining solvent were each added dropwise over 3 hours (hexafluoropropylene and chlorotrifluoroethylene among the fluoroolefins were liquefied and sampled). After the addition, tetrafluoroethylene was injected without liquefaction.) After the completion of the dropwise addition, the reaction was continued at the same temperature for 10 hours.
The reaction was carried out at 4 ° C. for 4 hours to obtain non-aqueous polymer dispersions D-1 to D-3 having good properties and no generation of blocks having the properties shown in Table 1.

Examples 1 to 4 The non-aqueous polymer dispersions, curing agents, curing catalysts and coloring materials shown in Table 1 were blended in the proportions shown in Table 2 and diluted with mineral spirit to an air sprayable viscosity. Each coating composition was prepared (the coating non-volatile components of the prepared coating compositions are shown in Table 2).

Then, an acrylic-urethane-based white coating film [base polymer, methyl methacrylate / ethyl acrylate / β-hydroxyethyl methacrylate /
Acrylic acid = 30/59/10/1 (weight ratio) isocyanate-cured coating film, pigment-rutile-type titanium oxide] coated zinc phosphate treated steel sheet (0.8 mm thick) The composition was spray-coated and cured under the conditions shown in Table 2 to obtain a (cured) coating film.

The coating film thus obtained was evaluated for the finished state of the coated surface, such as “chummy” or “blow”, and further exposed to a sunshine weatherometer for 4000 hours to examine the change in gloss. The results are shown in Table 2.

Comparative Example 1 A copolymer having the same composition as the fluoroolefin copolymer [I], which is a dispersion of the non-aqueous polymer dispersion D-1 used in Example 1, was prepared in methyl isobutyl ketone by a solution polymerization method. (NV 57.1%, G.Vis. Z-Z ₁ ), and a white paint was obtained with the same paint formulation as in Example 1. At this time, the nonvolatile matter of the coating was 33.2%. Thereafter, the same operation as in Example 1 was performed, and as a result, the finished state of the coated surface was "bulging", which was poor. The accelerated weather resistance test was not performed for the defective coating film.

Comparative Example 2 A copolymer having the same composition as the fluoroolefin copolymer [I], which is a dispersion of the non-aqueous polymer dispersion D-3 used in Example 4, was prepared in methyl ethyl ketone by a solution polymerization method ( NV51.5%, G.Vis. XY), and a mixed paint of white and red was obtained with the same paint formulation as in Example 4. At this time, the nonvolatile matter of the coating was 32.0%. Thereafter, the same operation as in Example 4 was performed, and as a result, the finished state of the coated surface was "bulging", which was poor. The accelerated weather resistance test was not performed for the defective coating film.

[Effect of the Invention] The fluoroolefin of the present invention and a vinyl monomer containing a hydroxyl group are used as essential monomer components, and the fluoroolefin copolymer [I] prepared from the monomer mixture is not dissolved. Non-aqueous dispersion type resin composition comprising, as an essential component, a non-aqueous polymer dispersion obtained by non-aqueous dispersion polymerization in an organic solvent in the presence of a dispersion stabilizer capable of dissolving or swelling in the organic solvent. As the product, it is possible to use an organic solvent having low optical reactivity and low solubility whose use in conventional hydroxyl group-containing fluoroolefin copolymers is restricted in terms of solubility. Therefore, the non-aqueous dispersion type resin composition of the present invention has the above-mentioned properties of the organic solvent to be used, that is, low pollution due to properties such as low photochemical reactivity and low solubility, and does not attack the undercoat film. It has excellent features. Further, in the non-aqueous polymer dispersion liquid which is an essential component of the non-aqueous dispersion type resin composition of the present invention, the viscosity is relatively low even if the polymer is of a high molecular weight type or a high nonvolatile type. The non-aqueous dispersion type resin composition of the present invention has excellent workability, such as being capable of coating a thick film, hardly sagging and reducing the amount of a volatile solvent used.

As described above, the non-aqueous dispersion type resin composition of the present invention is extremely useful for various uses such as coatings, sealing agents, and films.

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08F 218: 04) (56) References JP-A-61-272212 (JP, A) JP-A-62-292814 (JP, A) JP-A-61-19602 (JP, A) JP-A-62-116605 (JP, A) JP-A-62-243603 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 214/00-214/28 C08F 2 / 14,2 / 44 C08F 251/00-292/00 C08L 27/12-27/24

Claims (9)

(57) [Claims] 1. A monomer comprising a fluoroolefin and a vinyl monomer having a hydroxyl group as essential monomer components and, if necessary, other copolymerizable monomers. The mixture is a fluoroolefin copolymer [II] which can be dissolved or swelled in an organic solvent obtained from the monomer mixture and which does not dissolve the hydroxyl group-containing fluoroolefin copolymer [I]. A non-aqueous dispersion type resin composition comprising, as an essential film-forming component, a non-aqueous polymer dispersion obtained by non-aqueous dispersion polymerization in the presence of a dispersion stabilizer. 2. A monomer comprising a fluoroolefin and a vinyl monomer having a hydroxyl group as essential monomer components and, if necessary, further containing other copolymerizable monomers. The mixture is obtained from the monomer mixture, and is composed of a fluoroolefin-based polymer [II] that can be dissolved or swelled in the organic solvent in an organic solvent that does not dissolve the hydroxyl group-containing fluoroolefin copolymer [I]. In the presence of a dispersion stabilizer, a non-aqueous polymer dispersion obtained by non-aqueous dispersion polymerization, and a curing agent having reactivity with hydroxyl groups, characterized by containing as an essential film-forming component , A non-aqueous dispersion type resin composition. 3. A dispersion stabilizer mentioned above is -1: vinyl esters of aliphatic monocarboxylic acids having a fluoroolefin with an alkyl group of C ₄ -C _17, cyclohexanecarboxylic acid vinyl, C ₂ -C ₁₈ Other vinyl-based monomers (hereinafter, referred to as vinyl-based monomers) containing at least one selected from the group consisting of alkyl vinyl ethers having an alkyl group and cycloalkyl vinyl ethers as main components and copolymerizable therewith, if necessary. -1): copolymers obtained by copolymerizing monomer (2)), -1: unsaturated bond-containing polyolefin-based polymers, fluoroolefins and vinyl-based monomers (2) Graft copolymers obtained by copolymerizing at least one selected from the group consisting of: -2, -2: among the dispersion stabilizers of -1 and -1, respectively, Each unsaturated bond-containing copolymer obtained by subjecting a carboxyl group of a copolymer having a ruboxyl group to an addition reaction with an unsaturated bond-containing epoxy compound, -3, -3: each of the above-mentioned -1,- 1 among the respective dispersion stabilizers, each unsaturated bond-containing copolymer obtained by subjecting a monomer having a carboxylic anhydride group to an addition reaction to a hydroxyl group of a copolymer having a hydroxyl group, -4, -5: each above -2, each unsaturated bond-containing copolymers of -3, the graft obtained by copolymerizing a vinyl carboxylate having an alkyl group of C ₁ -C ₃ 2. At least one member selected from the group consisting of copolymers.
Or the composition according to 2. 4. The fluoroolefin copolymer [I] comprises (i) 15 to 70 parts by weight of a fluoroolefin,
(Ii) 1 to 40 parts by weight of a hydroxyl group-containing vinyl monomer and (iii) 0 to 84 parts by weight of other copolymerizable monomers so that the total amount is 100 parts by weight. The composition according to claim 1, 2 or 3, which is obtained by copolymerization. 5. The above-mentioned fluoroolefin copolymer [I], wherein the above-mentioned fluoroolefin (i) is
Selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and (per) fluoroalkyl trifluorovinyl ether having an alkyl group of C _{1 to} C ₁₈ , At least one
The composition according to claim 4, which is obtained by using a compound of a kind. 6. The fluoroolefin copolymer [I] is an alkyl vinyl ether having a C ₂ -C ₁₈ alkyl group, a cycloalkyl vinyl ether, a C ₁
-C ₁₇ comprising carboxylic acid vinyl esters having an alkyl group, vinyl benzoate, selected from p-tert-butylbenzoic acid vinyl and cyclohexane carboxylic acid group consisting of vinyl, those obtained by using at least one compound 4. The composition according to claim 1,2 or 3, wherein 7. The fluoroolefin copolymer [I] is a fluoroolefin copolymer containing 20 to 60% by weight of a fluoroolefin, and the dispersion stabilizer contains 15 to 60% by weight of a fluoroolefin. The composition according to any one of claims 1 to 6, which is a fluoroolefin-based polymer. 8. The composition according to claim 1, wherein the dispersion stabilizer is a polymer having a polymerizable double bond. 9. The method according to claim 2, wherein the curing agent having reactivity with a hydroxyl group is at least one compound selected from the group consisting of a polyisocyanate compound, a blocked polyisocyanate compound and an amino resin. A composition according to any one of the preceding claims.