JPS61272212A - Production of solvent-soluble type fluorine-contained resin having improved pigment dispersion - Google Patents

Abstract

PURPOSE:To obtain the titled resin having improved pigment dispersion without damaging high weather resistance of fluorine-contained resin, by polymerizing a vinyl monomer mixture comprising a fluoroolefin as an essential compound in the presence of a polymerizable double bond-containing polymer. CONSTITUTION:In the presence of a polymerizable double bond-containing polymer, a vinyl monomer mixture containing preferably 20-50mol% based on the total amount of the vinyl monomer mixture of a fluoroolefin (preferably tetrafluoroethylene, etc.) as an essential component, to give the aimed resin. A double bond-containing acrylic resin obtained by copolymerizing a hydroxyl group-containing vinyl monomer with another copolymerizable vinyl monomer is preferable as the polymerizable double bond-containing polymer. The polymerization of the vinyl monomer mixture in the presence of the polymer is preferably carried out at -20-130 deg.C at 5-60kg/cm<2> by solution pressure polymerization method.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a solvent-soluble fluororesin with improved pigment dispersibility, and more particularly, to a method for producing a solvent-soluble fluororesin using a polymerizable double bond-containing polymer. This invention relates to a method for producing a modified fluororesin, and its purpose is to provide a new and useful method for producing a modified fluororesin that can be widely used in paint resins, sealing resins, and the like.

[Prior art and problems to be solved by the invention]
Although solvent-soluble fluororesins are already known and have been disclosed in Japanese Patent Application Laid-open Nos. 57-34107, 59-102961, and 59-102962, paints made into paints according to such known techniques are Although pigment dispersibility is good for white pigments such as titanium oxide, there are difficulties in pigment dispersibility for other inorganic pigments and organic pigments, such as phenomena such as aggregation and separation of paint solutions. However, it is difficult to say that it is satisfactory.

On the other hand, in order to eliminate the above-mentioned drawbacks,
In inventions such as those described in Publication No. 46964, a modified fluororesin in which a vinyl monomer is polymerized in the presence of a polymerizable double bond-containing fluororesin has been proposed. A detailed examination of modified fluororesin revealed that although it is relatively good for inorganic pigments such as cardan plaque, it does not have sufficient pigment dispersibility for organic pigments. This is the current situation.

[Means for solving problems]

However, in view of the various drawbacks in the prior art as described above, the present inventors have made efforts to obtain a modified fluororesin with good pigment dispersibility without impairing the high degree of weather resistance of such fluororesin. As a result of the study, it was found that a modified fluororesin obtained by polymerizing a mixture of vinyl monomers containing fluoroolefin as an essential component in the presence of a polymer solution having polymerizable double bonds was found to contain inorganic pigments and organic pigments. The present invention has been completed based on the discovery that pigments have good dispersibility regardless of the type of pigment.

That is, the present invention provides a solvent-soluble type with particularly improved pigment dispersibility, which consists of polymerizing a vinyl monomer containing a fluoroolefin as an essential component in the presence of a polymer having a polymerizable double bond. The present invention provides a method for producing a fluororesin.

First, representative examples of the above-mentioned polymers having polymerizable double bonds include acrylic resins, alkyd resins, and oil-free alkyd resins having polymerizable double bonds, which are suitable from the viewpoint of pigment dispersibility. used for.

All of these polymers may be prepared according to conventional methods, and the method for introducing double bonds is, for example, in the case of addition polymerization polymers, hydroxyl groups are introduced in advance into the polymer to be obtained, and then this In the case of a method in which a double bond is introduced by adding an acid anhydride group-containing monomer such as maleic anhydride or itaconic anhydride to a hydroxyl group, or in the case of a condensation polymer, this method is used as a reaction raw material. Particularly effective is a method in which a material having a polymerizable double bond is used to directly introduce the double bond into the resin.

That is, in order to prepare an acrylic resin having double bonds, it is sufficient to first copolymerize a hydroxyl group-containing vinyl monomer and another vinyl monomer that can be copolymerized with it, and on the other hand,
To prepare alkyd resins having double bonds and oil-free alkyd resins, they must be obtained in advance according to well-known and commonly used synthetic methods. An alkyd resin obtained by using a fatty acid having a polymerizable double bond may be subjected to an addition reaction with a monomer containing a suspended acid anhydride group to the hydroxyl group of the polyester component. The acid anhydride group-containing monomer may be used as it is without being added to the hydroxyl group.

Among them, representative examples of the above-mentioned hydroxyl group-containing vinyl monomers include 2-hydroxyethyl (meth)acrylate,
2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate
acrylate), 3-chloro-2-hydroxypropyl (
hydroxyalkyl esters of (meth)acrylic acid such as meth)acrylate or polyethylene glycol mono(meth)acrylate; combinations of acid anhydride group-containing monomers such as maleic anhydride or itaconic anhydride and glycols such as ethylene glycol; (ethylenically unsaturated) double bond-containing hydroxyalkyl esters such as adducts; dihydroxyalkyl esters of polyhydric caldic acids such as maleic acid or fumaric acid containing (ethylenically unsaturated) double bonds; Examples include polyhydroxyalkyl esters; or hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether; representative examples of other vinyl monomers that can be copolymerized with such hydroxyl group-containing monomers include methyl (meth);
Acrylate, ethyl (meth)acrylate, butyl (
(Meth)acrylic acid esters such as meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate or benzyl (meth)acrylate: unsaturated dicarboxylic acids such as maleic acid, hexamaric acid or itaconic acid and methanol , diesters with monohydric alcohols such as ethanol or butanol; various vinyl esters such as vinyl acetate, vinyl benzoate or "Peova" (vinyl persate acid manufactured by Shell, Netherlands); "Viscoat 8";
F, 8FM, 3F or 3FMJ (Osaka Organic Chemistry)
(meth)acrylate monomer having a fluorine atom in the side chain], fluorocyclohexyl (meth) manufactured by Co., Ltd.
vinyl esters containing (per)fluoroalkyl groups, such as acrylate, non-perfluorocyclohexyl fumarate or N-i-so-glopyrno-4-fluorooctanesulfonamidoethyl (meth)acrylate; vinyl chloride, vinylidene chloride, ethylene or propylene; α-olefins such as styrene, α-methylstyrene, p-tart-butylstyrene, 0-methylstyrene or p-methylstyrene; (meth)acrylic acid, crotonic acid, maleic acid , carboxylic group-containing monomers or dicardic acids such as fumaric acid, itaconic acid or citraconic acid; acid anhydride group-containing monomers such as depleted monomers; (meth)acrylamide, N,N-dimethyl (meth)acrylamide, Carboxylic acid amide group-containing monomer a such as N-alkoxymethylated (meth)acrylamide, diacetone acrylamide or N-methylol (meth)acrylamide a: p-styrenesulfonamide, N-methyl-p-styrenesulfonamide or N , N-dimethyl-p-
Sulfonic acid amide group-containing monomers such as styrene sulfonamide: N,N-dialkylaminoalkyl (such as N,N-dimethylaminoethyl (meth)acrylate)
meth)acrylates or monomers containing an acid anhydride group such as dehydrated monomers and a compound having both an active hydrogen and a tertiary amino group capable of reacting with the acid anhydride group such as N,N-dimethylaminopropylamine. Tertiary amino group-containing monomers such as adducts; cyano group-containing monomers such as (meth)acrylonitrile; (ethylenically unsaturated) double bond-containing monomers such as (meth)acrylic acid hydroxyalkyl ester; Monomers having a phosphoric acid ester bond obtained by condensation reaction of phosphoric acid or saturated carboxylic acid with phosphoric acid or phosphoric acid esters; or monomers of 2-acrylamido-2-methyl-propanesulfonic acid. Examples include sulfonic acid group-containing monomers such as sulfonic acid group-containing monomers or organic amine salts thereof.

The amount of the hydroxyl group-containing monomer to be copolymerized varies depending on the molecular weight of the resulting vinyl copolymer resin, for example, acrylic resin, but is approximately 10% of the total copolymer resin component.
~50]! It is desirable that the copolymerizable vinyl monomer accounts for 1% of the copolymerizable vinyl monomer.

To prepare the above-mentioned hydroxyl group-containing vinyl copolymer resin, any known method such as solution polymerization method or solution pressure polymerization method may be used, but among them, solution radical polymerization method is the simplest and most suitable. . Typical solvents used in this case include hydrocarbons such as toluene, xylene, cyclohexane, n-hex/octane;
Solvents such as esters such as methyl acetate, ethyl acetate or gtylacetate; ketones such as acetone, methyl ethyl ketone, methyl imbutyl ketone, cyclohexano/or methyl amyl ketone; or amides such as dimethylformamide or dimethylacetamide;
Or a mixture of these.

Polymerization may be carried out in a conventional manner using such a solvent and various polymerization initiators such as azo or peroxide.

Further, in this case, a known and commonly used chain transfer agent such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol or α-methylstyrene dimer can also be used as a molecular weight regulator.

Next, the hydroxyl group-containing vinyl copolymer thus obtained is subjected to an addition reaction with an acid anhydride group-containing monomer as described above to obtain the desired polymerizable double bond-containing polymer, but the reaction is carried out at room temperature. This may be carried out at a temperature of from 150° C. to about 150° C. for 2 to 5 hours.

Here, the amount of the acid anhydride group-containing monomer to be added depends on the molecular weight of the hydroxyl group-containing vinyl copolymer that is the precursor, but there is one polymerizable double bond in one molecule of the polymer. It is appropriate that they be used in a proportion that is within the range of .about.3.

° On the other hand, typical polybasic acid components used in preparing alkyd resins having polymerizable double bonds and oil-free alkyd resins include isophthalic acid, terephthalic acid, orthophthalic acid, and 2.6- Natsutale dicarzanic acid, 4,4'-dubuenyl radical? acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid acids, adipic acid, azelaic acid, pimelic acid, superric acid, sepacic acid or dimeric fatty acids (dimer acids), trimesic acid, trimellitic acid, pyromellitic acid or cyclohexanetetracargenic acid, or alkyl esters thereof There are reactive derivatives such as anhydrides and anhydrides.

Typical examples of glycol components used in preparing the polyester component include ethylene glycol, propylene gelicol, trimethylene glycol, 1,4-butanediol, 1.3-butanediol, and 1.5-butanediol. -Alkylene glycols such as bentanediol, 1,6-hexanediol or neopentyl glycol, or optionally 1,4-
Aromatic or alicyclic glycols such as cyclohexane dimetatool, bishydroxyethyl terephthalate, or alkylene oxide adducts of (hydrogenated) bisphenol A can also be used, and monoepoxy compounds can also be used in combination as such glycol components. Of course it's scales.

Furthermore, as trivalent or higher polyol components, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, or mannitol, or polyester obtained by adding 6-caprolactone to the various glycol components listed above. Typical examples include compounds.

Furthermore, typical (unsaturated) fatty acids used in obtaining alkyd resins include octyl acid, palmitic acid, stearic acid, persatic acid, oleic acid, linoleic acid, or lyluic acid, as well as palm acid. Long chain monobases of 08 or more such as oil fatty acids, hydrogenated coconut oil fatty acids, tall oil fatty acids, castor oil fatty acids, rice bran oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, safflower oil fatty acids or dehydrated castor oil fatty acids These (unsaturated) fatty acids, such as acids, are appropriately selected in consideration of solubility in solvents, weather resistance of the coating film, economic efficiency, and the like.

In order to prepare the desired solvent-soluble fluororesin using the thus obtained polymer having a polymerizable double bond and a fluoroolefin as described below, it is necessary to A mixture of vinyl monomers containing a fluoroolefin as an essential component may be polymerized in the presence of the vinyl monomer.

The amount of this polymerizable double bond-containing polymer to be used is 0.1 to 50% by weight relative to 99.9 to 50% by weight of the vinyl monomer mixture that essentially tosses the other fluoroolefin. Appropriate.

If the amount of the polymerizable double bond-containing polymer is less than 0.1% by weight, pigment dispersibility will be lacking, and if it exceeds 50% by weight, the desired fluororesin will have poor weather resistance. Both are unfavorable because they make it difficult to obtain the desired characteristics.

Here, first, representative examples of the fluoroolefins include fluorine-containing α-olefins such as fluoroethylene, vinylidene fluoride, trifluoroethylene, tetrahydroethylene, and chlorotrifluoroethylene, such as hexafluoropropylene; Compounds having a fluorine atom in the main chain, such as trifluoromethyl trifluorovinyl ether or heptafluoroprobyl trifluorovinyl ether, etc., include tetrafluoroethylene, vinylidene fluoride, The use of chlorotrifluoroethylene or hexafluoropyrene is preferred.

Of course, such fluoroolefins may be used alone or in combination of two or more.

The amount of the fluoroolefin to be used is suitably within the range of 10 to 60 molt, preferably 20 to 50 molt, based on the total amount of the mixture of the fluoroolefin and other copolymerizable vinyl monomer. C, 60
If it exceeds molti, IO" will occur in the resulting solvent-soluble fluororesin, and the desired solvent-soluble fluororesin will lack compatibility with the curing agent, and on the other hand, If the amount is less than 10 moles, it will be difficult for the solvent-soluble fluororesin, which is the target product of the method of the present invention, to exhibit its excellent properties such as chemical resistance and weather resistance. Not preferred. Typical examples of other vinyl monomers that can be copolymerized with the fluoroolefin include cargenate vinyl esters, hydroxyalkyl vinyl ethers, and alkyl vinyl ethers. Typical examples include linear or vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl casilonate, vinyl caprate, vinyl caprate, vinyl persate, vinyl laurate, or vinyl stearate. Vinyl esters of branched aliphatic carboxylic acids; cycloaliphatic vinyl esters of vinyl cyclohexanecarboxylate; or vinyl benzoate;
Examples include aromatic vinyl esters such as vinyl p-tert-butylbenzoate and vinyl salicylate.

Second, specific examples of the above-mentioned hydroxyalkyl vinyl ether include hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, etc., and specific examples of the above-mentioned alkyl vinyl ether include U-methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-
ff rubinyl ether s 1so-butyl vinyl ether or tert-butyl vinyl ether and the like.

Furthermore, other nonhinyl monomers that can be copolymerized with fluoroolefins include α-olefins such as ethylene, propylene, or butene-1; vinyl chloride or vinylidene chloride, and other vinyl halides (vinylidene ): Aromatic vinyl compounds such as styrene, α-methylstyrene or vinyltoluene; Mono- or diesters of (ethylenically unsaturated) double bond-containing polybasic acids such as maleic acid or hexamaric acid; ( Nitrogen-containing vinyl compounds such as meth)acrylonitrile, (meth)acrylamide, N-methylolated (meth)acrylamide or N-1 toxymethyl(meth)acrylamide; or (ethylenic vinyl compounds such as (anhydrous) maleic acid or (anhydrous) itaconic acid) (Unsaturated) double bond-containing (anhydrous) polybasic compounds can also be used, and allyl alcohol or allyl glycidyl ether can also be used.

In carrying out the method of the present invention, a mixture of vinyl monomers containing the above-listed fluoroolefins as an essential component is mixed in the presence of various polymerizable double bond-containing polymers as listed above. As a method for polymerization, a polymerizable double bond-containing polymer is charged in advance into a reaction vessel, and then a vinyl monomer mixture containing fluoroolefin as an essential component is subjected to bulk polymerization or solution polymerization in the presence of a radical polymerization initiator. Batch, semi-continuous or continuous operations may be carried out according to known and commonly used techniques such as (pressure) polymerization.

Here, typical examples of the radical polymerization initiator include diacyl z4-oxides such as acetyl peroxide or pensoyl peroxide; ketone peroxides such as methyl ethyl ketone oxide or cyclohexanone peroxide;
Hydrogen peroxides such as hydrogen peroxide, tert-butyl hydroperoxide or cumenohydrono-oxide; dialkyl peroxides such as di-tert-butyl peroxide: tert-butyl peroxide;
azo compounds such as azobisisobutyronitrile or azobisinvaleronitrile; Sulfates; or tsucumyl peroxide, etc., but if necessary, it may be used in combination with an inorganic reducing agent such as sodium bisulfite or sodium pyrosulfite, or an organic reducing agent such as cobalt naphthenate or dimethylaniline. .

Among the various known and commonly used methods mentioned above as a method for such a copolymerization reaction, the solution pressure polymerization method is simple and simple;
Typical solvents that are particularly desirable for carrying out the method of the present invention include:
In addition to the above-mentioned various solvents used in the preparation of polymerizable double bond-containing polymers, especially in preparing hydroxyl group-containing vinyl copolymer resins, methanol, ethanol, 1so-gulononol, n- Butanol, l5
Examples include alcohol solvents such as o-butanol, 5ee-butanol, and ethylene glycol monoalkyl ether, and it goes without saying that two or more types may be used in combination.

Furthermore, in such copolymerization, various chain transfer agents such as those mentioned above can be used as molecular weight regulators.

Furthermore, the reaction temperature in such copolymerization is suitably within the range of -20°C to 130°C, and the reaction pressure is 1 to 100 cm/crn2, preferably 5 to 6 cm.
A range of 0'Kll/cm2 is appropriate.

Thus, the number average molecular weight of the modified fluororesin obtained according to the method of the present invention is suitably in the range of 5,000 to 30,000, and the hydroxyl value is suitably in the range of O to 200.

That is, when the modified fluororesin obtained according to the method of the present invention is used as a so-called lacquer composition without using a curing agent, the hydroxyl value may be 0;
When such a modified fluororesin is used as a curable composition together with a curing agent that is reactive with the hydroxyl groups in the resin,
Those having a hydroxyl value within the range of 5 to 200 are suitable.

The solvent-soluble fluororesin modified by the polymerizable double bond-containing polymer thus obtained can be mixed with various inorganic or organic pigments to form a paint and used as is, or
Alternatively, a cured coating film can be obtained by drying at room temperature in combination with a curing agent that is reactive with hydroxyl groups, or by baking.

The modified fluororesin obtained by the method of the present invention can be used in a wide range of applications including coating resins and sealing resins.

〔Example〕

Next, the present invention will be specifically explained using reference examples, working examples, comparative examples, applied examples, and comparative applied examples. In the following, all parts and parts are based on weight unless otherwise specified. .

Reference Example 1 (Example of Preparation of Polymerizable Double Bond-Containing Polymer) 400 parts of toluene, 200 parts of butyl acetate, and methyl methacrylate were placed in a reactor equipped with a stirring device, a thermometer, a nitrogen inlet tube, and a reflux condenser. 100 parts, 77.4 parts of ethyl acrylate, 2 parts of β-hydroxyethyl methacrylate
0 parts, 0.2 parts of "Light Ester PM J (phosphoric acid ester monomer manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), 0.4 parts of dimethylamine ethyl methacrylate, 2 parts of methacrylic acid, and tart-petite". Two parts of luperoxyoctate were charged, the temperature was raised to 90° C. in a nitrogen atmosphere, and the temperature was further maintained at the same temperature for 2 hours.

Next, at the same temperature, 400 parts of methyl methacrylate, 309.6 parts of ethyl acrylate, 80 parts of β-hydroxyethyl methacrylate, [Ditoester PM J
0.8 parts of dimethylaminoethyl methacrylate, 1 part of dimethylaminoethyl methacrylate
．． 6 parts, 8 parts of methacrylic acid, 200 parts of butyl acetate,
A mixture of 3 parts of tert-butyl peroxybenzoate and 5 parts of azobisisobutyronitrile t-
It was allowed to drip for 3 hours.

Immediately after the addition, the temperature was raised to 110°C and 3 parts of tert-butyl peroxyoctate and 20 parts of toluene were added.
After adding 0 part of the solution and maintaining the same temperature for 15 hours, a polymer solution with a nonvolatile content (NV) of 50%, a hydroxyl value of 21.6, and a number average molecular weight of 20,000 was obtained. . Next, the temperature of this polymer solution was lowered to 60°C, 9.8 parts of maleic anhydride and 9.8 parts of toluene were added, and the temperature was raised to 100°C and maintained at the same temperature for 5 hours.
A target polymer having a hydroxyl value of 50% and a hydroxyl value of 18.6 was obtained. Hereinafter, this will be abbreviated as polymer (a-1).

Reference Example 2 (same as above) 215 parts of adipic acid, 400 parts of hexahydrophthalic anhydride, and trimethylol 7'O
/4'n, 50 parts of ethylene glycol and 390.2 parts of neopentyl glycol,
The temperature was gradually raised to 230 t over 5 hours in a nitrogen stream, maintained at the same temperature until the acid value reached 10, and then the reaction system was cooled to below 100°C, and 250 parts of xylene was added to the oil. A solution of free alkyd resin was obtained. This material has a W of 80, a water group of 88.8, and a number average molecular weight of 1.
It was 010.

Next, this resin solution was cooled to 60°C, 147 parts of mannic anhydride and 36.8 parts of xylene were added, and 1
When the temperature was raised to 00° C. and the reaction was carried out by maintaining the same temperature for 5 hours, a desired polymer having a hydroxyl value of 80% and a hydroxyl value of 18.7 was obtained. Hereinafter, this will be abbreviated as polymer (a-2).

Examples 1 to 3 The polymer obtained in Reference Example 1 (
a-1), polymer (a-2) obtained in Reference Example 2, commercially available "Beccosol P-470-704 [Dainippon Ink Chemical Co., Ltd., alkyd resin with oil length of 65 using soybean oil] : NV=70%) and the solvent methyl isobutyl ketone in the proportions shown in Table 1, and further added ethyl vinyl ether (EVE), hydroxybutyl vinyl ether (HBVE), rPeova 9 J (C, (vinyl ester of tic acid), vinyl benzoate (VBz), and Tsuku-butyl PVJ (radical polymerization initiator manufactured by NOF Corporation) were added in predetermined amounts, and then incubated in a dry ice/methanol bath for 70 min.
The reactor was cooled to 0.degree. C. and nitrogen gas was blown into the reactor to replace the air inside the reactor.

Afterwards, the liquefied hexafluoropropylene (
RFP ) and chlorotrifluoroethylene (CTF
E) 'i A predetermined amount was charged and the inside of the vessel was sealed.

On the other hand, when using tetrafluoroethylene (TFE), use a pressure-resistant tube with pulp, repeat the same operation as above, and then pour this TFE into a cylinder at the stage of charging this TFE ft. It was press-fitted, the knob was closed, and it was weighed.

Each autoclave was placed in a rotary constant-temperature water bath heated to 60° C. and reactions were carried out separately for 16 hours, and then the reaction phase □ composition and each modified fluororesin were taken out.

Characteristic values (constant values) for each modified fluororesin
was measured. The results are summarized in the same table.

In addition, the amount of each raw material charged in the same table is shown in parts, and the number of moles is also written in parentheses. In addition, the polymer (a-3
) is “Pe2cozol P-470-70, J, VV-9
shall each mean "Peoba 9".

Comparative Examples 1 to 3 Control unmodified fluororesins were obtained in the same manner as Examples 1 to 3, except that no polymerizable double bond-containing polymer was used.

Those resin characteristic values (constant values) are also summarized in Table 1.

Application Examples 1 to 4 and Comparative Application Examples 1 to 4 For 100 parts of each modified or unmodified fluororesin obtained in Examples 1 to 3 and Comparative Examples 1 to 3,
Pigments and thinners were separately blended in the proportions shown in Table 2, and then kneaded in a sand mill for 1 hour to prepare 6 color pastes.

Each color paste is then prepared as a paint solution by simply diluting it with thinner to a spray viscosity without the addition of a hardening agent, or a prescribed amount of hardening agent as shown in the table is added to each color pace. The solution was then diluted with thinner to a spray viscosity to prepare a paint bath solution.

After that, 0,8■ was degreased with petroleum benzene.
A colored (modified) fluororesin film was obtained by spray painting on a thick mild steel plate and then under drying or curing conditions as shown in the same table.

The degree of gloss of each cured coating film was compared and examined.

The results are summarized in the same table, and the notes in the table are as follows.

(Note 1) Furnace type car manufactured by Mitsubishi Chemical Corporation? This is a black with a pigment concentration (pwc) of 3.
It was used in an amount such that 4.

(Note 2) A cyanine pigment manufactured by Dainippon Ink and Chemicals was used in an amount such that the PWC was 11%.

(Note 3) A red pigment manufactured by Imperial Chemical Industries Ltd., UK, was used so that the PWC was 12.

(Note 4) A yellow pigment manufactured by the same company, with a pwc of 20
%.

(Note 5) Xylene/Toluene/Ethyl acetate/Butyl acetate/Selonlupeacetate) = 40/20/10/20/1
A mixed bath agent having a weight ratio of 0 (weight ratio) was used.

(Note 6) [Spray/I/1000J [: Aromatic hydrocarbon mixture manufactured by Maruzen Oil ■]/n-Pugnol = 70/
A mixed solvent of 30 (weight ratio) was used.

(Note 7) When the kneaded color paste is left at room temperature for one month, if sedimentation, separation, or aggregation of the pigment occurs in the kneaded product, it is evaluated as "x"; The case where no abnormality was observed in the object was evaluated as "◎".

(Note 8) Polyincyanate resin manufactured by Nippon Polyurethane Industry ■; Incyanate content = 21.3%, NY = 1
00%, which is NCO/OH=1
/ 1 (equivalence ratio).

(Note 9) Hexamethyl etherified methylolmelamine resin manufactured by Sumitomo Chemical ■; NV = Zoo%.
This is a (modified) fluororesin/Sumimar M-100CJ = 70/30 (solid content weight ratio)
It was used so that

(Note 10) Curing catalyst manufactured by King, USA (Note 11)
Type A: Dry naturally for 1 week at room temperature Tyzo B: 3 at 60℃
After 0 minutes of forced drying, leave it at room temperature for 5 days Type C: Forced dry at 140°C for 30 minutes (Note 12) 6
0 magic specular reflectance (indicated by @) [Effects of the invention] As shown in Table 2, when the modified fluororesin obtained according to the method of the present invention is kneaded with a pigment, It is known that it provides a stable color pace with no precipitation or agglomeration, and also provides a coating film with excellent gloss.

Attorney: Patent Attorney Katsutoshi Takahashi Procedural Amendment June 2, 1985 Manabu Shiga, Commissioner of the Patent Office1, Indication of the case Patent No. 113060 of 19852, Name of the invention: Improved pigment dispersibility Process for producing solvent-soluble fluoropolymer 3, relationship with the amendment case Patent applicant: 3-35-58 Sakashita, Itabashi-ku, Tokyo 174
8) Dainippon Ink & Chemicals Co., Ltd. Representative Yo Mura
Kuni Shigeru 4, Agent: Dainippon Ink & Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Phone number: Tokyo (03) 272-4511 (Main representative)
8B76) Patent attorney Katsutoshi Takahashi 5, date of amendment order 6, "Detailed explanation of the invention" column 7 of the specification subject to amendment, content of amendment ill page 23, lines 1-2 of the specification The description of 'tert-butyl peroxybenzoate' is '
Corrected to tert-butyl peroxyoctate''J.

(2) Description in lines 5 and 6 of the same page tert-
'butyl peroxyoctate' is corrected to 'tert-butyl peroxybenzoate.

Written amendment to the above procedure July 9, 1985 Michibe Uga, Commissioner of the Patent Office1, Case description 1985 Patent Application No. 1130602, Name of the invention Solvent-soluble fluororesin with improved pigment dispersibility Manufacturing method 3, relationship with the amendment case
88) Dainippon Ink & Chemicals Co., Ltd. Representative: Shigeru Kuni Mura 4, Agent Address: 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Dainippon Ink & Chemicals Co., Ltd. Telephone: Tokyo (03) 272-4511 (Dainippon Ink & Chemicals Co., Ltd.) representative)(
8876) Patent attorney Katsutoshi Takahashi 5, date of amendment order 6, "Detailed description of the invention" column 7 of the specification subject to the amendment, content of the amendment (1) Page 25, line 4 of the specification amend the description as follows.

rOpe 9” (manufactured by Shell in the Netherlands, a parsatie with an alkyl group called C1.

(2) Statement on page 29, line 5 of the specification "Cyanine type" “Corrected to phthalocyanine type j.

(3) "Table 2" on page 32 of the specification is amended as follows.

Claims (1)

[Claims] 1. A method for improving pigment dispersibility, which is characterized by polymerizing a vinyl monomer mixture containing a fluoroolefin as an essential component in the presence of a polymer having a polymerizable double bond. A method for producing solvent-soluble fluoropolymer. 2. Claim 1, wherein the polymer having a polymerizable double bond is at least one resin selected from the group consisting of an acrylic resin, an alkyd resin, and an oil-free alkyd resin. The method described in section. 3. Claim 1, characterized in that the vinyl monomer mixture containing the above-mentioned fluoroolefins as an essential component is a mixture of fluoroolefins, carboxylic acid vinyl esters, hydroxyalkyl vinyl ethers, and alkyl vinyl ethers. The method described in.