JPH0798915B2 - Resin composition for paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel and useful coating resin composition,
More specifically, the present invention relates to a resin composition containing a specific modified fluororesin as an essential component and having particularly good pigment dispersibility.

[Conventional technology]

Solvent-soluble fluororesins are disclosed in JP-A-57-34107, 59-1.
Although it is already well known as disclosed in JP-A Nos. 02961 and 59-102962, the paint prepared according to such a known technique has a pigment dispersibility in a white pigment such as titanium oxide. Although it is relatively good, it is not satisfactory for other inorganic pigments, and in addition for organic pigments, because it has drawbacks in pigment dispersibility, such as phenomena such as aggregation and separation of the coating solution. hard.

On the other hand, Japanese Patent Publication No. 59-
In the invention as described in JP 46964, JP 59-41321 A and JP 59-51953 A, vinyl monomers are polymerized in the presence of a fluororesin containing a polymerizable double bond. Although a modified fluororesin of such a form has been proposed, and such a modified fluororesin is treated as having good pigment dispersibility, it has been verified by the inventors of the present invention that an inorganic pigment such as carbon black is used. However, it was found that the pigment does not have sufficient pigment dispersibility with respect to organic pigments, although it exhibits relatively good pigment dispersibility.

[Problems to be solved by the invention]

Thus, as long as the prior art is followed, the high degree of weather resistance inherent in the fluororesin is inevitably impaired, even though the pigment dispersibility is particularly good, to obtain a novel resin composition for coating, Rather, it seems to be the most difficult technique.

However, in view of the recognition of the present situation and the existence of various drawbacks in the prior art, the present inventors have found that the pigment dispersibility,
In particular, the inventors have earnestly begun research in search of a resin composition for paints having excellent dispersibility in all pigments regardless of whether they are inorganic pigments or organic pigments and having extremely high practicality.

Therefore, the problem to be solved by the present invention, depending on the first, the high degree of weather resistance of the fluororesin originally,
In particular, to obtain a novel resin composition for paints, which has good pigment dispersibility without impairing it, and also has good dispersibility for all pigments, regardless of whether they are inorganic pigments or organic pigments. An object of the present invention is to provide a highly practical resin composition for paints.

[Means for solving problems]

Therefore, the present inventors have focused on the problems to be solved by the above-described invention, and have a high degree of weather resistance of the fluororesin, without impairing anything at all, among others,
In order to obtain a novel and useful modified fluororesin having good pigment dispersibility, as a result of extensive studies, as a result, in the presence of a resin solution having a polymerizable unsaturated double bond, a fluoroolefin is used as an essential monomer. The specific modified fluororesin obtained by polymerizing a mixture of vinyl monomers as the body component has a pigment dispersibility, and in particular, good dispersibility for all pigments regardless of whether they are inorganic pigments or organic pigments. Shown together, by using such a specific modified fluororesin, for the first time, having a good dispersibility in all pigments, to find that an extremely highly practical resin composition for coating is obtained, Here, the present invention has been completed.

That is, the present invention basically, as an essential component,
In the presence of a polymer having a polymerizable double bond, a copolymer resin obtained by polymerizing a vinyl monomer mixture containing a fluoroolefin as an essential monomer component, and a solvent, or As an essential component, in the presence of a polymer having a polymerizable double bond, a copolymer resin obtained by polymerizing a vinyl monomer mixture containing a fluoroolefin as an essential monomer component, and a curing agent. The present invention is intended to provide a resin composition for coating material, which comprises a resin and a pigment, if necessary.

Here, as typical examples of the above-mentioned polymer having a polymerizable double bond, an acrylic resin, an alkyd resin, an oil-free alkyd resin, etc., each containing the polymerizable double bond are pigment-dispersible polymers. It is preferable from the point.

All such polymers may be prepared according to a conventional method, and as a method for introducing this double bond, for example, in the case of an addition polymerization type polymer, a hydroxyl group is introduced into the polymer to be obtained in advance, and then, , To this hydroxyl group, such as maleic anhydride, acrylic acid anhydride or itaconic acid anhydride,
A method of introducing a double bond by subjecting various acid anhydride group-containing monomers to an addition reaction, or, in the case of a condensation polymer, directly using a reaction raw material having this polymerizable double bond. The method of introducing a double bond into the resin is particularly effective.

That is, in order to prepare an acrylic resin having a polymerizable double bond, first, a vinyl monomer having a hydroxyl group and another vinyl monomer copolymerizable therewith may be copolymerized, and In order to prepare an alkyd resin or an oil-free alkyd resin having a polymerizable double bond, an acid anhydride group-containing monomer as described above is previously prepared for the hydroxyl group of the polyester component obtained according to a well-known conventional synthetic method. It may be subjected to an addition reaction, and in particular, in the alkyd resin obtained by using the fatty acid having the polymerizable double bond, the acid anhydride group-containing monomer is not added to the hydroxyl group as it is and May be used in.

Among them, typical examples of the hydroxyl group-containing vinyl monomer are 2-hydroxyethyl (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Hydroxyalkyl esters of (meth) acrylic acid such as acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate or polyethylene glycol mono (meth) acrylate; acid anhydride group-containing unit such as maleic anhydride or itaconic anhydride Double-bond-containing hydroxyalkyl ester carboxylic acids such as adducts of compounds with glycols such as ethylene glycol; Polymerizable double-bond containing dihydroxyalkyl esters of polyvalent carboxylic acids such as maleic acid or fumaric acid Polyhydroxyalkyl esters; or hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, etc., and a typical example of other vinyl monomers copolymerizable with such a hydroxyl group-containing monomer is methyl (meth). Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) such as acrylate or benzyl (meth) acrylate (meth) acrylic acid esters; maleic acid,
Diesters of unsaturated dicarboxylic acids such as fumaric acid or itaconic acid and monohydric alcohols such as methanol, ethanol or butanol; vinyl acetate, vinyl benzoate or "Veova" (made by Shell in the Netherlands,
Various vinyl esters such as (versic acid vinyl ester); "Viscoat 8F, 8FM, 3F or 3FM"
[(Meth) acrylates having a fluorine atom in the side chain, manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or Ni-propyl perfluorooctane sulfonamide Perfluoroalkyl group-containing vinyl esters such as ethyl (meth) acrylate; α-olefins such as vinyl chloride, vinylidene chloride, ethylene or propylene; styrene, α-methylstyrene, p-tert-butylstyrene, o-methylstyrene Or aromatic vinyl monomers such as p-methylstyrene; carboxyl group-containing monomers or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid; Acid anhydride group-containing unit such as S; (meth) acrylamide,
Carboxamide group-containing monomers such as N, N-dimethyl (meth) acrylamide, N-alkoxymethylated (meth) acrylamide, diacetone acrylamide or N-methylol (meth) acrylamide; p-styrenesulfonamide, N -Methyl-p-styrenesulfonamide or N, N-dimethyl-p-styrenesulfonamide containing sulphonic acid amide group-containing monomers; N, N-dialkyl such as N, N-dimethylaminoethyl (meth) acrylate Aminoalkyl (meth) acrylates, or acid anhydride group-containing monomers such as those listed above, and active hydrogen capable of reacting with an acid anhydride group such as N, N-dimethylaminopropylamine and a tertiary amino group Tertiary amino group-containing monomers such as adducts with compounds; cyano group-containing such as (meth) acrylonitrile Monomers; Obtained by condensation reaction of (ethylenically unsaturated) double bond-containing carboxylic acid such as (meth) acrylic acid hydroxyalkyl ester, that is, hydroxyalkyl ester of unsaturated carboxylic acid with phosphoric acid or phosphoric acid ester. Having a phosphoric acid ester bond; or 2-acrylamido-
Examples thereof include sulfonic acid group-containing monomers such as 2-methyl-propanesulfonic acid or organic amine salts thereof.

The amount of the hydroxyl group-containing monomer to be copolymerized is different depending on the molecular weight of the obtained vinyl-based copolymer resin, for example, an acrylic resin, but is generally 10 to 10 in all the copolymer resin components.
It is preferably within a range of occupying 50% by weight, and thus the remaining 90 to 50% by weight may be appropriately selected from other copolymerizable vinyl monomers.

To prepare the hydroxyl group-containing vinyl copolymer resin described above, any known method such as a solution polymerization method or a solution pressure polymerization method may be used, but among them, the solution radical polymerization method is the most convenient and suitable. is there. Typical solvents used at that time are hydrocarbons such as toluene, xylene, cyclohexane, n-hexane or octane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; methyl acetate, ethyl acetate or There is a solvent such as an ester-based solvent such as butyl acetate; or an amide-based solvent such as dimethylformamide or diethylacetamide, or a mixture thereof.

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

At that time, a known and commonly used chain transfer agent such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol or α-methylstyrene dimer may be used as a molecular weight regulator.

Then, the hydroxyl group-containing vinyl copolymer thus obtained is subjected to an addition reaction with the acid anhydride group-containing monomer as described above to obtain the objective polymerizable double bond-containing polymer. The reaction at this time is from room temperature. It may be carried out at a temperature of up 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 polymer as a precursor, but the polymerizable double bond is 1 to 1 molecule in one molecule of the polymer. It is suitable to use it in such a ratio that it is introduced within the range of 3.

On the other hand, typical polybasic acid components used in preparing an alkyd resin having a polymerizable double bond or an oil-free alkyd resin are isophthalic acid, terephthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid. , 4,4'-diphenylmethanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenehexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, fumaric acid, Itaconic acid, succinic acid, glutaric acid, adipic acid, mazelaic acid, pimelic acid, suberic acid, sebacic acid or dimer fatty acid (dimer acid), or trimesic acid, trimellitic acid, pyromellitic acid or cyclohexanetetracarboxylic acid, Or It is reactive derivatives, such as those of the alkyl ester or anhydride.

Further, as typical examples of the glycol component used in preparing the polyester component, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5
Alkylene glycols such as -pentanediol, 1,6-hexanediol or neopentyl glycol, or if necessary, 1,4-cyclohexanedimethanol, bishydroxyethyl terephthalate or alkylene oxide of (hydrogenated) bisphenol A. As a matter of course, aromatic or alicyclic glycols such as adducts can be used, and a monoepoxy compound can also be used together as such a glycol component.

Furthermore, as the trivalent or higher polyol component, glycerin, trimethylolethane, trimethylolpropane,
Typical examples are pentaerythritol, dipentaerythritol, sorbitol, and polyester compounds obtained by adding ε-caprolactone to the various glycol components listed above.

Furthermore, typical examples of (unsaturated) fatty acids used in obtaining the alkyd resin include octylic acid, palmitic acid, stearic acid, versatic acid, oleic acid, linoleic acid or linoleic acid, and palm oil. C ₈ or more long-chain monobasic acid such as oil fatty acid, hydrogenated coconut oil fatty acid, tall oil fatty acid, castor oil fatty acid, rice bran oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, safflower oil fatty acid or dehydrated castor oil fatty acid These (unsaturated) fatty acids are appropriately selected in consideration of solubility in a solvent, weather resistance of a coating film, economical efficiency, and the like.

The copolymer resin thus obtained, which is an essential component of the composition of the present invention, that is, the various polymerizable double bonds listed above, is prepared by using the polymer having a polymerizable double bond thus obtained and a fluoroolefin as described below. To prepare a fluororesin modified with a polymer containing a polymer, a mixture of vinyl monomers containing fluoroolefin as an essential monomer component in the presence of the polymer having a polymerizable double bond is polymerized. Good.

The amount of the polymerizable double bond-containing polymer used is 0.1 to 50% by weight based on 99.9 to 50% by weight of the mixture with the vinyl monomer containing the other fluoroolefin as an essential monomer component. Is appropriate.

When the polymerizable double bond-containing polymer is less than 0.1% by weight, the pigment dispersibility is insufficient, and when it exceeds 50% by weight, the weather resistance of the copolymer resin as an essential component of the composition of the present invention is Since it becomes difficult to obtain excellent properties such as properties, both are not preferable.

Here, as typical ones of the above-mentioned fluoroolefins, ethylene fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene,
Compounds having a fluorine atom in the main chain, such as fluorine-containing α-olefins such as chlorotrifluoroethylene or hexafluoropropylene; or perfluoroalkyl perfluorovinyl ethers such as trifluoromethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether Among them, the use of tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene or hexafluoropropylene is preferable.

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

The amount of the fluoroolefin used is 10 to 60 mol%, preferably 20 to 50 mol%, based on the total amount of the mixture of the fluoroolefin and another vinyl monomer copolymerizable with the fluoroolefin. If it exceeds 60 mol%, the resulting copolymer resin, that is, the modified fluororesin will have "turbidity", or the copolymer resin will lack compatibility with the curing agent. When the amount is less than 10 mol%, excellent properties such as chemical resistance and weather resistance originally possessed by this copolymer resin which is an essential component of the composition of the present invention are difficult to be expressed, and therefore, both are preferable. Absent.

Typical other vinyl monomers copolymerizable with the fluoroolefin include carboxylic acid vinyl esters, hydroxyalkyl vinyl ethers and alkyl vinyl ethers. First, specific examples of the carboxylic acid esters include acetic acid. Vinyl, vinyl of linear or branched aliphatic carboxylic acids such as vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl versatate, vinyl laurate or vinyl stearate. Esters; vinyl esters of alicyclic carboxylic acids such as cyclohexanecarboxylic acid vinyl ester; or various aromatic carboxylic acid vinyl esters such as vinyl benzoate, vinyl p-tert-butylbenzoate or vinyl salicylate And so on.

Next, specific examples of the above-mentioned hydroxyalkyl vinyl ethers include hydroxyethyl vinyl ether, hydroxypropyl vinyl ether or hydroxybutyl vinyl ether, and specific examples of the above-mentioned alkyl vinyl ethers include methyl vinyl ether, ethyl vinyl ether and n-propyl. Examples thereof include vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether and tert-butyl vinyl ether.

Further, other vinyl monomers copolymerizable with fluoroolefins include α-olefins such as ethylene, propylene or butene-1; vinyl halides (vinylidene chloride) excluding fluoroolefins such as vinyl chloride or vinylidene chloride. ) Type; aromatic vinyl compound such as styrene, α-methylstyrene, p-tert-butylstyrene, o-methylstyrene or p-methylstyrene; containing (ethylenically unsaturated) double bond such as maleic acid or fumaric acid Mono- or diesters of polybasic acids; nitrogen-containing vinyl compounds such as (meth) acrylonitrile, (meth) acrylamide, N-methylolated (meth) acrylamide or N-butoxymethyl (meth) acrylamide; or (anhydrous) maleic acid or (Anhydrous) itaconic acid Such to the like can be used (ethylenically unsaturated) double bond-containing (anhydrous) polybasic acids, more can be used, such as allyl alcohol or allyl glycidyl ether.

In preparing the copolymer resin as an essential component of the composition of the present invention, that is, the modified fluororesin, in the presence of various polymerizable double bond-containing polymers as described above, the fluoroolefins listed above are added. The mixture of vinyl monomers as an essential monomer component may be polymerized. Specifically, this polymerizable double bond-containing polymer is charged in advance in a reaction vessel, and then the radical polymerization initiator is added. The vinyl monomer mixture containing a fluoroolefin as an essential monomer component in the presence of is subjected to batch operation, semi-continuous operation or continuous operation according to known conventional techniques such as bulk polymerization or solution (pressure) polymerization. You can follow.

Here, typical examples of the radical polymerization initiator include diacyl peroxides such as acetyl peroxide or benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide; hydrogen peroxide, tert-butyl. Hydroperoxides such as hydroperoxide or cumene hydroperoxide; Dialkyl peroxides such as di-tert-butyl peroxide; Alkyl peroxyesters such as tert-butyl peroxyacetate or tert-butyl peroxypivalate Azo compounds such as azobisisobutyronitrile or azobisisovaleronitrile; persulfates such as ammonium persulfate or potassium persulfate; Although the like dicumyl peroxide, if necessary, may be used in combination with such such organic reducing agents of the reducing agent or cobalt naphthenate or dimethylaniline sodium bisulfite or such inorganic sodium pyrosulfite.

Among the various known conventional methods described above as the method of the copolymerization reaction, the solution pressure polymerization method is also simple,
Although it is particularly desirable in the present invention, a typical solvent used at that time is a solvent used in the preparation of a polymerizable double bond-containing polymer, particularly a hydroxyl group-containing vinyl polymer. In addition to the various solvents mentioned above, methanol, ethanol, iso-
Propanol, n-butanol, iso-butanol, sec
There are alcohol solvents such as butanol or ethylene glycol monoalkyl ether, and it goes without saying that two or more kinds may be used in combination.

Further, in such copolymerization, various chain transfer agents as described above can be used as the molecular weight modifier.

Furthermore, the reaction temperature for such copolymerization is −
A temperature in the range of 20 ° C to 130 ° C is suitable, and a reaction pressure in the range of 1 to 100 kg / cm ² , preferably 5 to 60 kg / cm ² .

The number average molecular weight of the copolymer resin, which should be referred to as a modified fluororesin thus obtained, is suitably in the range of 5,000 to 30,000, and the hydroxyl value is suitably in the range of 0 to 200.

That is, when the obtained modified fluororesin copolymer resin is used as a so-called lacquer composition without using a curing agent, the hydroxyl value may be 0, while
When the modified fluororesin is used as a curable composition together with a curing agent having reactivity with the hydroxyl group in the resin, it is 5 to 20.
Those having a hydroxyl value within the range of 0 are suitable.

As described above, the hydroxyl value may be about zero, but in most cases, it has a hydroxyl value within a specific range, and the preferred hydroxyl value is in the range of 10 to 100. And particularly preferably in the range of 20 to 50.

Next, if necessary, a curing agent component may be added to the composition of the present invention, and as such a curing agent,
The above-mentioned copolymer resin which is an essential component of the composition of the present invention, that is, aminoplast or (block) polyisocyanate resin having reactivity with the hydroxyl group in the modified fluororesin, or polybasic acid-based compound can be used.

First of all, as a typical thing like this aminoplast,
Condensation obtained by reacting an amino group-containing compound component such as melamine, urea, acetoguanamine, benzoguanamine, spiroguanamine or steroganamin with an aldehyde compound component such as formaldehyde, paraformaldehyde, acetaldehyde or glyoxal by a known and conventional method. There are reaction components and those obtained by modifying these condensates with alcohol, and any of them can be used as long as they are commonly used for paints.

Of these, preferred are those obtained by partially or completely etherifying C ₁ -C ₄ alcohols.

Specific examples of the aminoplast include hexamethyletherified methylolmelamine, hexabutyletherified methylolmelamine, methylbutyletherified methylolmelamine, methyletherified methylolmelamine, butyletherified methylolmelamine or iso-butyletherified methylolmelamine, or various condensations thereof. Examples thereof include methyl etherified methylol melamine from the viewpoint of compatibility with the copolymer resin (modified fluororesin).

Next, specific examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; cyclic aliphatic diisocyanates such as xylylene diisocyanate or isophorone diisocyanate;
Organic diisocyanates themselves such as aromatic diisocyanates such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate, or adducts of each of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins or water, or the above. As mentioned above, polymers of each organic diisocyanate, and further isocyanate biuret are listed. Typical examples of commercially available products thereof are "Bernock D-750, -800, DN-950, -970 or 15 −455 ”
[These are products of Dainippon Ink and Chemicals, Inc.], "Desmodur L, N, HL, or IL" (product of Bayer, West Germany), "Takenate D-102, -202, -110N or -123N" ( Takeda Pharmaceutical Co., Ltd.], "Coronate L, HL, EH or 203" [Japan Polyurethane Industry Co., Ltd. product] or "Duranate 24A-90CX" [Asahi Kasei Co., Ltd. product].

Next, as typical ones of the above-mentioned blocked polyisocyanate compounds, those obtained by blocking each of the above-listed polyisocyanate compounds with a known and commonly used blocking agent are shown. Commercially available products include "Barnock D-550", "Dainippon Ink and Chemicals, Inc.", "Takenate B-815-N".
(Takeda Pharmaceutical Co., Ltd. product), "ADDITO
L) VXL-80 "(product of Hoechst, West Germany) or" Coronate 2507 "[product of Nippon Polyurethane Industry Co., Ltd.].

Furthermore, as the polybasic acid curing agent, an acrylic resin having two or more carboxyl groups in one molecule, a polyester resin having two or more carboxyl groups in one molecule,
A typical example is pyromellitic acid.

The amount of these various curing agents used is such that the amount of the curing agent is 50 to 1 part by weight based on 50 to 99 parts by weight of the modified fluororesin as an essential component of the composition of the present invention, that is, the copolymer resin. A suitable solid content weight ratio is appropriate.

When a (block) polyisocyanate compound is used, about 0.3 to 3 equivalents of effective isocyanate groups in the (block) polyisocyanate compound is used with respect to 1 equivalent of hydroxyl groups in the copolymer resin (modified fluororesin). It is suitable to mix in a ratio.

The resin composition for coating material of the present invention thus obtained can be used as it is as a transparent coating material, or can be used as a colored coating material in a form in which a pigment is kneaded and dispersed.

As described above, typical pigments that can be added to the composition of the present invention as needed include inorganic pigments such as titanium oxide or carbon black;
Examples include organic pigments such as quinacridone-based or azo-based pigments; and metal powders such as aluminum powder, copper powder or zinc powder.

Further, if necessary, for example, when a curing agent is used, the composition of the present invention may be mixed with a curing catalyst, and various resins and solvents, or flow regulators and color separation preventive agents. Various well-known and commonly used additives such as an agent, an antioxidant, an ultraviolet absorber or a silane coupling agent can also be incorporated.

Among them, when the curing agent is a (block) polyisocyanate compound, examples of the curing catalyst include dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, triethylamine or diethanolamine, and then the curing agent is amino. In the case of plast, paratoluenesulfonic acid, phosphoric acid or an alkyl ester of phosphoric acid, or "Beckamine P-19
8 "[Product of Dainippon Ink and Chemicals, Inc.] and" Nycure 155, 2500X, X-49-110, 5225 or 3525 "(product of King, USA) dinonylnaphthalene disulfonic acid, dodecylbenzene sulfone Examples thereof include acids or blocked products of these organic amines.

The amount of the curing catalyst used is 100% of the total solid content of the copolymer resin (modified fluororesin) and the curing agent.
A suitable range is 0 to 10 parts by weight with respect to parts by weight,
It should be appropriately determined depending on the curing temperature and time.

Next, typical examples of the above-mentioned resins include fibrin derivatives (fibrin-based resin) such as nitrocellulose or cellulose acetate butyrate, vinyl chloride-vinyl acetate copolymer resin, oil-free alkyd resin, alkyd resin, There are epoxy resins, ketone resins, petroleum resins, and (meth) acrylic resins that may contain styrene, and the above-mentioned solvents are used when preparing the copolymer resin (modified fluororesin). Such various compounds and mixtures thereof. However, when a (block) polyisocyanate compound is used as the curing agent, it goes without saying that use of such a solvent that reacts with an isocyanate group should be avoided.

Thus obtained coating resin composition of the present invention, by a conventional method, is applied by a known method such as spray coating, brush coating or roll coater, at room temperature when using an unblocked polyisocyanate compound as a curing agent. To about 120 ° C to 5 ° C to 40 ° C, while other types of curing agents such as blocked polyisocyanate compounds and aminoplasts are used at 60 to 250 ° C for 5 seconds to 40 minutes. A cured coating film is obtained.

INDUSTRIAL APPLICABILITY The composition of the present invention is for general baking such as home appliances, for exteriors such as buildings, roof tiles, or coil coating such as PCM, or for automobiles, more specifically for automobiles, enamel paint, metallic base paint or clear. It can be used as a paint or the like and for forming a surface protective film of glass or ceramic products.

〔Example〕

Next, the present invention will be specifically described with reference to Reference Examples, Examples and Comparative Examples. In the following, all parts and% are based on weight unless otherwise specified.

Reference Example 1 (Preparation Example of Polymerizable Double Bond-Containing Polymer) In a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser, 400 parts of toluene, 200 parts of butyl acetate, methyl methacrylate 100 parts, ethyl acrylate 77.
4 parts, 20 parts of β-hydroxyethyl methacrylate,
"Light Ester PM" 0.2 parts of [Kyoeisha Yushi Kagaku Kogyo Co., Ltd. phosphate ester type monomer], 0.4 parts of dimethylaminoethyl methacrylate, 2 parts of methacrylic acid and t
Two parts of ert-butyl peroxyoctate were charged, the temperature was raised to 90 ° C. in a nitrogen atmosphere, and the temperature was maintained 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, 0.8 parts of "light ester PM", 1.6 parts of dimethylaminoethyl methacrylate, 8 parts of methacrylic acid, acetic acid. A mixture of 200 parts of butyl, 3 parts of tert-butyl peroxyoctate and 5 parts of azobisisobutyronitrile was added dropwise over 3 hours.

Immediately after completion of the dropping, the temperature was raised to 110 ° C., 3 parts of tert-butylperoxybenzoate and 200 parts of toluene were added, and the mixture was kept at the same temperature for 15 hours.
%, The hydroxyl value was 21.6, and the polymer solution had a number average molecular weight of 20,000.

Next, this polymer solution was cooled to 60 ° C., charged with 9.8 parts of maleic anhydride and 9.8 parts of toluene, heated to 100 ° C. and kept at the same temperature for 5 hours, and when NV was 50%, and A target polymer having a hydroxyl value of 18.6 was obtained. Hereinafter, this is abbreviated as a polymer (a-1).

Reference Example 2 (Same as above) In a reactor equipped with a stirrer, a thermometer, a nitrogen introducing pipe and a reaction product water distilling pipe, 215 parts of adipic acid, 400 parts of hexahydrophthalic anhydride, 44.6 parts of trimethylolpropane.
Parts, 50 parts of ethylene glycol and 390.2 parts of neopentyl glycol were charged, the temperature was gradually raised to 230 ° C. over 5 hours under a nitrogen atmosphere, and the reaction system was kept at the same temperature until the acid value became 10. Was cooled to 100 ° C. or lower, and 250 parts of xylene was added to obtain an oil-free alkyd resin solution. This had an NV of 80%, a hydroxyl value of 88.8 and a number average molecular weight of 1010.

Then, this resin solution was cooled to 60 ° C., 147 parts of maleic anhydride and 36.8 parts of xylene were added, the temperature was raised to 100 ° C., and the reaction was carried out at the same temperature for 5 hours. %
And a target polymer having a hydroxyl value of 18.7 was obtained. Hereinafter, this is abbreviated as a polymer (a-2).

Reference Examples 3 to 5 (Preparation Example of Modified Fluorine Resin) A polymer (a-1) obtained in Reference Example 1 and a polymer (a-2) obtained in Reference Example 2 were placed in a stainless pressure tube. Table 1 shows commercially available "Beckol P-470-70" (produced by Dainippon Ink and Chemicals, Inc., alkyd resin with soybean oil length of 65; NV = 70%) and solvent methyl isobutyl ketone. Charged in proportion, and further ethyl vinyl ether (EVE), hydroxybutyl vinyl ether (HBV
E), "VeoVa 9" (manufactured by The Netherlands Shell, vinyl esters of versatic acid with a C ₈ comprising alkyl group), benzoic acid vinyl ester (VBZ) and "PERBUTYL PV" [manufactured by NOF Corp. Of the radical polymerization initiator], and then in a dry ice / methanol bath at -70
It was cooled to 0 ° C., and nitrogen gas was blown into it to replace the air in the system.

Thereafter, a predetermined amount of liquefied and collected hexafluoropropylene (HFP) and chlorotrifluoroethylene (CTFE) was charged, and the system was sealed.

On the other hand, only when using tetrafluoroethylene (TFE), use a pressure resistant tube with a valve, repeat the same operation as above, then press this TFE from the cylinder at the stage of charging this TFE, and open the valve. Closed and weighed.

When each autoclave was placed in a rotary constant temperature water bath heated to 60 ° C. and reacted for 16 hours separately, each reaction product, that is, each modified fluororesin was obtained.

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

In the same table, the charged amount of each raw material is shown by the number of parts, and the number of moles is also shown in parentheses. Further, the polymer (a-
3) means "Beckozol P-470-70", and VV-9 means "Veoba 9".

Reference Examples 6 to 8 (Preparation Example of Fluororesin for Control) Unmodified fluorine for control as in Reference Examples 3 to 5 except that the use of the polymerizable double bond-containing polymer was changed to be completely absent. A resin was obtained.

The characteristic values (constant values) are also shown in Table 1.

Reference Example 9 (Preparation Example of Polymerizable Double Bond-Containing Polymer) In the same reaction vessel as in Reference Example 1, 400 parts of toluene, 200 parts of n-butyl acetate and 100 parts of methyl methacrylate were added.
Parts, 97.6 parts of ethyl acrylate, 0.4 parts of dimethylaminoethyl methacrylate and 2 parts of methacrylic acid, and 2 parts of tert-butyl peroxyoctoate were charged and heated to 90 ° C. in a nitrogen atmosphere. And kept at the same temperature for 2 hours.

Then, to this, 400 parts of methyl methacrylate, 378.76 parts of ethyl acrylate, 11.7 parts of β-hydroxyethyl methacrylate, 1.6 parts of dimethylaminoethyl methacrylate and 8 parts of methacrylic acid, and 3 parts of tert-butyl peroxyoctoate. A mixture of 4 parts of azobisisobutyronitrile and 200 parts of n-butyl acetate was added dropwise over 3 hours.

Immediately after completion of the dropping, the temperature was raised to 110 ° C., and 3 parts of tert-butyl peroxyoctoate and 20 parts of toluene were added.
By adding 0 part and holding at the same temperature for 15 hours, the nonvolatile content (NV) is 50%, the hydroxyl value is 2.5,
Moreover, a polymer solution having a number average molecular weight of 23,000 was obtained.

Then, this resin solution was cooled to 60 ° C., charged with 9.8 parts of maleic anhydride and 9.8 parts of toluene,
The temperature was raised to 0 ° C., and the temperature was maintained at the same temperature for 5 hours to obtain a solution of the target polymer having an NV of 50% and a hydroxyl value of zero. Hereinafter, the polymer (a-
4) is abbreviated.

Reference Example 10 (Preparation Example of Modified Fluorine Resin) In a reaction container similar to Reference Examples 3 to 5, the polymer (a-4) obtained in Reference Example 9 and methyl isobutyl ketone as a solvent were charged in the first order. Charge the mixture as shown in the table (additional portion), and add ethyl vinyl ether (EVE), VV-9 and "perbutyl PV" at the proportion as shown in the table, and then add in a dry ice / methanoe bath. Then, it was cooled to −70 ° C., and nitrogen gas was blown thereinto to replace the air in the system.

Then, a predetermined amount of liquefied and collected CTFE was charged and sealed.

After that, this pressure tube was put in a rotary constant temperature bath heated to 60 ° C and reacted for 16 hours. As a result, NV was 48.7.
%, And a solution of the target resin having a hydroxyl value of zero was obtained. Hereinafter, this is abbreviated as resin (b-4).

The results of comparative examination of the degree of gloss of the resin (b-4) are shown in Table 2 (additional amount).

Examples 1 to 5 and Comparative Examples 1 to 5 As shown in Table 2, relative to 100 parts of each modified or unmodified fluororesin obtained in Reference Examples 3 to 5 and Reference Examples 6 to 8, Pigments and thinners were separately mixed in proportions and then kneaded in a sand mill for 1 hour to prepare various color bases.

Then, each color base is made into a coating solution by simply diluting it to a spray viscosity with a thinner without adding a curing agent, or each color base is mixed with a predetermined amount of a curing agent as shown in the same table. After that, it was diluted with a thinner to a spray viscosity to obtain a coating solution.

Thereafter, a 0.8 mm thick mild steel plate degreased with petroleum benzine was spray-painted, and then a colored (modified) fluororesin coating film was obtained under the drying or curing conditions shown in the same table.

The degree of gloss of each cured coating film was compared and examined. The results are summarized in the table, and (Note) in the table is as follows.

(Note 1) Furnace type carbon black manufactured by Mitsubishi Kasei Co., Ltd., with a pigment concentration (PWC) of 3
It was used in an amount such that

(Note 2) Phthalocyanine pigment manufactured by Dainippon Ink and Chemicals, Inc., which was used in an amount such that PWC was 12%.

(Note 3) A red pigment manufactured by Imperial Chemical Industries of England, which was used so that PWC was 12%.

(Note 4) A yellow pigment manufactured by the same company, which was used so that PWC was 20%.

(Note 5) A mixed solvent of xylene / toluene / ethyl acetate / butyl acetate / cellosolve acetate = 40/20/10/20/10 (weight ratio) was used.

(Note 6) "Swazol 1000" [Aromatic hydrocarbon mixture manufactured by Maruzen Oil Co., Ltd.] / N-butanol = 70/30 (weight ratio)
The following mixed solvent was used.

(Note 7) When the kneaded meat color base is allowed to stand at room temperature for one month, when the sedimentation, separation or agglomeration of the pigment occurs in this kneaded meat product, it is evaluated as “x”. The case where no abnormalities were observed at all was evaluated as "A".

(Note 8) Polyisocyanate resin manufactured by Nippon Polyurethane Industry Co., Ltd .; isocyanate content = 21.3%, NV = 100
%, And used such that NCO / OH = 1/1 (equivalent ratio).

(Note 9) Block polyisocyanate resin manufactured by the same company;
Effective isocyanate content = 11.8%, NV = 81%, and used so that NCO / OH = 1/1 (equivalent ratio).

(Note 10) Hexamethyletherified methylolmelamine resin manufactured by Sumitomo Chemical Co., Ltd .; NV = 100%, which is (modified) fluororesin / “Sumimar M-100”.
C ”= 70/30 (solid content weight ratio).

(Note 11) Curing catalyst manufactured by King of the United States (Note 12) Type A: Natural drying at room temperature for 1 week Type B: Forced drying at 60 ° C for 30 minutes, then standing at room temperature for 5 days Type C: 140 ° C at 30 Forced drying for 13 minutes (Note 13) Displayed as 60 degree specular reflectance (%).

[Effects of the Invention] As is clear from the results shown in Table 2, the resin composition for coating composition of the present invention gives a stable color base without any silence or aggregation when it is kneaded with the pigment. It is known that it gives a coating film having excellent gloss.

Claims (12)

[Claims] 1. A method of polymerizing a mixture of a fluoromonomer and a vinyl monomer having a hydroxyl group-containing vinyl monomer as an essential monomer in the presence of a polymer having a polymerizable unsaturated double bond. Copolymer resin obtained by, and a solvent, containing as an essential component, and, if necessary,
A resin composition for paint, which also contains a pigment. 2. A method of polymerizing a mixture of a fluoroolefin and a vinyl monomer containing a hydroxyl group-containing vinyl monomer as an essential monomer in the presence of a polymer having a polymerizable unsaturated double bond. Copolymer resin obtained by, and a curing agent, as an essential component, and further, if necessary,
A resin composition for paint, which also contains a pigment. 3. The polymer having a polymerizable unsaturated double bond is at least 1 selected from the group consisting of acrylic resins, alkyd resins and oil-free alkyd resins.
A composition according to claim 1 or 2 which is of the species. 4. The composition according to claim 1, wherein the copolymer resin has a hydroxyl value of 5 to 200. 5. The method according to claim 1 or 2, wherein the mixture of vinyl monomers contains a fluoroolefin and a vinyl carboxylate, a hydroxyalkyl vinyl ether and / or an alkyl vinyl ether. Composition. 6. The composition according to claim 2, wherein the curing agent is a compound having reactivity with a hydroxyl group in the copolymer resin. 7. The curing agent is aminoplast.
The composition according to claim 2 or 6. 8. The method according to claim 2 or 6, wherein the curing agent is a methyl etherified methylol melamine resin.
Item 8. The composition according to any of items 1 to 7. 9. The composition according to claim 2 or 6, wherein the curing agent is a non-blocked polyisocyanate compound. 10. The method according to claim 2 or 6, wherein the curing agent is a blocked polyisocyanate compound.
The composition according to the item. 11. The method according to any one of claims 2, 6 and 9, wherein the curing agent is an unblocked polyisocyanate compound having an isocyanurate ring in the structure of the curing agent. The composition according to claim 1. 12. The above-mentioned curing agent is a blocked polyisocyanate compound having an isocyanurate ring in the structure of the curing agent. The composition according to any one of claims 2, 6 and 10.