JPH10101984A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition which has weather resistance inherent in fluorocarbon resins and does not sag in its application because it has a high drying rate through it contains mineral turpentine oil desirable from the viewpoint of the environmental protection as the solvent. SOLUTION: This composition comprises mineral turpentine oil (solvent), 25-90wt.% fluorocopolymer soluble therein, 6-75wt.% nonfluorocopolymer insoluble therein, and optionally 0-35wt.% nonfluorocopolymer soluble therein. The fluorocopolymer is one having a resin OH value of 5-120mgKOH/g and obtained by copolymerizing 20-55mol% fluoroolefin with 1-25wt.% polymerizable hydroxy compound, 0.1-10mol% 10-15C linear unsaturated fatty acid and 15-75mol% another vinyl compound copolymerizable therewith, and the nonfluorocopolymer insoluble in mineral turpentine oil is dispersed in the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for a fluororesin coating using a mineral terpene as a solvent.

[0002]

2. Description of the Related Art Conventionally, fluororesin coatings utilizing the excellent weather resistance of a fluorocopolymer have been industrialized. Particularly recently, a solvent-soluble fluorine-based copolymer having a cured site has been synthesized (for example, JP-A-57-34107, JP-A-61-57609, etc.), and is used for construction, automobile, and chemical. It is widely used as a weather-resistant paint in fields such as industry. The main component of these paint resins is a fluorine-containing monomer such as chlorotrifluoroethylene, tetrafluoroethylene or vinylidene fluoride, and a hydrocarbon-based monomer such as vinyl ester or vinyl ether should be used as a copolymer component. This increases the solubility of the fluororesin.

[0003] However, in the current tide of the regulation of the emission of organic solvents, a case where a synthetic resin that is soluble in a mineral terpene or a solvent naphtha-based petroleum solvent is used for coating, especially an acrylic urethane resin soluble in a petroleum solvent. Continue to expand the market. As a result, there is a growing demand for repainting properties coated with such petroleum-based solvent-soluble resins.However, conventional fluorine-based paints use organic solvents such as xylene and butyl acetate as the main component of the thinner. The surface of the coating film coated with the molten resin was damaged, and repelling and discoloration were likely to occur, making it difficult to use. To address this problem, mineral turpen-soluble fluororesin paints are also commercially available, but because of the non-crosslinked lacquer type, the solvent resistance, water resistance, stain resistance and the like were insufficient. In recent years, water-based or powder-type paints that place importance on the environment and suppress the emission of organic solvents have been put into practical use, but have not yet surpassed solvent-type paints in terms of coating film performance. More recently, a mineral terpen-soluble polyisocyanate has been developed, and a mineral terpen-soluble fluororesin paint having a cured site is being developed.

[0004]

However, it has been pointed out that mineral terpenes generally take a long time to dry a coating film due to a low evaporation rate, and that the coating material drips during construction.

[0005]

Means for Solving the Problems As a result of detailed examination of a fluororesin coating, the present inventors have found that a crosslinkable fluorine-based copolymer soluble in mineral terpen and substantially fluorine dispersed in mineral terpen are dispersed. By mixing a non-aqueous emulsion containing no paint, a paint composition having excellent paint properties such as excellent weather resistance of the coating film and quick drying and less dripping in the coating operation was found, and the present invention was completed.

That is, according to the present invention, an amount of a solvent necessary for forming a paint, and a fluorine-based copolymer 25 soluble in the solvent are used.
~ 90% by weight, non-fluorinated copolymer insoluble in said solvent 6 ~
75% by weight, optionally 0 to 35% by weight of a non-fluorinated copolymer soluble in the solvent, and a coating composition comprising 100% by weight of a total solid content, wherein the solvent is a mineral terpene;
20 to 55 mol% of a fluoroolefin, 1 to 25 mol% of a polymerizable compound having a hydroxy group, and 0.1 to 10 of a linear unsaturated fatty acid having 10 to 15 carbon atoms.
Mol%, other copolymerizable vinyl compounds 15 to 7
5 to 120 mg of OH value obtained by copolymerizing 5 mol%
It is a KOH / g fluorine-based copolymer, and a non-fluorine-based copolymer insoluble in the solvent is dispersed in the coating composition.

[0007] The coating composition of the present invention is in a state where solid particles are dispersed in a fluorine-based copolymer solution. Therefore, even if the amount of the solvent is reduced, the varnish viscosity can be reduced. The effect that the evaporation rate can be increased can be expected, and as a result, it is considered to be a composition for a fluororesin paint which is less likely to sag during coating and has good drying properties. Here, it is presumed that the periphery of the particles of the non-fluorine-based copolymer is wet with the fluororesin, and the outermost surface of the coating film is substantially composed of only the fluororesin. Therefore, it is considered that the coating composition of the present invention was able to exhibit a high weather resistance inherent to a fluororesin coating, despite including a resin component containing no fluorine.

Hereinafter, the present invention will be described in detail. The fluoroolefin used in the fluorine-based copolymer according to the present invention is chlorotrifluoroethylene, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, hexafluoroisobutene, etc. 20 to 55 mol% of the monomer. If it is less than 20 mol%, the weather resistance of the coating film will be low,
If it exceeds 55 mol%, the solubility in mineral terpenes will decrease.

The hydroxy-containing polymerizable compound used in the fluorine-based copolymer according to the present invention is an allyl ether, vinyl ether, crotonic acid-modified compound, or the like. For example, alkylene glycol monoallyl ethers such as ethylene glycol monoallyl ether, propylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, and hydroxyalkyl allyl ethers such as hydroxybutyl allyl ether , Hydroxyalkyl vinyl ethers such as hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether and hydroxyhexyl vinyl ether; alkylene glycol monovinyl ethers such as diethylene glycol monovinyl ether and polyethylene glycol monovinyl ether; croton Crotonic acid-modified compounds such as hydroxyethyl is employed. Among them, alkylene glycol monoallyl ether increases the solubility of the fluorine-based copolymer, and is therefore preferably used for part or all of the hydroxy-containing polymerizable compound. The amount of these hydroxy group-containing polymerizable compounds is 1 to 1 of all monomers.
25 mol% and an OH value of 5 to 120 mg KOH /
g is copolymerized. The composition of the hydroxy group-containing compound is less than 1 mol% or the OH value is 5 mg KO
If it is less than H / g, the amount of cross-linked sites is small, the weather resistance and solvent resistance of the coating film are not sufficient, and the merits of using a two-pack cross-linking paint are not exhibited. On the other hand, if the molar ratio or the OH value exceeds 120 mgKOH / g, the solubility in mineral terpenes decreases, which is not preferable.

The linear unsaturated fatty acid having 10 to 15 carbon atoms used in the fluorine-based copolymer according to the present invention is represented by the general formula X-CH = CH- (CH ₂ ) _n -COOH ( _where X is hydrogen An atom or CH ₃ , wherein n is 6 to 1
It is an integer of 1. ), Specifically, 9-hendecenoic acid, 10-hendecenoic acid, 11-dodesenic acid, 14-pentadecenoic acid, and the like.
Those having an unsaturated double bond at the terminal are preferable, and 10-hendecenoic acid having high polymerizability is particularly preferable. The acid groups introduced into the resin are involved in useful effects such as a catalytic effect in a crosslinking reaction and an effect of improving pigment dispersibility. However, when a linear unsaturated fatty acid having 9 or less carbon atoms is used, a mineral terpene may be used. It is not preferable because the solubility is reduced, the resin is apt to gel during polymerization or coating, or the surface properties of the coating film are poor, so that the skin becomes tingled and the gloss becomes poor. The copolymerization amount of the linear unsaturated fatty acid used in the present invention,
0.1 to 10 mol% of all monomers. When the amount is less than 0.1 mol%, the pigment dispersibility of the paint prepared from the obtained fluorocopolymer is low. When the amount exceeds 10 mol%, the solubility of the fluorocopolymer in mineral terpen is reduced or the composition is cured. The pot life after the addition of the agent may be shortened, which is not preferable.

The copolymerizable vinyl compound used in the fluorine-based copolymer according to the present invention is not particularly limited, but preferably includes vinyl esters, vinyl ethers, allyl ethers and olefins. As the vinyl ester, an ester compound having a carbonyl group in the molecule which is polymerizable, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl laurate, myristic acid Vinyl, vinyl palmitate, vinyl stearate, vinyl versatate 9, vinyl versatate 10 and vinyl benzoate. Also,
Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether. Also,
As the allyl ether, for example, ethyl allyl ether, butyl allyl ether, benzyl allyl ether,
Allyl glycidyl ether, cyclohexyl allyl ether and the like are used. Ethylene, propylene and the like are used as olefins. Further, vinylsilane-based compounds, (meth) acrylic acid esters as exemplified in the later part of the present specification, and the like can also be used. These monomers may be used in combination of two or more kinds, and the composition thereof is 15 to 75 mol% of the total monomers. If it is less than 15 mol%, solubility in mineral terpen does not appear,
If it exceeds 75 mol%, the weather resistance of the coating film is undesirably reduced.

As the polymerization method of the fluorine-based copolymer according to the present invention, a usual radical polymerization method can be adopted, and as the polymerization form, solution polymerization, emulsion polymerization, suspension polymerization and the like are used without any particular limitation. In solution polymerization, there is no particular limitation on the solvent, mineral terpene, isoparaffin, paraffin,
Petroleum naphtha solvents such as naphthene mixed solvents, toluene,
Aromatic solvents such as xylene, alcohol solvents such as isopropanol and butanol, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone can be used widely. Solution polymerization in a mineral terpene is most preferred because no solvent change is required. Emulsion polymerization and suspension polymerization are carried out in water. The temperature of the polymerization step depends on the radical polymerization initiator used, but is usually from 0 to 130 ° C. The radical initiator is not particularly limited. For example, dicarbonates such as diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate and di-2-ethylhexylperoxydicarbonate, or n-heptafluorobutyric Diacyl peroxides such as peroxide, lauroyl peroxypivalate and t-butyloxy neodecanoate; alkyl peroxides such as di-t-butyl peroxide and t-butyl cumyl peroxide; Examples thereof include ordinary peroxide-based radical initiators such as peroxyesters such as valate and t-butylperoxyneodecanoate. In addition, azo initiators, redox initiators, metal salt initiators, and the like can be used.

The molecular weight of the fluorocopolymer according to the present invention is not particularly limited, but is in the range of 1,000 to 50,000 (number average molecular weight; styrene equivalent) depending on the required strength and flexibility of the coating film. It is more preferable, and more preferably about 3,000 to 30,000. 1,00
If it is less than 0, the weather resistance and flexibility of the coating film are reduced, and 3
When it is more than 000, a high viscosity is caused in the preparation of a coating material, which causes a disadvantage that it is difficult to handle.

As the non-fluorinated copolymer according to the present invention, those obtained from various monomers, both copolymers soluble and insoluble in mineral terpenes, are used. For example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, N-hexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, i-nonyl (meth) acrylate, (meth) acrylic acid (Meth) acrylates such as stearyl, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl laurate , Vinyl myristate, vinyl palmitate, vinyl stearate, versatic vinyl 9 Glycol ester ethers, more olefins such as ethylene, propylene, isobutylene, vinyl chloride and the like, allyl ethers such as methyl vinyl ether, ethyl vinyl ether, ethyl allyl ether or cyclohexyl vinyl ether,
It is a copolymer obtained by copolymerizing one or more types such as styrene and acrylonitrile.

Further, as the comonomer of the non-fluorinated copolymer according to the present invention, a compound having a functional group in the molecule can be used. For example, 2-hydroxyethyl (meth) acrylate, ( 2-hydroxypropyl (meth) acrylate, 3-hydroxyethyl (meth) acrylate,
Hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, α-β ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, ω Carboxybiscaprolactone mono (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylate and other amide group-containing polymerizable compounds, glycidyl (meth) acrylate, glycidyl ( Examples thereof include, but are not limited to, an epoxy group-containing polymerizable compound such as (meth) allyl ether.

Among these monomers, a non-fluorinated copolymer obtained from a monomer mixture mainly composed of (meth) acrylates or a monomer mixture mainly composed of vinyl esters Is preferred because of its excellent compatibility with the fluorine-based copolymer. In order to obtain a non-fluorinated copolymer such as this which is insoluble in mineral terpene, the molecular chain of the alkyl group, which may have a functional group, is short (meth).
It is preferred that the selection be made to contain a relatively large amount of acrylate. For example, methyl (meth) acrylate,
It is preferable to use those having an alkyl group having 1 to 3 carbon atoms, such as ethyl (meth) acrylate and hydroxyethyl (meth) acrylate, in an amount of 40 mol% or more, preferably 60 mol% or more. On the other hand, in order to obtain a substance insoluble in mineral terpene, it is preferable to select a relatively large amount of a (meth) acrylate having a long molecular chain of an alkyl group which may have a functional group.

The preparation of the coating composition of the present invention can be carried out according to a conventional method for producing a non-aqueous emulsion. That is, it can be obtained by polymerizing a monomer as a raw material of a non-fluorine-based copolymer in a solution in which a fluorine-based copolymer is dissolved in a mineral terpene in the presence of a polymerization initiator. In the production of the coating composition of the present invention, well-known auxiliaries and techniques in radical polymerization can be appropriately used according to the purpose. For example, the auxiliary agent includes a decomposition accelerator for the polymerization initiator, a chain transfer agent for controlling the degree of polymerization, and the like. Examples of the method include divided addition and sequential addition of a solvent, a monomer, or a polymerization initiator.

Another method for producing the coating composition of the present invention is as follows: a method of forming a composition in a mineral terpene solution of a fluorinated copolymer polymerized in a mineral terpene or a solvent and exchanging the solvent. It is also possible to employ a method of mixing the mineral terpene solution of the obtained fluorine-based copolymer with a non-aqueous emulsion of a non-fluorinated copolymer prepared separately. In this case, the solution phase of the non-aqueous emulsion of the non-fluorine-based copolymer may contain the non-fluorine-based copolymer dissolved in the mineral terpene. Further, if necessary, a non-fluorinated copolymer soluble in a mineral terpene can be added. Commercially available non-aqueous emulsions as described below contain about 30 to 80% by weight of insoluble particles, and generally have a high content of insoluble non-fluorinated copolymer components as much as possible. Preferably, one is used.

In preparing the coating composition of the present invention, a non-fluorinated copolymer prepared as a non-aqueous emulsion using a mineral terpene as a medium is commercially available. This is an easy and preferred method. Examples of such products include, but are not limited to, for example, Paraloid NAD-10 manufactured by Rohm and Haas Co., and U-3367, U-3391, and U-3398A manufactured by Nippon Carbide Industries.

The non-fluorinated copolymer insoluble in the mineral terpene forming such a non-aqueous emulsion has a particle diameter of 0.01 to 10 μm, preferably 0.1 to 10 μm, from the viewpoint of dispersion stability.
It is about 0.5 to 5 μm, more preferably about 0.1 to 1 μm. Although the molecular weight is not particularly limited,
00 to 500,000 (number average molecular weight; styrene equivalent)
And more preferably 30,
It is about 000 to 300,000. The molecular weight of the non-fluorinated copolymer soluble in the mineral terpene forming the non-aqueous emulsion is not particularly limited, but may be 10,000 or less.
It is preferably in the range of 0 to 500,000 (number average molecular weight; in terms of styrene), and more preferably 30,0.
It is about 00 to 300,000.

The solids content of the coating composition of the present invention comprises a fluorine-based copolymer soluble in mineral terpen, a non-fluorine-based copolymer insoluble in mineral terpen, and a non-fluorine-based copolymer optionally soluble in mineral terpen. Although it is composed of a copolymer, the fluorine-based copolymer is 25 to 90% by weight, preferably 30 to 70% by weight.
6 to 75% by weight, preferably 20 to 60% by weight of a non-fluorinated copolymer insoluble in mineral terpen,
Non-fluorinated copolymer optionally soluble in mineral terpen 0
３５35% by weight, preferably 0-25% by weight. Of these, the fluorine-based copolymer is 30 to 70% by weight, the non-fluorine-based copolymer insoluble in mineral terpen is 20 to 60% by weight, and the non-fluorine-based copolymer optionally soluble in mineral terpen is 0%. Most preferably, it is ２５25% by weight.
If the amount of the fluorine-based copolymer is less than 25% by weight, the weather resistance of the coating film is inferior. If the amount exceeds 90% by weight, the amount of the insoluble non-fluorine-based copolymer is small and the effect of preventing dripping can be obtained. Not so desirable. If the non-fluorinated copolymer insoluble in mineral turpen is 6% by weight, the effect of preventing sagging cannot be obtained, so that it is not preferable. If it exceeds 75% by weight, a smooth coating film cannot be obtained and the weather resistance is poor, so that it is not preferable. .
Further, it is not necessary to intentionally blend a copolymer soluble in mineral turpen, but it can be used at less than 35% by weight.

The coating composition of the present invention is adjusted to a required concentration by using a thinner as appropriate according to the coating method. As this thinner, a mineral terpene can be preferably used, and a petroleum naphtha-based solvent such as a mixed solvent of isoparaffin, paraffin and naphthene is also preferable. In addition, depending on the usage conditions, aromatic solvents such as toluene and xylene, alcohol solvents such as isopropanol and butanol, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone are widely used. Can be used.

In the fluororesin coating composition of the present invention, general-purpose crosslinkers such as polyisocyanate crosslinkers and melamine crosslinkers soluble in mineral terpenes can be used without limitation. In particular, a polyisocyanate having reduced polarity is preferably employed. A coating film coated by adding these crosslinking agents becomes a toughened coating film having excellent weather resistance. Specifically, as a polyisocyanate, a petroleum solvent,
Hexamethylene diisocyanate soluble in mineral terpenes and the like, non-yellowing polyisocyanate such as isophorone diisocyanate or polysocyanurate prepared therefrom, polyisocyanate adduct, polyisocyanate block, for example, TP-100, TP of Nippon Polyurethane Industry -703, TPLS2071 of Sumitomo Bayer Urethane, Duranate TS of Asahi Kasei Kogyo
A100, TSS100 and the like are mentioned as preferable ones, but it is a matter of course that equivalent or similar products can be used, and the present invention is not limited to these.

The coating composition of the present invention prepared as described above contains a resin soluble in a mineral terpene, such as an acrylic polyol, a polyvinyl ester, a silicone compound, a polyalkylene glycol, an alkyd resin,
Vegetable oil and the like can be added. Further, ultraviolet absorbers, light stabilizers, rust preventives, dispersants, anti-dripping agents, pigments, dyes and the like can be added.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

[0026]

【Example】

[Synthesis Example 1] SU with an electromagnetic stirrer and a capacity of 2 liters
In an S-made autoclave, 63 g (10 mol%) of ethylene glycol monoallyl ether, 10-hendecenoic acid 2
2.9 g (2 mol%), 80 g of vinyl pivalate (10
Mol%), 434 g (38 mol%) of versatic vinyl 9-acid, mineral terpen (LAWS manufactured by Shell Japan)
300 g (35 parts by weight based on 100 parts by weight of monomer), t-butyl peroxypivalate (manufactured by NOF Corporation)
After charging 8 g and repeating degassing and replacement with nitrogen gas three times, 288 g (40 mol%) of chlorotrifluoroethylene was charged, and polymerization was carried out at 55 ° C. for 20 hours in the presence of 3 g of sodium carbonate decahydrate. Was. After the completion of the polymerization, the content was taken out after purging the remaining monomer, and a resin varnish dissolved in a mineral turpent was obtained. This was filtered and the concentration was adjusted with a mineral terpen to obtain a transparent fluororesin varnish having a solid content of 60% by weight. Table 1 shows the OH value and acid value of the obtained fluororesin.

[0027]

[Table 1]

CTFE: Chlorotrifluoroethylene TFE: Tetrafluoroethylene VPv: Vinyl pivalate V-9: Vinyl versatate 9 EVE: Ethyl vinyl ether CHVE: Cyclohexyl vinyl ether EGMAE: Ethylene glycol monoallyl ether HBVE: Hydroxybutyl vinyl ether HDA: 10 -Hendesenoic acid LAWS: Mineral turpentine (loin) manufactured by Shell Japan Solubility: ○ soluble, × insoluble [Synthesis Examples 2 to 3] Polymerization was carried out in the same manner as in Synthesis Example 1 with the composition shown in Table 1. In each case, after the polymerization was completed, the residual monomer was purged, and the content was taken out. As a result, a resin varnish dissolved in a mineral turpent was obtained. This was filtered and the concentration was adjusted with a mineral terpen to obtain a transparent fluororesin varnish having a solid content of 60% by weight. Table 1 shows the OH value and acid value of the obtained fluororesin.

[Synthesis Examples 4 and 5] Polymerization was carried out in the same manner as in Synthesis Example 1 with the composition shown in Table 1. In each case, after completion of the polymerization, the content was taken out after purging the remaining monomer. As a result, the content was opaque and was not completely dissolved in the mineral turpentine. In Synthesis Examples 4 and 5, the copolymerization amount of the fluoroolefin is as large as 57 mol% or more. Neither measurement of the OH value nor the acid value was performed.

Example 1 200 parts by weight of titanium oxide CR90 manufactured by Ishihara Sangyo Co., Ltd. were uniformly mixed with 100 parts by weight of the solid content of the fluororesin varnish prepared in Synthesis Example 1, and then dispersed in a mineral turpentine. Acid ester / styrene non-aqueous emulsion (Nitetsu U-3367 manufactured by Nippon Carbide Industrial Co., Ltd .: about 70 particles in solids)
%, Average particle diameter of about 0.3 μm)
A main part of a white paint was prepared by adding parts by weight.

Next, 0.2 parts by weight of a leveling agent BYK301 manufactured by Big Chemie Co., and isocyanurate-type polycisocyanate (Duranate TSS100) prepared from hexamethylene diisocyanate manufactured by Asahi Kasei Kogyo Co., Ltd. Was added thereto, and diluted with a mineral terpene (LAWS) to obtain a paint. Next, this was spray-coated on an aluminum plate so as to have a thickness of about 40 microns, and dried and cured at room temperature for 10 days.

Using the coated plate produced as described above,
The measurement was performed for each item such as anti-dripping property, solvent resistance, water resistance, weather resistance, and color difference. Table 2 shows the results.

[0033]

[Table 2]

<Evaluation method>-Drying to the touch: The time until the stickiness almost disappears by touching the finger after painting. ○: within 3 hours, Δ: within 5 hours, x: any longer.・ Sag prevention: Five minutes after painting, the painted plate is set to be vertical and the paint dripping is observed. Not dripping (no change) ○, hard to droop △, dripping ×. -Solvent resistance: Tarpen rubbing test. Rub 100 times with absorbent cotton containing a mineral turpentine and observe the coating film surface. No change, scratches, dissolution. Water resistance: The coating film is immersed in water (50 ° C.) for 10 days, and the surface is observed. No change ○, blister △, no peeling or gloss ×. -Weather resistance: accelerated test by 5000 hours of sunshine weatherometer (60-degree gloss retention before and after the test). -Color difference: ΔE measurement. After 6 months of outdoor exposure, the color difference before and after exposure (JIS-Z8730) was measured (exposure location, Kawagoe City, Saitama Prefecture).

[Examples 2 to 5] Using the fluororesin varnish prepared in Synthesis Examples 1 to 3, the solid content was 1 in the same manner as in Example 1.
The titanium oxide CR90 (manufactured by Ishihara Sangyo Co., Ltd.) was added to 00 parts by weight using a dispersing mill at the addition amount shown in Table 2, and then dispersed in a mineral turpentine. Nitetsu U-3398A: about 70% of particles in solids, average particle diameter of about 0.9 μm) were mixed as solids in the amounts shown in Table 2 to prepare a base material for a white paint.

Next, a leveling agent BYK301 (manufactured by Big Chemie) and duranate TSS100 were added to each of the base materials of the obtained white paints, and diluted with a mineral turpentine (LAWS) to obtain paints. Next, this was spray-coated on an aluminum plate so as to have a thickness of about 40 microns, and dried and cured at room temperature for 10 days.

Using the coated plate manufactured as described above,
The measurement was performed for each item such as anti-dripping property, solvent resistance, water resistance, weather resistance, and color difference. Table 2 shows the results. [Comparative Examples 1 and 2] Using the fluororesin varnish prepared in Synthesis Examples 1 and 2, disperse a titanium oxide CR90 (manufactured by Ishihara Sangyo Co., Ltd.) in an amount shown in Table 2 with respect to a solid content of 100 parts by weight in the same manner as in Example 1. Then, the non-aqueous emulsion dispersed in the mineral turpent was mixed in the amount indicated in Table 2 as a solid content to prepare a main component of a white paint.

Next, a leveling agent BYK301 (manufactured by Big Chemie) and duranate TSS100 were added to the main ingredients of each of the obtained white paints, and diluted with a mineral turpentine (LAWS) to obtain paints. Next, this was spray-coated on an aluminum plate so as to have a thickness of about 40 microns, and dried and cured at room temperature for 10 days.

Using the coated plate prepared as described above,
The measurement was performed for each item such as anti-dripping property, solvent resistance, water resistance, weather resistance, and color difference. Table 2 shows the results.

[0040]

EFFECTS OF THE INVENTION The paint composition of the present invention has the effect of facilitating the coating operation by preventing the paint from sagging at the time of application by increasing the drying speed while using a mineral turpentine which is environmentally preferable as a solvent. To play.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI (C09D 127/12 133: 06) (C09D 127/12 133: 20) (C09D 127/12 125: 04) (C08F 214/24) 214: 26 216: 18 220: 04) (C09D 129/00 133: 06)

Claims (8)

[Claims] 1. An amount of a solvent necessary for forming a coating material, 25 to 90% by weight of a fluorine-based copolymer soluble in the solvent, and 6 to 75% by weight of a non-fluorinated copolymer insoluble in the solvent. A coating composition comprising 0 to 35% by weight of a non-fluorinated copolymer optionally soluble in the solvent and 100% by weight of a total solid content,
The solvent is a mineral terpene, and the fluorine-based copolymer is
20 to 55 mol% of a fluoroolefin, 1 to 25 mol% of a polymerizable compound having a hydroxy group, 0.1 to 10 mol% of a linear unsaturated fatty acid having 10 to 15 carbon atoms, and other copolymerizable vinyl compounds 15 A fluorinated copolymer having an OH value of 5 to 120 mgKOH / g obtained by copolymerizing 75 mol%, and a non-fluorinated copolymer insoluble in the solvent,
A coating composition, which is dispersed in the coating composition. 2. The coating composition according to claim 1, wherein the solvent is used in an amount necessary for forming the coating, 30 to 70% by weight of a fluorine-based copolymer soluble in said solvent, 20 to 60% by weight of an insoluble non-fluorinated copolymer, optionally 0 to 25% by weight of a non-fluorinated copolymer soluble in the solvent, and
A coating composition comprising 0% by weight. 3. The coating composition according to claim 1, wherein the polymerizable compound having a hydroxy group is at least one compound selected from alkylene glycol monoallyl ethers. 4. A linear unsaturated fatty acid having 10 to 15 carbon atoms, wherein
The coating composition according to any one of claims 1 to 3, wherein the composition is 0-hendesenoic acid. 5. The method according to claim 1, wherein the non-fluorinated polymer is a polymer obtained by polymerizing one or more monomers selected from (meth) acrylates, acrylonitrile and styrene. Compositions for paints. 6. The coating composition according to claim 1, wherein the non-fluorinated polymer is a polymer obtained by copolymerizing at least one selected from vinyl esters. 7. A coating composition according to claim 1, further comprising a polyisocyanate soluble in a mineral terpene as a curing agent. 8. The process for producing a coating composition according to claim 1, wherein said non-fluorinated emulsion is dispersed as a non-aqueous emulsion in a mineral terpen in a fluorine-based copolymer which is solid or dissolved in a mineral terpen. A method for producing a coating composition, comprising mixing a copolymer.