JP2956166B2 - Fluorine-containing vinyl polymer composition - Google Patents

Description

The present invention relates to a novel and useful curable resin composition. More specifically, it comprises a hydroxyl group-containing fluoropolymer and a specific blocked isocyanate compound as essential components, and is particularly excellent in that it can be used as a paint useful for coating on a bendable metal plate or the like. The present invention relates to a fluorine-containing vinyl polymer composition which has weather resistance and is excellent in gloss and flexibility.

[Prior art] Conventionally, a painted metal material that has been painted in advance prior to forming or assembling a steel material or so-called processing is compared to a method in which the metal material is processed and then painted. Because of its advantages in terms of economy, labor saving, and de-pollution, it is widely used mainly for various building materials such as roofing materials, outer wall materials, and duct shutters.

In recent years, there has been an increasing demand for long-term weather resistance of this type of coated metal material.

In this regard, paints using polyvinylidene fluoride as a binder have been used in response to such demands.However, such paints are themselves satisfactory in terms of weather resistance and flexibility. In the formation of the coating film, from the place where heating at a high temperature for several minutes or more is necessary, the coating productivity is inferior, furthermore, from the place where the gloss or transparency of the coating film is insufficient or insufficient, There are various problems such as difficulty in performing cosmetic finishing.

[Problems to be Solved by the Invention] As described above, a conventional coating agent is capable of providing a coated material having extremely excellent gloss and also excellent weather resistance and flexibility. The fact is that has not been found.

Therefore, the object of the present invention is to eliminate all the various problems in the prior art as described above, and to provide a resin composition which is extremely excellent in weather resistance and also excellent in gloss and flexibility. To be.

Means for Solving the Problems Accordingly, the present inventors have conducted intensive studies mainly in accordance with the object of the present invention as described above. As a result, a specific fluoropolymer and a specific blocked isocyanate compound were obtained. By applying and curing a resin composition containing, as an essential component, that is, a paint using a fluoropolymer composition, it has, for the first time, extremely excellent gloss, in addition to weather resistance and flexibility. The inventors have found that an excellent coated product can be obtained, and have completed the present invention.

That is, the present invention provides, as essential components, a fluorine-containing vinyl polymer (A) having at least two hydroxyl groups in one molecule on average, and a diisocyanate compound (b-1)
And a long-chain diol having a carbon chain (b-2) in the presence of an isocyanurate-forming catalyst to obtain a blocked isocyanate compound (B) obtained by blocking an isocyanate compound having an isocyanurate ring. And a fluorine-containing vinyl polymer composition comprising:

Here, the above-mentioned hydroxyl-containing vinyl-containing polymer (A) has an average of two or more hydroxyl groups in one molecule, and when the number of hydroxyl groups is less than 2, It is not preferable because the durability of the coating film is reduced.

Examples of the hydroxyl group-containing vinyl-containing polymer (A) include, for example, 15 to 15 of the fluorine-containing vinyl monomer (a-1).
75% by weight and 1 to 1 of the hydroxyl group-containing vinyl monomer (a-2)
30% by weight and 5 to 5 of other copolymerizable monomer (a-3)
Those obtained by copolymerization with 85% by weight are exemplified as particularly typical ones.

When the amount of the fluorine-containing vinyl monomer (a-1) used is less than the above range, the durability of the coating film is reduced, and when the amount exceeds the above range,
Any of them is not preferable because the coating workability is reduced.

If the amount of the hydroxyl group-containing vinyl monomer (a-2) is less than the above range, the solvent resistance and durability of the coating film will be reduced. If the amount exceeds the above range, the flexibility of the coating film and the like will inevitably decrease, so that any of them is not preferable.

Particularly typical examples of the fluorine-containing vinyl monomer (a-1) include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, and pentafluoropropylene. Or fluorine-containing α-olefins such as hexafluoropropylene; or trifluoromethyltrifluorovinylether, pentafluoroethyltrifluorovinylether or
Perfluoroalkyl perfluorovinyl ether such as heptafluoropropyl trifluorovinyl ether and (per) fluoroalkyl vinyl ether (however, the number of carbon atoms of the alkyl group is 1 to 18 in each case)
It's not going to happen. ), Among which vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, a (per) fluoroalkyl vinyl ether having an alkyl group of 1 to 18 carbon atoms, or a carbon atom of an alkyl group It is desirable to use (per) fluoroalkyl trifluorovinyl ether having a number of 1 to 18.

Particularly typical examples of the hydroxyl group-containing vinyl monomer (a-2) include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 3-hydroxybutyl vinyl ether. 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether or 6
Vinyl ethers having a hydroxyl group such as -hydroxyhexyl vinyl ether; addition reaction products of these various vinyl ethers with ε-caprolactone; 2-hydroxyethyl (meth) allyl ether, 3-hydroxypropyl (meth) allyl ether, Hydroxypropyl (meth) allyl ether, 4-hydroxybutyl (meth) allyl ether, 3-hydroxybutyl (meth) allyl ether, 2-hydroxy-2-methylpropyl (meth) allyl ether, 5-hydroxypentyl (meth) allyl Hydroxyl-containing allyl ethers such as ether or 6-hydroxyhexyl (meth) allyl ether; addition reaction products of these various allyl ethers with ε-caprolactone; 2-hydroxyethyl (meth) acrylate, 2-hydrido Kishipuropiru (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3
Hydroxyl-containing (meth) acrylates such as -hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate or polypropylene glycol mono (meth) acrylate; There is a main component of an addition reaction between (meth) acrylate and ε-caprolactone.

If only typical representative examples of the other copolymerizable monomer (a-3) are given as examples, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl Vinyl ether, tert-butyl butenyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether,
Alkyl vinyl ethers or substituted alkyl vinyl ethers such as 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, benzyl vinyl ether or phenylethyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether; vinyl-2,2 -Dimethyl propanoate, vinyl-
2,2-dimethylbutanoate, vinyl-2,2-dimethylpentanoate, vinyl-2,2-dimethylhexanoate, vinyl-2-ethyl-2-methylbutanoate, vinyl-2-ethyl- 2-methylpentanoate, vinyl-3-chloro-2,2-dimethylpropanoate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, lauric acid vinyl, such as resins aliphatic carboxylic acid vinyl such branched aliphatic carboxylic acid vinyl, branched aliphatic carboxylic acids vinyl C _10, branched aliphatic carboxylic acids or vinyl stearate C ₁₁ of C _9; cyclohexanecarboxylic acid vinyl, methyl Vinyl cyclohexanecarboxylate,
Vinyl esters of carboxylic acids having a cyclic structure, such as vinyl benzoate or p-tert-butyl vinyl benzoate; acrylic esters, such as methyl acrylate, ethyl acrylate, butyl acrylate or cyclohexyl acrylate; methyl methacrylate, ethyl methacrylate, Methacrylic esters such as butyl methacrylate, cyclohexyl methacrylate or benzyl methacrylate; α-olefins such as ethylene, propylene or butene-1; various halogenated olefins except fluoroolefin such as vinyl chloride or vinylidene chloride; styrene , Α
An aliphatic vinyl compound such as methylstyrene or vinyltoluene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldiethoxysilane, vinyltris (β-methoxyethoxy) silane, allyltrimethoxysilane, trimethoxy Silyl ethyl vinyl ether, triethoxysilyl ethyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, methyldiethoxysilylpropyl vinyl ether,
Monomers containing a hydrolyzable silyl group, such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane or γ- (meth) acryloyloxypropylmethyldimethoxysilane An amino group-containing amide unsaturated monomer such as N-dimethylaminoethyl (meth) acrylamide, N-dimethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide or N-diethylaminopropyl (meth) acrylamide; Dimers; dimethylaminoethyl (meth)
Dialkylaminoalkyl (meth) acrylates such as acrylate or dimethylaminoethyl (meth) acrylate; tert-butylaminoethyl (meth) acrylate, tert-bitylaminopropyl (meth) acrylate, aziridinylethyl (meth) acrylate, Amino group-containing monomers such as pyrrolidinylethyl (meth) acrylate or piperidinylethyl (meth) acrylate; or carboxyl groups such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid Monomers.

From the viewpoint of increasing the polymerization yield of the fluorine-containing vinyl polymer (A) itself, it is desirable to use alkyl vinyl ethers, cycloalkyl vinyl ethers, hydroxyl-containing vinyl ethers, and carboxylic acid vinyl esters. The type and amount of the monomer may be appropriately determined from the viewpoints of coating workability and coating film performance such as weather resistance.

In order to prepare the fluorine-containing vinyl polymer (A) component, a radical polymerization initiator is used to carry out a polymerization reaction using known techniques such as emulsion polymerization, suspension polymerization, bulk polymerization or solution polymerization. As such radical polymerization initiators, dialsyl peroxides such as acetyl peroxide or benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide; hydrogen peroxide, tert-butyl hydroperoxide or cumene Hydroperoxides such as hydroperoxide; dialkyl peroxides such as di-tert-butyl peroxide or dicumyl peroxide; tert-butylperoxyacetate or tert
-Alkyl peroxy esters such as -butyl peroxypivalate; azo compounds such as azobisisobutyronitrile or azobisisovaleronitrile; or persulfates such as potassium persulfate or ammonium persulfate. Things.

As the polymerization reaction method, there are various known methods as described above. Among them, it is preferable to use bulk polymerization or solution polymerization. Further, in the form of the obtained copolymer as it is, for example, a solution type paint The solution polymerization method is particularly desirable from the viewpoint that it can be used as a resin composition for use.

As a particularly typical example of the solvent used in preparing the fluorine-containing copolymer by a solution polymerization method,
Aromatic hydrocarbons such as benzene, toluene or xylene; aliphatic hydrocarbons such as n-pentane, n-hexane or n-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane or ethylcyclohexane Mixed hydrocarbons such as mineral spirits; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, n-hexanol, n-octanol;
Alcohols such as 2-ethylhexanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol onobutyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether; dimethoxyethane, tetrahydrofuran,
Dioxane, diisopropyl ether or di-n-
Ethers such as butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone or isophorone; methyl acetate, ethyl acetate;
Esters such as n-propyl acetate, isopropyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate; Or chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, trichloroethane or terachlorethane, and N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate.

Such organic solvents may be used alone or in combination of two or more.

In order to prepare the fluorine-containing vinyl polymer (A) from the above-mentioned monomer components by a solution polymerization method, all monomers, a polymerization initiator and a solvent are charged into a reactor at a time and polymerized. Into a reactor charged with fluorinated vinyl monomers and a solvent, a monomer other than the fluorinated vinyl monomers and a polymerization initiator are added either continuously or by dividing, respectively, for polymerization. For example, a method in which all the monomers and the polymerization initiator are added to the reactor charged only with the solvent in a continuous or divided manner and polymerized can be applied.

In the above, the solvent-soluble type fluorine-containing vinyl copolymer has been mainly described. However, as a matter of course, the polymer may be in the form of a so-called non-aqueous dispersion dispersed in a solvent, or It may also contain particles that have been gelled.

Next, the blocked isocyanate compound (B) which is another essential component of the fluorine-containing vinyl polymer composition of the present invention will be described.

A diisocyanate compound (b-) which is a component (essential raw material component) of the blocked isocyanate compound (B)
Particularly typical examples of 1) include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,0-decamethylene diisocyanate, and 1,12-
There are alkylene diisocyanate compounds having 4 to 20 carbon atoms such as dodecamethylene diisocyanate, 1,16-hexadecamethylene diisocyanate and 1,18-octadecamethylene diisocyanate, and if desired, 1,3- or 1,4-diisocyanatocyclohexane, 1,3- or 1,4-bis (isocyanatomethyl) -cyclohexane, 3-isocyanatomethyl-
Cycloalkylenediisodianate compounds such as 3,5,5-trimethylcyclohexyl isocyanate and isopropylidene-bis (4-cyclohexyl isocyanate) may be used.

However, since the cycloalkylenediisocyanate compound has a hard structure, from the viewpoint of obtaining a flexible resin composition aimed at by the present invention, it is usually within a range of up to 40% by weight based on the alkylenediisocyanate compound. Should be used together.

Preferred as long-chain diol (b-2) having a carbon chain described above, which is used as one of the constituent elements of the blocked isocyanate compound, and particularly typical diols include 1,10-decanediol and 1,10-decanediol. Examples thereof include alkylene diols having 10 to 50 carbon atoms, such as hydrogenated dimer of 12-dodecanediol, 12-hydroxystearyl alcohol and oleyl alcohol.
If particularly desired, use a hydrogenated conjugated diene oligomer diol having a number average molecular weight of about 400 to 1,000, for example, hydrogen butadiene diol, or a diol of an ethylene / propylene copolymer oligomer having a number average molecular weight of the above degree. Or, or may be used in combination with the alkylene diol, and if particularly desired,
An ester diol represented by the following general formula [I] (referring to a diol containing a very small amount of ester group in a long-chain diol having a carbon chain) or used in combination with the above-mentioned alkylene diol May be.

HO-R ₁ -OCR ₂ -COR ₁ -OH ... [I] The long-chain diol comprising a diol carbon chain of the present invention (b
It is needless to say that mixing or using a small amount of monoalcohol or triol with respect to -2) is acceptable as long as the properties of the blocked isocyanate compound (B) are not significantly impaired.

In producing the blocked isocyanate compound (B), the long-chain diol (b
-2) is in the range of 1 to 40% by weight, more preferably, the total charged amount of diisocyanate (b-1),
It is appropriate to use within a range of 2 to 30% by weight, and the long-chain diol (b-2) having such a carbon chain and the diisocyanate compound (b-1) are simply mixed and heated,
Although it is possible to derive a polyisocyanate by a urethanization reaction, the desired final blocked isocyanate compound (B) and a fluorine-containing vinyl polymer containing at least two hydroxyl groups on average in one molecule as described above. In order to maintain good compatibility with the union (A), a polyisocyanate containing an isocyanurate ring is preferable.

In the production of polyisocyanate having an isocyanurate ring, a compound having a low electron density and a strongly cationic atom (group) is usually used as an isocyanuration catalyst.
The long-chain diol (b-2) having a carbon chain and the diisocyanate compound (b-
1) is reacted in the presence of such an isocyanurate-forming reaction catalyst, whereby an isocyanurate ring-containing polyisocyanate can be easily obtained.

As the isocyanuration catalyst that can be used in the present invention, it is needless to say that a compound containing an atom (group) having a low electron density and a strong cation property is appropriate. Just to illustrate
N, N, N-trimethyl-N-2-hydroxypropylammonium p-tert-butylbenzoate represented by the following structural formula [II], sodium ethylate or sodium propionate, etc. , The following equation The N, N, N-trimethyl-N-2-hydroxypropylammonium para-tert-butylbenzoate represented by is itself suitable for the production of polyisocyanate because of its easy purification.

In general, it is appropriate to use the catalyst in an amount of 10 to 100 ppm, preferably 20 to 500 ppm, based on the diisocyanate compound (b-1) as a dilute solution with an organic solvent.

The blocked isocyanate compound (B) can be obtained by reacting the polyisocyanate thus obtained with a compound generally known as a blocking agent as shown below.

Among such blocking agents, to mention only typical ones, oxime compounds such as methyl ethyl ketone oxime or methyl isobutyl ketone oxime; lactam compounds such as δ-caprolactam; or amide compounds such as acetanilide or octylic anilide; or isopropyl Alcohol or n-
Various compounds having a so-called active hydrogen atom, such as alcohols such as butyl alcohol, and further, compounds such as acetylacetone and ethyl acetoacetate, which generate an active hydrogen atom by tautomerism, are also examples of the blocking agent. Can be mentioned.

The desired curable resin composition is prepared using the thus obtained essential constituents of the composition of the present invention, each of which is a hydroxyl-containing vinyl-containing vinyl polymer (A) and a blocked isocyanate compound (B). In this case, both of these components may be simply mixed according to a conventional method.

In addition, for example, in preparing a coating material using the resin composition of the present invention, it is preferable to use a known and commonly used curing catalyst as necessary.

Particularly representative of such curing catalysts are various organometallic compounds such as dibutyltin dilaurate, dibutyltin diacetate, tin dioctylate or cobalt naphthenate; or 1,4-diazabicyclo- (2.2.2) -octane or There are various amine compounds such as 1,8-diazabicyclo- (5.4.0) -undecene-7.

If necessary, for example, a coloring pigment and / or a metal powder can be used.

At that time, in order to impart these aesthetics, it is preferable to use the fluorinated vinyl polymer (A) at a ratio of 5 to 200 parts by weight with respect to 100 parts by weight.

In addition, if necessary, various known and commonly used additives such as various resins and solvents, flow control agents, anti-separation agents, antioxidants, ultraviolet absorbers, light stabilizers or silane coupling agents. Of course, agents can be added.

Particularly typical examples of the various resins include cellulose resins such as nitrocellulose or cellulose acetate butyrate, vinyl chloride / vinyl acetate copolymer resins, ketone resins, petroleum resins, acrylic polymers, oil-free alkyds. There are a resin, an alkyd resin and an epoxy resin.

As the above-mentioned solvents, the above-mentioned solvents and their mixtures, such as those used for preparing the above-mentioned fluorine-containing vinyl polymer (A), are used.

As a method of applying a paint obtained using the resin composition of the present invention, a usual method such as a roll coater, an air spray, an airless spray, or an electrostatic coating can be applied.

After painting, for example, at a temperature of 100 to 300 ° C, for a few seconds to
By heating for about 60 minutes, a cured coating film can be obtained.

〔Example〕

Next, the present invention by reference examples, examples and comparative examples,
More specifically, in the following, parts and%
All are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Fluorovinyl-Containing Polymer (A) Form] In a 2-liter stainless steel autoclave sufficiently purged with nitrogen, 10 p-tert-butylvinylbenzoate was added.
0 parts, "VeoVa 9" (manufactured by The Netherlands Shell, the C ₉ comprising branched aliphatic carboxylic acid vinyl esters) of 390
Parts, 4-hydroxybutyl vinyl ether 110 parts, n-butyl acetate 430 parts, azobisisovaleronitrile (ABVN) 15 parts, tert-butyl peroxyoctoate (TBPO) 10 parts and "Sanol LS- 765 "(an amine compound manufactured by Sankyo Co., Ltd.).

Next, the liquefied and collected chlorotrifluoroethylene
400 parts are injected and reacted with stirring at 60 ° C for 15 hours. When the nonvolatile content (NV) reaches 67%, the mixture is cooled to room temperature, and 318 parts of xylene is added to increase the NV to 55%. A solution of the copolymer was obtained. Hereinafter, this is abbreviated as copolymer (A-1).

Reference Example 2 (same as above) The same procedure as in Reference Example 1 was repeated except that the monomer composition was changed to "Vova 9" 250 parts 4-hydroxybutyl 100〃 vinyl ether ethyl vinyl ether 150〃 chlorotrifluoroethylene 500〃. Is cooled to room temperature at the point where 68% is reached, 60 parts of xylene is added, and NV
A 55% solution of the desired copolymer was obtained. Hereinafter, this is abbreviated as copolymer (A-2).

Reference Example 3 (same as above) NV was 68% in the same manner as Reference Example 1 except that the composition of the monomer was changed to 410 parts of cyclohexyl vinyl ether, 4-hydroxybutyl 100 °, vinyl ether chlorotrifluoroethylene 490 °. At room temperature, add 346 parts of xylene,
Was 55% to obtain a solution of the target copolymer. Hereinafter, this is abbreviated as copolymer (A-3).

Reference Example 4 [Preparation Example of Isocyanate Compound (B)] In a 5-liter glass four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, an air cooling tube, and a thermometer, a “Desmodur 3,500 g of "H" (hexamethylene diisocyanate manufactured by Bayer AG, West Germany)
And 716.3 g of "Crosanol" (12-hydroxystearyl alcohol manufactured by Henkel; purity: about 80%).

Next, an oil bath was attached to the flask, and the temperature was raised to 65 ° C. while stirring, so that the contents of the flask became a homogeneous liquid.

Subsequently, after maintaining at the same temperature for 2 hours, the temperature was lowered to 55 ° C.

As an isocyanuration catalyst, 3.4 g of a 20% butyl cellosolve solution of N, N, N-trimethyl-N-2-hydroxypropylalmonium p-tert-butylbenzoate was added in portions and added at a temperature of 60 ° C. for 3 hours. After reacting, 3.4 g of 7% xylene solution of monochloroacetic acid
Was added to deactivate the isocyanurate-forming catalyst, and the isocyanurate-forming reaction was terminated.

After the reaction mixture was cooled to room temperature, 1,000 g thereof was subjected to molecular distillation to obtain 549.4 g (conversion rate: 55.0%) of an isocyanate compound having an isocyanurate ring as a distillation residue.

Next, 200 g of this isocyanate compound, 57 g of methylkeethyl toxime, 37 g of xylene and 42 g of cellosolve acetate were placed in a 500 ml glass four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and exhaust port.
g.Additionally, 0.5 g of dibutyltin diacetate was added as a urethanization reaction catalyst, the temperature was raised to 70 ° C., and the temperature was maintained at that temperature for 3.5 hours.There was no unreacted isocyanate group. Was confirmed by chemical analysis to terminate the reaction.

The target blocked isocyanate compound thus obtained was a viscous liquid, having an NV of 75.3% and an effective isocyanate content of 8.7%. Hereinafter, this is abbreviated as B-1.

Reference Example 5 (same as above) As the diisocyanate compound, the amount of hexamethylene diisocyanate used was changed to 3,290 g, and 210 g of “Takenate 500” [Takeda Pharmaceutical Co., Ltd.
Xylylene diisocyanate) was changed to use 210 g of the same isocyanuration catalyst liquid.
The isocyanuration reaction was carried out in exactly the same manner as in Reference Example 4, except that 7 g was used, to obtain 4,219 g of a reaction mixture in which the catalyst had been deactivated.

1,003 g of the obtained reaction mixture was subjected to molecular distillation to obtain 522 g (cyclization ratio: 52.1%) of an isocyanate compound having an isocyanurate ring as a distillation residue.

Next, 200 g of this isocyanate compound, 53 g of methylkeethyl toxime, 38 g of xylene and 40 g of cellosolve acetate were placed in a 500 ml glass four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and exhaust port.
g.Additionally, 0.5 g of dibutyltin diacetate was added as a urethanization reaction catalyst, the temperature was raised to 70 ° C., and the temperature was maintained at that temperature for 3.5 hours.There was no unreacted isocyanate group. Was confirmed by chemical analysis to terminate the reaction.

The blocked isocyanate compound thus obtained is
It was a viscous liquid with an NV of 75.6% and an effective isocyanate content of 8.3%. Hereinafter, this is referred to as B-
Abbreviated as 2.

Reference Example 6 (same as above) As the diisocyanate compound, the amount of hexamethylene diisocyanate used was 2,100 g, and "Takenate 60
0 "[1,3-bis (isocyanatomethyl) -cyclohexane manufactured by Takeda Pharmaceutical Co., Ltd.]
An isocyanuration reaction was carried out in the same manner as in Reference Example 4 except that 3.9 g of the same isocyanurate-forming catalyst solution was also used, and 4,215 g of a reaction mixture in which the catalyst had expired was used.
I got

1,001 g of the obtained reaction mixture was subjected to molecular distillation to obtain 541.7 g of an isocyanate compound having an isocyanurate ring (conversion rate: 54.2 g) as a distillation residue.

Next, 200 g of this isocyanate compound, 55 g of methyl keethyl toxime, 38 g of xylene and 40 g of cellosolve acetate were placed in a 500 ml glass four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and exhaust port.
g.Additionally, 0.5 g of dibutyltin diacetate was added as a urethanization reaction catalyst, the temperature was raised to 70 ° C., and the temperature was maintained at that temperature for 3.5 hours.There was no unreacted isocyanate group. Was confirmed by chemical analysis to terminate the reaction.

The blocked isocyanate compound thus obtained is
It was a viscous liquid with an NV of 75.2% and an effective isocyanate content of 8.6%. Hereinafter, this is referred to as B-
Abbreviated as 3.

Reference Example 7 (same as above) The method was changed so that 3,500 g of 1,3-bis (isocyanatomethyl) -cyclohexane and 245 g of 12-hydroxystearyl alcohol were used, and 6.6 g of the same catalyst solution was used. , Isocyanuration reaction is 70
In the same manner as in Reference Example 4 except that the temperature was changed to ° C, 3,750 g of a reaction mixture in which the catalyst had been deactivated was obtained.

1,001 g of the obtained reaction mixture was subjected to molecular distillation to obtain 491.7 g (conversion rate: 49.2%) of an isocyanate compound having an isocyanurate ring as a distillation residue.

The isocyanate content of the isocyanate compound is 17.1
%Met.

Next, 195 g of this isocyanate compound and 64 parts of methylketoxime were placed in a 500 ml glass four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and exhaust port.
g, 38 g of xylene and 40 g of cellosolve acetate, and as a urethanization reaction catalyst, 0.5 g of dibutyltin diacetate was added, and the temperature was raised to 70 ° C.
After 3.5 hours, it was confirmed by chemical analysis that there was no unreacted isocyanate group, and the reaction was terminated.

The target blocked isocyanate compound thus obtained was a viscous liquid, having an NV of 75.4% and an effective isocyanate content of 9.3%. Hereinafter, this is abbreviated as B-4.

Examples 1 to 4 and Comparative Example 1 First, a pigment was dispersed in each resin composition obtained in each Reference Example as it was in the mixing ratio shown in Table 1, and then the dissociation of the blocking agent was performed. Dibutyltin laurate as a catalyst was also added, and “Solvesso 15
0 "(exxon aromatic hydrocarbon solvent) / acetic acid-
The mixture was diluted with a mixed solvent of n-butyl / cyclohexane = 75/15/10 (weight ratio) with Ford Cup No. 4 so as to be 120 seconds to obtain various white paints.

Each paint and a commercially available, hydroxyl-free vinylidene fluoride-based white paint as a control were applied to a zinc phosphate treated steel sheet (0.3 mm thick) on which a baked coating film of an epoxy resin primer was formed in advance. Each was separately applied by a roll coater so as to have a dry film thickness of 15 μm, and then heat-cured for 1 minute so that the substrate temperature was 220 ° C. to obtain a coated steel sheet.

However, only in the case of the control commercial paint, a continuous coating film was not formed by such heat curing.

Then, when the heating was continued for another 10 minutes at the same temperature, a continuous coating film was obtained.

Next, the coating performance of each coated steel sheet was compared and examined. The results are collectively shown in the same table.

The “bending resistance” was comprehensively visually determined as to the presence or absence of “crack” or “peeling” of the bent portion.

The "weather resistance" is measured using an accelerated weather resistance tester (Light Control Dupanel) manufactured by Suga Test Instruments Co., Ltd.

[Effects of the Invention] As described above, the fluorine-containing vinyl polymer composition of the present invention is particularly excellent in weather resistance,
Moreover, it has excellent gloss and flexibility, and is extremely practical.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 18 / 62,18 / 80,18 / 10 C09D 175/04

Claims (7)

(57) [Claims] 1. A fluorinated vinyl polymer (A) having an average of at least two hydroxyl groups in one molecule, a diisocyanate compound (b-1) and a long-chain diol (b-2) having a carbon chain. A fluorine-containing vinyl polymer composition comprising, as an essential component, a blocked isocyanate compound (B) obtained by blocking a polyisocyanate compound obtained by reacting. 2. The method according to claim 1, wherein the fluorine-containing vinyl polymer (A) is
15 to 75% by weight of the fluorine-containing vinyl monomer (a-1), 1 to 30% by weight of the hydroxyl group-containing vinyl monomer (a-2), and another copolymerizable monomer (a- The fluorine-containing vinyl polymer composition according to claim 1, which is obtained by copolymerizing 3) with 5 to 85% by weight. 3. The method according to claim 1, wherein the fluorine-containing vinyl polymer (A) is
As the fluorine-containing vinyl monomer (a-1), tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinyl fluoride, vinylidene fluoride, and an alkyl group having 1 to 18 carbon atoms (per) fluoro The compound is obtained using at least one compound selected from the group consisting of an alkyl vinyl ether and a (per) fluoroalkyl trifluorovinyl ether having 1 to 18 carbon atoms in the alkyl group.
3. The fluorine-containing vinyl polymer composition according to item 1. 4. A method according to claim 1, wherein the fluorovinyl polymer (A) is
As the other copolymerizable monomer (a-3),
The fluorine-containing vinyl polymer composition according to claim 1 or 2, which is obtained using at least one compound selected from the group consisting of alkyl vinyl ethers, cycloalkyl vinyl ethers, and carboxylic acid vinyl esters. 5. The method according to claim 1, wherein the blocked isocyanate compound (B) is a diisocyanate compound (b-1).
The fluorine-containing vinyl polymer composition according to claim 1, which is obtained by using an alkylene diisocyanate having 4 to 20 carbon atoms. 6. A method according to claim 1, wherein the blocked isocyanate compound (B) is a long-chain diol (b) having a carbon chain.
The fluorine-containing vinyl polymer composition according to claim 1, wherein the composition is obtained by using an alkylene diol having 10 to 50 carbon atoms as -2). 7. The above-mentioned blocked isocyanate compound (B) is replaced by the above-mentioned diisocyanate compound (b-1)
And a long-chain diol having a carbon chain as described above (b-2)
The fluorine-containing vinyl polymer composition according to claim 1, which is obtained by blocking a polyisocyanate compound having an isocyanurate ring, which is obtained by reacting a polyisocyanate compound in the presence of an isocyanurate-forming catalyst.