JPH0532726A - Fluorine-containing resin and coating material composed mainly of the same resin - Google Patents

Abstract

PURPOSE:To provide the subject resin composed of specified constituting components, excellent in gloss, solubility, compatibility, water resistance, shelf life, weather resistance and chemical resistance and useful for a coating material, etc. CONSTITUTION:An objective resin composed of (A) 0.01-20mol% unit represented by formula I (R<1> is H, 1-18C alkyl or 1-8C acyl; R<2>-R<5> are 1-18C alkyl; R<6> is divalent organic group; R<7>-R<9> are H or 1-2C alkyl; X and Y are imino or 0; i, j, k, l and m are 0 or 1), (B) 20-80mol% unit shown by formula II (V, X, Y and Z are H, F, Cl, 1-6C alkyl, etc.) and (C) 3-80mol% unit represented by formula III (W is univalent organic group having cyclic hydrocarbon; R<10> is divalent organic group; R<11> and R<1> are H or 1-2C alkyl).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing resin and a paint containing it as a main component.

[0002]

Fluorine-containing resins have hitherto been widely used in many fields because they are extremely excellent in heat resistance, mechanical properties, chemical resistance, weather resistance and the like. One of its uses is as a coating film forming component of paint.
For example, a fluororesin paint using a tetrafluoroethylene polymer or a vinylidene fluoride polymer is known,
Since it has excellent lubricity, non-adhesiveness, weather resistance and chemical resistance, it is used as a coating material in the fields of chemical industry, food, construction, machinery and the like.

However, the fluororesin coating composition has a drawback that it needs to be baked at a high temperature and the range of use is inevitable. Therefore, in recent years, it is soluble in an organic solvent and at room temperature. Attempts have been made to develop solvent-based paints using a fluorine-containing resin having a curable reactive group. By the way, examples of the fluorine-containing resin soluble in an organic solvent include, for example, JP-A-57-34107 and JP-A-61-275311.
JP-A-61-157609 and JP-A-62-1742.
No. 13, JP-A No. 63-182312, and the like, copolymers of fluoroolefins and vinyl monomers copolymerizable therewith are known.

However, in these copolymers, an alkyl vinyl ether or a special vinyl ester of carboxylic acid is used as a copolymerization component, but these copolymerization components give flexibility to the coating film, but on the other hand, In addition to lowering the hardness, the coating film has low gloss and is insufficient in compatibility with the curing agent. Further, among these fluorine-containing resins, those having a hydroxyl group, which are particularly useful for coating materials, have a problem of poor storage stability such as high molecular weight or gelation over time.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a fluorine-containing resin in which the above-mentioned problems of the prior art have been solved, that is, the solubility in an organic solvent and the compatibility with a curing agent are excellent, and the storage stability is excellent. Another object of the present invention is to provide a fluorine-containing resin, and a fluorine-based coating composition containing this as a main component, which is glossy, hard, and capable of giving a coating film having excellent weather resistance.

[0006]

Means for Solving the Problems As a result of intensive studies in view of the above points, the present inventors have solved the above problems by introducing a functional group having a specific structure into the side chain of a fluororesin. After finding what to obtain, the present invention has been completed. That is, the present invention is: A fluorine-containing resin comprising the following components. Formula (A);

[0007]

[Chemical 4]

Unit represented by 0.01 to 20
Mol% (B) formula;

[0009]

[Chemical 5]

Unit represented by 20 to 80 mol% (C) formula;

[0011]

[Chemical 6]

A fluorine-based coating composition containing 3 to 80 mol% of a unit represented by and the above-mentioned fluorine-containing resin as a main component. Hereinafter, the present invention will be described in detail. The fluorine-containing resin having the above-mentioned (A), (B) and (C) as a constitutional unit according to the present invention is (b) copolymerized with a vinyl monomer corresponding to each constitutional unit, or (b) the above ( A), (B) and at least one part of the hydroxyl groups of the fluorine-containing fluororesin containing the following formula (D-1) as constituents are reacted with at least one cyclic hydrocarbon group-containing monoisocyanate. can get.

Formula (D-1):

[0014]

[Chemical 7]

Unit represented by 3 to 80 mol% First, (a) (when copolymerizing vinyl monomers corresponding to the respective constitutional units) will be described. In the fluorine-containing resin of the present invention, the vinyl monomer forming the unit (A) is represented by the formula (a)

[0016]

[Chemical 8]

What is represented by is used. Specific examples of the vinyl monomer include, for example, 4- (meth) acryloyloxy-2,2,6,6, -tetramethylpiperidine and 4- (meth) acryloyloxy-1,2,2.
6,6, -Pentamethylpiperidine, 4- (meth) acryloyloxy-1-acetyl-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6 6, -pentaethylpiperidine,
4- (meth) acryloyloxyethyloxy-1,
(Meth) acrylic acid ester derivatives such as 2,2,6,6, -pentamethylpiperidine, 4- (meth) acryloylamino-2,2,6,6, -tetramethylpiperidine, 4- (meth) acryloylamino -1, 2, 2,
Acrylamide derivatives such as 6,6, -pentamethylpiperidine and 4- (meth) acryloylamino-1-acetyl-2,2,6,6, -tetramethylpiperidine, 4-
Crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-1,2,2
Crotonic acid ester derivatives such as 6,6, -pentamethylpiperidine, 4-vinyloxy-2,2,6,6, -tetramethylpiperidine, 4-vinyloxy-1,2,
2,6,6, -Pentamethylpiperidine, 4-vinyloxy-1-acetyl-2,2,6,6, -tetramethylpiperidine, 4-vinyloxy-1,2,2,6,6
-Pentaethylpiperidine, 4- (2-vinyloxyethyloxy) -1,2,2,6,6, -pentamethylpiperidine, vinyl-9-aza-3-ethyl-8,8,
9,10,10-Pentamethyl-1,5-dioxaspiro [5,5] -3-undecylmethyl ether, vinyl-9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5 -Vinyl ether derivatives such as dioxaspiro [5,5] -3-undecylmethyl ether, 4-
Allyloxy-2,2,6,6, -tetramethylpiperidine, 4-allyloxy-1,2,2,6,6, -pentamethylpiperidine, 4-allyloxy-1-acetyl-2,2,6,6, -Tetramethylpiperidine, Allyl-9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro [5,5] -3-
Examples include allyl derivatives such as undecyl methyl ether, allyl-9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro [5,5] -3-undecylmethyl ether, and the like. be able to. These may be used alone or in combination of two or more.

In the fluorine-containing resin of the present invention, (A)
The content of the unit is 0.01 to 20 mol%, preferably 0.1.
It is necessary to be in the range of 05 to 10 mol%. If this content is less than 0.01 mol%, the storage stability is poor, and 2
If it exceeds 0 mol%, the water resistance and chemical resistance decrease. In the fluorine-containing resin of the present invention, the vinyl monomer forming the unit (B) is represented by the formula (b)

[0019]

[Chemical 9]

What is represented by is used. Specific examples of such a vinyl monomer include, for example,

[0021]

[Chemical 10]

Fluoroethylene such as;

[0023]

[Chemical 11]

A fluoropropene system such as;

[0025]

[Chemical 12]

Examples thereof include fluoroolefin compounds having 4 or more carbon atoms. Among these, among these,
(B ') expression

[0027]

[Chemical 13]

The fluoroethylene compounds and fluoropropene compounds are preferable represented by, in particular tetrafluoroethylene (CF ₂ = CF _2), chlorotrifluoroethylene (CF ₂ = CFCl) and hexafluoropropene (CF ₂ = CFCF ₃₎ is It is suitable. These fluoroolefins may be used alone or in combination of two or more.

In the fluorine-containing resin of the present invention, (B)
The content of the unit is 20 to 80 mol%, preferably 40 to 6
It should be in the range of 0 mol%. If this content is less than 20 mol%, the weather resistance is insufficient, and if it exceeds 80 mol%, the solubility in organic solvents is reduced. In the fluorine-containing resin of the present invention, the vinyl monomer forming the (C) unit is represented by the formula (c)

[0030]

[Chemical 14]

What is represented by is used. Such a vinyl monomer is obtained by reacting a hydroxyl group-containing vinyl monomer represented by the formula (d-1) with at least one cyclic hydrocarbon group-containing monoisocyanate.

[0032]

[Chemical 15]

Specific examples of these hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether,
4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether and other hydroxyalkyl vinyl ethers, 2-hydroxyallyl vinyl ether, 4-hydroxybutyl allyl ether and other hydroxyalkyl allyl ethers, 2-hydroxyethyl (meth) acrylate, 4-hydroxy Typical examples are hydroxyl group-containing (meth) acrylates such as propyl (meth) acrylate, 2-hydroxyethyl crotonate, hydroxyl group-containing crotonic acid esters such as 4-hydroxypropyl crotonate, and allyl alcohol.
Of these, hydroxyalkyl vinyl ethers are preferable because of their good reactivity with fluoroolefins. These hydroxyl group-containing vinyl monomers may be used alone or in combination of two or more.

Examples of the cyclic hydrocarbon group-containing monoisocyanate include isocyanate groups of monoisocyanates such as cyclohexyl isocyanate, alkyl-substituted cyclohexyl isocyanate, benzyl isocyanate, and methyl-cyclohexane isocyanate. Furthermore, 3-isocyanatomethyl-3,5,5-
Trimethylcyclohexyl isocyanate; (IPD
I), 1,3- (or 1,4) bis (isocyanatomethyl) cyclohexane; (hydrogenated XDI), 1,3- (or
1,4) bis (isocyanatomethyl) benzene; (XD
I), 1,3- (or1,4) bis (α, α-dimethylisocyanatomethyl) benzene; (TMXDI), 1,3
-(Or1,4) diisocyanatocyclohexane, 1-
Cyclic hydrocarbon group-containing diisocyanate monomers such as methyl-1,3- (or1,4) diisocyanatocyclohexane (hydrogenated TDI), bis (4-isocyanatocyclohexyl) methane; (hydrogenated MDI) 2 Only one of the two isocyanate groups is
Obtained by reacting with a monovalent active hydrogen compound such as propanol, isopropanol, n-butanol, isobutanol, hexanol, cyclohexanol, benzyl alcohol, 2-ethylhexyl alcohol, dipropylamine, dibutylamine, diisobutylamine, dicyclohexylamine. Examples include monoisocyanate compounds, so-called half block compounds.

These so-called half block compounds are generally obtained by reacting a corresponding diisocyanate monomer and an active hydrogen compound under diisocyanate excess conditions, preferably at an NCO / OH equivalent ratio of 6 or more. The excess isocyanate monomer is removed and purified to obtain a mixture containing a half block as a main component.

As mentioned above, it is essential that the isocyanates used in the present invention have a cyclic saturated hydrocarbon group or an aromatic ring. For example, phenyl isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, etc. Those in which an isocyanate group is directly bonded to the aromatic ring as described above are not preferable because they cause a defect in the weather resistance of the coating material.

These monoisocyanates can be used by appropriately mixing them, and optionally, aliphatic monoisocyanates such as butyl isocyanate, hexyl isocyanate, 2-ethylhexyl isocyanate and octadecyl isocyanate, And / or hexamethylene diisocyanate, 3,3,5- (or 3,5,5-)
It is also possible to use a mixture with an aliphatic diisocyanate such as trimethyl trimethylhexamethylene diisocyanate, or a diisocyanate such as the above-mentioned cyclic hydrocarbon group-containing diisocyanate.

When the above-mentioned hydroxyl group-containing vinyl monomer is reacted with at least one cyclic hydrocarbon group-containing monoisocyanate to obtain a cyclic hydrocarbon group-containing vinyl monomer, The OH group and the NCO group of the isocyanates may be reacted in an equivalent amount to obtain the desired vinyl monomer containing a cyclic hydrocarbon group and then subjected to copolymerization, or at an NCO / OH equivalent ratio of 3 / 100-100 /
100, preferably 10/100 to 70/100 in the range of the hydroxyl group-containing vinyl monomer excess conditions, and after reacting in the presence of other copolymerizable vinyl monomer if necessary,
It may be subjected to a desired copolymerization reaction. Furthermore, it is also possible to charge the desired vinyl monomer and the isocyanate component at the same time into the reactor to carry out the polymerization reaction and the urethane group forming reaction at the same time. A solvent may or may not be used in the reaction, but it is possible to use a solvent such as toluene, xylene, ethyl acetate, butyl acetate, cellosolve acetate, methyl ethyl ketone, or methyl isobutyl ketone, and to accelerate the reaction. Therefore, for example, a known urethanization reaction promoting catalyst such as dibutyltin dilaurate can be added.

The reaction temperature is usually selected from room temperature to about 120 ° C. The progress of the reaction is traced by following the decrease of the NCO group by, for example, infrared absorption spectrum or titration, and the reaction is usually terminated when the NCO group disappears. In the fluorine-containing resin of the present invention, the content of the (B) unit needs to be in the range of 3 to 80 mol%, preferably 5 to 50 mol%. If this content is less than 3 mol%, the compatibility with the curing agent and the coating film hardness will be poor, and if it exceeds 80 mol%, the weather resistance will decrease.

The fluorine-containing resin of the present invention can be used in the presence or absence of a solvent in the above formulas (a), (b) and (c).
It can be produced by copolymerizing a predetermined proportion of a vinyl monomer mixture having the formula as an essential component with a polymerization initiator, an ionizing radiation or the like as a polymerization initiation source. As the polymerization initiator, a water-soluble one or an oil-soluble one is appropriately used depending on the type of polymerization or desired.

Examples of the oil-soluble initiator include azo compounds such as azobisisobutyronitrile and 2,2'-azobis- (2,4-dimethylvaleronitrile), t-butyl peroxypivalate and t-butyl. Peroxyester type peroxides such as peroxyisobutyrate, octanoyl peroxide, diacyl peroxide type peroxides such as lauroyl peroxide, dialkyl peroxydicarbonate type peroxides such as diisopropyl peroxydicarbonate, Examples thereof include dialkyl peroxide type peroxides such as benzoyl peroxide.

As the water-soluble polymerization initiator, for example, a persulfate such as potassium persulfate, hydrogen peroxide, or a redox initiator composed of a combination of these with a reducing agent such as sodium hydrogen sulfite and sodium thiosulfate, and further ,
Inorganic initiators such as those in which a small amount of iron, ferrous salt, silver nitrate, etc. coexist, dibasic acid peroxides such as disuccinic acid peroxide, diglutaric acid peroxide, and monosuccinic acid peroxide, azobi Examples include organic initiators such as perisobutylamidine dibasic acid salt. The amount of these polymerization initiators to be used is appropriately selected depending on the type, the copolymerization reaction conditions, etc., but 0.005 to 5% by weight, preferably 0.05 to the total amount of the monomers usually used. To 0.5% by weight.

The polymerization method is not particularly limited and, for example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be used. From the viewpoint of stability of the polymerization reaction operation, etc. Solvents such as lower alkyl-substituted benzenes such as xylene and toluene, esters such as butyl acetate, ketones such as methyl isobutyl ketone, alcohols such as t-butanol, and saturated halogenated hydrocarbons having one or more fluorine atoms are used as a solvent. The solution polymerization method, the emulsion polymerization method in an aqueous medium, the bulk polymerization method that does not require separation from the solvent, and the like are preferably used.

Further, the polymerization system is not particularly limited, and any of batch system, anti-continuous system and continuous system can be used. The reaction temperature in the copolymerization reaction is usually -30.
Within the range of to + 150 ° C, it is appropriately selected depending on the type of the polymerization initiation source and the polymerization medium, and is usually 0 to 100 ° C, preferably 1
It is selected in the range of 0 to 90 ° C. The reaction pressure is not particularly limited, but it is selected within the range of normal pressure to 100 kg / cm ² . Further, the copolymerization reaction can be carried out by adding an appropriate chain transfer agent.

Then, as a method for producing the fluorine-containing resin of the present invention, at least a part of the hydroxyl groups of the hydroxyl-containing fluorine-containing resin containing (b) ((A), (B) and (D-1) as constituents. And at least one cyclic hydrocarbon group-containing monoisocyanate are reacted with each other.). Formula (A);

[0046]

[Chemical 16]

Unit represented by: 0.01 to 20
Mol% (B) formula;

[0048]

[Chemical 17]

Unit represented by 20 to 80 mol% (D-1) formula;

[0050]

[Chemical 18]

Units represented by 3 to 80 mol% Hydroxyl group-containing fluororesin which also contains (A), (B) and (D-1) as a constituent component is a vinyl monomer corresponding to each constituent unit. Obtained by copolymerizing the formula (a), the formula (b) and the formula (d-1) by the same method as the above-mentioned (a) (copolymerizing vinyl monomers corresponding to respective constitutional units). To be

Formula (a);

[0053]

[Chemical 19]

Formula (b);

[0055]

[Chemical 20]

Formula (d-1);

[0057]

[Chemical 21]

Specific examples of these vinyl monomers are the same as those exemplified in (a). In the reaction of the hydroxyl group-containing fluororesin thus obtained with the cyclic hydrocarbon group-containing monoisocyanates, OH of the hydroxyl group-containing fluororesin is obtained.
The equivalent ratio of the group to the NCO group of the isocyanate is usually 3
/ 100 to 100/100, preferably 10/100 to
It is set in the range of 70/100. For the reaction temperature, the use of solvent and reaction accelerating catalyst, the confirmation method of the reaction end point, etc.,
According to the reaction between the hydroxyl group-containing vinyl monomer and the cyclic hydrocarbon group-containing monoisocyanate described in (a).

Specific examples of the cyclic hydrocarbon group-containing monoisocyanates are the same as those exemplified in (a). The above-mentioned (a); a method of copolymerizing vinyl monomers corresponding to the respective constitutional units, or (b); at least a part of the hydroxyl groups of the fluorine-containing resin having a hydroxyl group and at least one cyclic hydrocarbon group-containing monomer. The fluorine-containing resin of the present invention obtained by the method of reacting with an isocyanate has the formula (A):

[0060]

[Chemical formula 22]

Unit represented by 0.01 to 20
Mol% (B) formula;

[0062]

[Chemical formula 23]

Unit represented by 20 to 80 mol% (C) formula;

[0064]

[Chemical formula 24]

The unit represented by the formula (3) is composed of 3 to 80 mol%, but in addition to the units (A), (B) and (C), the (D) functional group is contained within a range not exceeding 50 mol%. It is desirable to include a copolymerized unit of a group-containing vinyl monomer and / or (E) a copolymerized unit of another vinyl monomer. Examples of the functional group-containing vinyl monomer forming the unit (D) include a hydroxyl group-containing vinyl monomer represented by the formula (d-1) and an epoxy group-containing vinyl monomer represented by the formula (d-2). And a hydrolyzable silyl group-containing vinyl monomer represented by the formula (d-3).

[0066]

[Chemical 25]

[0067]

[Chemical formula 26]

[0068]

[Chemical 27]

Hydroxyl group-containing vinyl monomer [(d-1) formula]
(A); (the same as those exemplified in the method of copolymerizing vinyl monomers corresponding to the respective constitutional units. Epoxy group-containing vinyl monomer [(d-2) formula] For example,

[0070]

[Chemical 28]

And the like. Specific examples of the hydrolyzable silyl group-containing vinyl monomer [(d-3) formula] include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, allyltrimethoxysilane, and allyltriethoxysilane. , Allyldimethoxymethylsilane, vinyloxypropyltrimethylsiloxysilane, vinyloxyethoxypropyltrimethylsiloxysilane, 3-trimethoxysilylpropyl (meth) acrylate and the like.

The functional group-containing vinyl monomer forming the unit (D) may be used alone or in combination of two or more kinds. Examples of the other copolymerizable vinyl monomer forming the unit (E) include olefins such as ethylene, propylene and isobutylene,
Haloolefins such as vinyl chloride and vinylidene chloride, vinyl acetate, vinyl n-butyrate, vinyl benzoate, pt-
Vinyl butyl benzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate, vinyl laurate, and other carboxylic acid vinyl esters, isopropenyl acetate, isopropyl isopropenyl, and other carboxylic acid isopropenyl esters, ethyl vinyl ether , Propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether,
Chain alkyl vinyl ethers such as neopentyl vinyl ether, 2-ethylhexyl vinyl ether and octyl vinyl ether, fluorovinyl ethers such as pentafluoroethyl vinyl ether and 2-perfluorooctylethyl vinyl ether, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, phenyl Aryl vinyl ethers such as vinyl ether, aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether, aromatic vinyl compounds such as styrene and vinyltoluene Allyl formate, allyl acetate, allyl butyrate, allyl benzoate, allyl cyclohexanecarboxylate, allyl cyclohexylpropionate Allyl esters such as, allyl ethyl ether, allyl Allyl ethers such as phenyl ether, butyl (meth) acrylate, methyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy-4
-(2-methacryloxyethoxy) benzophenone, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoropropylomethyl (meth) acrylate, perfluoromethylmethyl (meth) acrylate, 2-perfluorooctyl Esters of acrylic acid and methacrylic acid such as ethyl (meth) acrylate and perfluoroisononylmethyl (meth) acrylate, acrylamides such as acrylamide and N-methylol acrylamide, and Japanese Patent Application No. 2-10.
Examples thereof include endocyclic vinyl ethers such as those shown in No. 1695.

These vinyl monomers may be used alone or in combination of two or more. In the fluorine-containing resin of the present invention, within a range not exceeding 50 mol%,
(D) Copolymerized unit of functional group-containing vinyl monomer and /
Alternatively, those containing a unit in which (E) another vinyl monomer is copolymerized can be copolymerized to form the functional group-containing vinyl monomer forming the (D) unit and / or the (E) unit forming copolymer. It can be obtained by using other vinyl monomers as copolymerization components within a range not exceeding 50 mol%.

The molecular weight of the fluorine-containing resin of the present invention is determined by gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent and monodisperse polystyrene having a known molecular weight as a standard substance. Is in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and the glass transition temperature (Tg) is usually -50 to 120 ° C, preferably -1.
It is 0 to 100 ° C.

The fluorine-containing resin of the present invention having such a composition, molecular weight, and glass transition temperature is soluble in an organic solvent, has excellent compatibility with a curing agent, and has good storage stability. A cured coating film of a coating material containing a fluorine-containing resin as a main component has gloss and hardness and excellent weather resistance.
In the fluorine-containing resin of the present invention, when a hydroxyl group-containing vinyl monomer is used as the functional group-containing vinyl monomer forming the (D) unit, the obtained fluorine-containing resin contains a hydroxyl group as a curing site. By using a curing agent used in ordinary thermosetting acrylic paints, for example, polyvalent isocyanates, block isocyanate-based curing agents, melamine curing agents, urea resin curing agents, polybasic acid curing agents, etc. It can be cured by heating.

Furthermore, the hydroxyl group-containing fluororesin can be cured at room temperature by using polyisocyanates. As the polyvalent isocyanates,
For example, non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate and adducts thereof, polyvalent isocyanates having an isocyanurate ring, and the like are preferably mentioned. A polyvalent isocyanate having an isocyanurate ring with good solubility is suitable. When using these polyvalent isocyanates for room temperature curing, known catalysts such as dibutyltin dilaurate may be added to accelerate curing.

In the fluororesin of the present invention, when an epoxy group-containing vinyl monomer is used as the functional group-containing vinyl monomer forming the (D) unit, the obtained fluororesin has a cured site. By using a polyaddition type curing agent such as polyamines, acid anhydrides, polyphenols and polymercaptans or a catalyst type curing agent such as imidazole and BF _{3 as} a curing agent, It can be heat-cured or room-temperature cured.

Further, in the fluorine-containing resin of the present invention,
As the functional group-containing vinyl monomer forming the (D) unit,
When a hydrolyzable silyl group-containing vinyl monomer is used, the obtained fluororesin contains a hydrolyzable silyl group as a curing site, and is used as an amine compound such as butylamine or dibutyltin dilaurate. It can be moisture cured using a curing catalyst.

The fluorine-containing resin of the present invention can be used as a lacquer type coating material when it does not contain the (D) unit. The present invention, together with the novel fluororesin described above, provides a fluorine-based coating composition containing this as a main component, and when the fluororesin is used as a solution type coating, various solvents may be used. it can.

Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, alcohols such as n-butanol, esters such as n-butyl acetate, ketones such as methyl isobutyl ketone, glycols such as ethyl cellosolve. Examples thereof include ethers and various commercially available thinners. The solution-type paint is prepared by homogenizing the fluorine-containing resin and the solvent using a mixer which is usually used for preparing paints, such as a ball mill, a paint shaker, a sand mill, a jet mill, a three-roll mill and a kneader. It can be carried out by mixing. At this time, if desired,
A pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent, an antigelling agent, an ultraviolet absorber and the like can be added.

[0081]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to the embodiments. In addition, all% in the examples indicate% by weight. Molecular weights of various resins: Determined from a polystyrene standard calibration curve using gel permeation chromatography.

(Device used) Device: Shimadzu LC-3A Column: Tosoh Corporation TSKgel G-5000 HXL TSKgel G-4000 HXL TSKgel G-2000 HXL Detector: Shimadzu RID-6A Data processing: Shimadzu C- R4A carrier: Tetrahydrofuran Glass transition temperature (Tg) of various resins; measured using the following equipment and measurement conditions.

Equipment used: Differential thermal / thermogravimetric simultaneous measurement apparatus (manufactured by Seiko Instruments Inc.) SSC 5000DS
C 200 measurement conditions: -40 to 120 ° C. temperature rise (5 ° C./min) hydroxyl value; measured according to JIS K-0070. Gloss, Flexibility, Adhesion (Al): JIS K-540
It measured according to 0. Coating hardness: Measured according to ISO-1522. Weather resistance: Determined according to ASTM G-53. Infrared absorption spectrum (IR spectrum): Measured using FT-IR-5M type manufactured by JASCO Corporation.

[0084]

Example 1 The inside of a stainless steel autoclave equipped with a stirrer having an internal volume of 1 liter was replaced with nitrogen gas three times.
Then, 49 g of 4-hydroxybutyl vinyl ether,
25 g of cyclohexyl isocyanate, 74 g of xylene
Was charged and reacted at 80 ° C. for 6 hours. Thereafter, 1.3 g of 4-methacryloyloxy-1,2,2,6,6, -pentamethylpiperidine and 5 parts of isobutyl vinyl ether.
7 g, 117 g of chlorotrifluoroethylene, 175 g of xylene and 2.8 g of octanoyl peroxide as an initiator were charged, and polymerization was carried out at 73 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced copolymer solution was taken out. The produced copolymer solution was reprecipitated with n-hexane and dried. The yield of the copolymer was 238 g.

The number average molecular weight of the obtained copolymer was 8,2.
00, the fluorine content is 22.9%, and the hydroxyl value is 51.
mgKOH / g, glass transition temperature was 28 ° C. The IR spectrum of the obtained fluororesin is shown in FIG.

[0086]

Example 2 The inside of an autoclave with a stirrer made of stainless steel and having an inner volume of 1 liter was replaced with nitrogen gas three times.
Then, 65 g of 4-hydroxybutyl vinyl ether,
Cyclohexyl isocyanate 38g, xylene 103
g was charged and the reaction was performed at 80 ° C. for 6 hours. Then 4-
Methacryloyloxy-2,2,6,6-tetramethylpiperidine 2.5 g, isobutyl vinyl ether 43
g, chlorotrifluoroethylene 117 g, xylene 1
63 g and 2.8 g of octanoyl peroxide as an initiator were charged, and polymerization was carried out at 73 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced copolymer solution was taken out. This copolymer solution was reprecipitated with n-hexane and dried. The yield of the copolymer was 252 g.

The number average molecular weight of the obtained copolymer was 8,9.
00, fluorine content 21.4%, hydroxyl value 60
mgKOH / g, glass transition temperature was 32 ° C.

[0088]

Example 3 The inside of an autoclave with an internal volume of 1 liter and made of a stainless steel and equipped with a stirrer was replaced with nitrogen gas three times.
Then, 49 g of 4-hydroxybutyl vinyl ether,
25 g of cyclohexyl isocyanate, 2.5 g of 4-allyloxy-1,2,2,6,6-pentamethylpiperidine, 57 g of isobutyl vinyl ether and 249 g of xylene were charged and reacted at 80 ° C. for 6 hours. Then, 117 g of chlorotrifluoroethylene and 2.8 g of octanoyl peroxide as an initiator were charged, and
Polymerization was performed at 3 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced copolymer solution was taken out. This copolymer solution was reprecipitated with n-hexane and dried. The yield of the copolymer was 231 g.

The number average molecular weight of the obtained copolymer was 7,9.
00, the fluorine content is 22.9%, and the hydroxyl value is 52.
mgKOH / g, glass transition temperature was 27 ° C.

[0090]

Example 4 222 g of 3-isocyanamethyl-3,
5,5-trimethylcyclohexyl isocyanate (I
PDI) and 7.4 g of isobutyl alcohol 10
After reacting at 0 ° C. for 3 hours, excess IPDI was removed and purified using a thin film evaporator to obtain a half block body of isobutyl alcohol of IPDI having a purity of 93%.

Next, the inside of the stainless steel autoclave with an agitator having an internal volume of 1 l was replaced with nitrogen gas three times. There, 54 g of 4-hydroxybutyl vinyl ether, 59 g of the above half block, vinyl-9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-
6 g of dioxaspiro [5,5] -3-undecylmethyl ether, 52 g of isobutyl vinyl ether and 288 g of xylene were charged and reacted at 80 ° C. for 6 hours. Then, 117 g of chlorotrifluoroethylene and 2.8 g of octanoyl peroxide as an initiator were charged, and
Polymerization was performed at 3 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced copolymer solution was taken out. The obtained fluorine-containing copolymer was reprecipitated with n-hexane and dried. The yield of the copolymer was 276 g.

The number average molecular weight of the obtained copolymer was 9,5.
00, the fluorine content is 19.8% and the hydroxyl value is 51.
mgKOH / g, glass transition temperature was 33 ° C.

[0093]

Example 5 The inside of an autoclave with a stirrer made of stainless steel and having an internal volume of 1 liter was replaced with nitrogen gas three times.
Then, 49 g of 4-hydroxybutyl vinyl ether,
25 g of cyclohexyl isocyanate, 74 g of xylene
Was charged and reacted at 80 ° C. for 6 hours. Then, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine 3 g, 2-perfluorooctylethyl methacrylate 9 g, 2-hydroxyethyl methacrylate 9 g, isobornyl methacrylate 24 g, isobutyl vinyl ether 58 g, chloro. 117 g of trifluoroethylene, 220 g of xylene, and 4.6 g of t-butylperoxypivalate as an initiator were charged, and polymerization was carried out at 67 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced copolymer solution was taken out. This copolymer solution was reprecipitated with n-hexane and dried. The yield of the copolymer was 282 g. The number average molecular weight of the obtained copolymer was 10,900, and the fluorine content was 21.3.
%, The hydroxyl value was 55 mgKOH / g, and the glass transition temperature was 40 ° C.

[0094]

Example 6 The inside of a stainless steel autoclave with an agitator having an inner volume of 1 liter was replaced with nitrogen gas three times.
Then, 74 g of 4-hydroxybutyl vinyl ether,
2.0 g of 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 86 g of isobutyl vinyl ether, 176 g of chlorotrifluoroethylene, 336 g of xylene and 4.2 g of octanoyl peroxide as an initiator, 73 Polymerization was performed at 8 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced copolymer solution was taken out. This copolymer solution was reprecipitated with n-hexane and dried. The yield of copolymer was 317 g.

The number average molecular weight of the obtained copolymer was 7,6.
00, the fluorine content is 25.4%, and the hydroxyl value is 10
It was 5 mgKOH / g and the glass transition temperature was 21 ° C.
This is referred to as a copolymer A. Copolymer A 100 g 111
g of xylene and 11 g of cyclohexyl isocyanate were added to dibutyl tin dilaurate 20 p
pm (vs. solid content) was added as a catalyst, until the disappearance of the NCO group was confirmed by infrared absorption spectrum (IR), 8
The reaction was carried out at 0 ° C for 4 hours. The obtained fluororesin solution is
The solid content was 50%, the number average molecular weight was 9,300, and the hydroxyl value of the resin content was 51 mgKOH / g.

[0096]

Example 7 100 g of the copolymer A obtained in Example 6 was dissolved in 126 g of xylene, and 26 g of the half block of IPDI obtained in Example 4 with isobutyl alcohol was mixed with 20 pp of dibutyltin dilaurate.
m (vs. solid content) was added as a catalyst, and until the disappearance of the NCO group was confirmed by infrared absorption spectrum (IR),
The reaction was carried out at ℃ for 4 hours.

The resulting fluororesin solution had a solid content of 50
%, Number average molecular weight 10,600, resin hydroxyl group value 43 m
It was gKOH / g.

[0098]

Examples 8 to 14 Each fluororesin obtained in Examples 1 to 5 was adjusted to a solid content of 50% with xylene, or the fluororesin solution obtained in Examples 6 and 7 (solid content 50%) as the main agent and "Duranate TPA" (manufactured by Asahi Kasei Kogyo Co., Ltd.) as a curing agent, NCO / OH = 1.
After being blended with each other so as to become / 1, the coating was performed by adjusting the Ford cup # 4 to 15 seconds with xylene as a thinner. After the obtained coating film was baked at 120 ° C. for 1 hour, the coating film physical properties (coating appearance, coating film gloss, coating film hardness, flexibility, adhesion (Al), light resistance) were evaluated.

Each of the fluororesins obtained in Examples 1 to 5 was adjusted to a solid content of 50% with xylene, or the fluororesin solution obtained in Examples 6 and 7 (solid content of 50%). ) In glass bottles and stoppered tightly, then 5
The storage stability was evaluated by keeping the temperature at 0 ° C. for 30 days to trace the change in viscosity. The respective results are shown in Table 1.

[0100]

[Comparative Example 1] 7.7 g of potassium carbonate was charged into an autoclave made of stainless steel and having an internal volume of 1 liter, and the inside of the autoclave was replaced with nitrogen gas three times. Then, 23 g of 4-hydroxybutyl vinyl ether, 80 g of isobutyl vinyl ether, 117 g of chlorotrifluoroethylene, 220 g of xylene and 2.8 g of octanoyl peroxide as an initiator were charged, and polymerization was carried out at 73 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced copolymer solution was taken out. After potassium carbonate was filtered off from this copolymer solution, it was reprecipitated with n-hexane and dried. The yield of the copolymer was 212 g.

The number average molecular weight of the obtained copolymer was 8,1.
00, the fluorine content is 25.9%, and the hydroxyl value is 46.
mgKOH / g, glass transition temperature was 21 ° C.

[0102]

[Comparative Example 2] 7.7 g of potassium carbonate was charged into an autoclave made of stainless steel and having an internal volume of 1 liter, and the inside of the autoclave was replaced with nitrogen gas three times. Then, 49 g of 4-hydroxybutyl vinyl ether, 25 g of cyclohexyl isocyanate, and 74 g of xylene were charged and reacted at 80 ° C. for 6 hours. Then 57 g of isobutyl vinyl ether, 1 chlorotrifluoroethylene
17 g xylene 174 g and octanoyl peroxide 2.8 g as an initiator were charged, and polymerization was carried out at 73 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced copolymer solution was taken out. After potassium carbonate was filtered off from this copolymer solution, it was reprecipitated with n-hexane and dried. The yield of the copolymer was 238 g.

The number average molecular weight of the obtained copolymer was 8,8.
00, the fluorine content is 22.9%, and the hydroxyl value is 45.
mgKOH / g, glass transition temperature was 28 ° C.

[0104]

Comparative Example 3 100 g of Copolymer A dissolved in 111 g of xylene and 11 g of n-hexyl isocyanate were added with 20 ppm of dibutyltin dilaurate (as a solid content) as a catalyst, and an infrared absorption spectrum (I
The reaction was carried out at 80 ° C. for 1 hour until the disappearance of the NCO group was confirmed in R).

The obtained fluororesin solution had a solid content of 50.
%, Number average molecular weight 8,800, resin component hydroxyl value 51 mg
It was KOH / g.

[0106]

[Comparative Examples 4 to 7] Each of the fluororesins obtained in Comparative Examples 1 and 2 adjusted to a solid content of 50% with xylene, the fluororesin solution obtained in Comparative Example 3, and the copolymer A. As the main agent, and "Duranate TPA" (manufactured by Asahi Kasei Kogyo Co., Ltd.) as a curing agent so that NCO / OH = 1/1, and then mixed with xylene as a thinner in Ford Cup # 4 for 15 seconds. Was adjusted and painted. After baking the obtained coating film at 120 ° C. for 1 hour, coating film properties (coating appearance, coating gloss, coating hardness, flexibility, adhesion (Al),
The weather resistance) was evaluated.

The fluororesins obtained in Comparative Examples 1 and 2 each having a solid content of 50% adjusted with xylene, the fluororesin solution obtained in Comparative Example 3, and copolymer A
Put each in a glass bottle and stopper tightly.
It was kept for a day, the change in viscosity was traced, and the storage stability was evaluated. The respective results are shown in Table 1.

[0108]

[Table 1]

[0109]

As is clear from the above results, according to the present invention, the storage stability is good, the organic solvent is soluble and the compatibility with the curing agent is excellent, and the composition can be cured at room temperature. The fluororesin can be easily applied. Further, the fluorine-based coating material of the present invention containing the fluorine-containing resin as a main component can give a coating film which is glossy, hard and has excellent weather resistance under mild conditions. It is useful as a baking paint for boards and aluminum sashes, or as a normally dry paint that can be applied on site.

Further, regarding the material of the equipment, in addition to metallic materials, inorganic materials such as glass and concrete, FRP,
It is preferably used for coating plastics such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride and polyvinylidene chloride, and organic materials such as wood. Further, the fluorine-based paint is also useful in specific applications such as automobile top coats, exterior colored glass, and cement roof tiles.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the fluorine-containing resin obtained in Example 1.

Claims (2)

[Claims] 1. A fluorine-containing resin comprising the following constituents. Formula (A) Unit represented by 0.01 to 20 mol% (B) Formula A unit represented by 20 to 80 mol% (C) Formula: Unit represented by 3 to 80 mol% 2. A coating material containing the fluorine-containing resin according to claim 1 as a main component.