JPH04366114A - Fluororesin and coating material containing the same as major component - Google Patents

Abstract

PURPOSE:To obtain a fluororesin which is excellent in solubility in organic solvents and compatibility with hardeners and gives a rigid coating film having excellent weatherability, by forming a molecular structure made up of a plurality of specific structural units in a predetermined proportion. CONSTITUTION:The title resin has a molecular structure made up of 0.01-40mol% units represented by formula I and/or formula II (wherein R<4> and R<5> each is H or a 1-5C alkyl; R<6> is H or an alkoxycarbonyl; M is an alkali metal or a basic N or P compound having a pKa of 6 or more; m is 0 or 1; and n is 0 when M is an alkali metal or a quaternary ammonium ion, and is 1 when M is neither of the two), 20-80mol% units represented by formula III (wherein V, X, Y, and Z each is H, F, Cl, or a 1-6C (halo)alkyl, provided that at least one thereof is F), and 3-80mol% units represented by formula IV (wherein W is a monovalent organic group having a cyclic hydrocarbon group; R<7> is a divalent organic group; and R<8> and R<9> each is H or a 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 new fluororesin and a coating material containing the same as a main component.

0002

BACKGROUND OF THE INVENTION Conventionally, fluororesins have been widely used in many fields because of their excellent heat resistance, mechanical properties, chemical resistance, weather resistance, etc. One of its uses is as a film-forming component in paints. For example, fluororesin paints using tetrafluoroethylene polymers, vinylidene fluoride polymers, etc. are known.
Since this material has excellent lubricity, non-adhesiveness, weather resistance, and chemical resistance, it is used as a coating material in fields such as the chemical industry, food, architecture, and machinery. However, the above-mentioned fluororesin paints require baking at high temperatures, which inevitably limits their range of use. Attempts have been made to develop solvent-based paints using fluororesins with reactive groups.

By the way, examples of fluorine-containing resins soluble in organic solvents include, for example, JP-A No. 57-34107, JP-A No. 61-275311, JP-A No. 61-57609, JP-A No. 62-174213, Japanese Patent Publication No. 63-182312
Copolymers of fluoroolefins and vinyl monomers that can be copolymerized with the fluoroolefins are known, as disclosed in Japanese Patent Publication No. However, in these copolymers, alkyl vinyl ethers and special carboxylic acid vinyl esters are used as copolymerization components, but while these copolymerization components give flexibility to the coating film, they also reduce the hardness of the coating film. In addition, the coating film has low gloss and has insufficient compatibility with the curing agent.

The present applicant has conducted extensive studies on the use of fluoroolefin copolymers as paint bases, and by introducing cyclic hydrocarbon groups into the side chains of fluorine-containing copolymers via urethane bonds, the above-mentioned results can be achieved. I found a solution to the problem. However, even with the above-mentioned fluororesin, it has been found that when used as a paint base, it is necessary to improve its dispersibility depending on the type of pigment used in combination, and it is necessary to improve its adhesion to the substrate depending on the form of use. did.

[0005]

[Problems to be Solved by the Invention] The present invention provides a fluororesin that solves the problems of the prior art, that is, a fluororesin that has good solubility in organic solvents and compatibility with curing agents, and The purpose is to provide a fluorine-based paint that has gloss as a main component, provides a hard coating film with excellent weather resistance, and also has improved affinity with pigments and adhesion to substrates. It is something that

[0006]

[Means for Solving the Problem] As a result of intensive research in view of the above points, the present inventors have discovered that the above problems can be solved by introducing a functional group with a specific structure into a fluororesin. This discovery led to the completion of the present invention. That is, the present invention provides; (1) a fluororesin comprising the following constituents; (A) Formula;

[0007]

[C4]

Unit expressed by 0.
01-40 mol% (B) formula;

[0009]

[C5]

Unit expressed as 0010 20
~80 mol% Formula (C);

[0011]

[C6]

[0012] Units represented by: 3 to 80 mol% and (1) A fluorine-based paint containing the above-mentioned fluororesin as a main component. The present invention will be explained in detail below. The fluororesin according to the present invention having the above-mentioned (A), (B), and (C) as constituent units can be obtained by (a) copolymerizing vinyl monomers corresponding to each constituent unit, or (b) by copolymerizing the vinyl monomers corresponding to the respective constituent units. By reacting at least a part of the hydroxyl groups of a hydroxyl group-containing fluororesin containing A), (B) and the following formula (D-1) with at least one cyclic hydrocarbon group-containing monoisocyanate. can get.

(D-1) Formula;

[0014]

[C7]

Unit represented by 3~
80 mol% First, (a) (the case where vinyl monomers corresponding to each structural unit are copolymerized) will be explained. As the vinyl monomer forming the unit (A) in the fluororesin of the present invention, formula (a-■) and/or (a-
■) Formula

[0016]

[Chemical formula 8]

The following expression is used. Specific examples of the vinyl monomer include acrylic acid, methacrylic acid,
Crotonic acid, fumaric acid, maleic acid, half esters of fumaric acid, half esters of maleic acid, etc., and compounds containing these acids and alkali metals, or nitrogen atoms or phosphorus atoms, whose acid-base balance Among these, crotonic acid and its salts are preferred. These may be used alone or in combination of two or more.

[0018] Further, examples of the basic compound containing a nitrogen atom or a phosphorus atom and having a pKa of 6 or more include amines, phosphines, and the like. Specific examples of amines include diethylamine, dipropylamine, N-methylethanolamine, diethanolamine, dimethylcyclohexylamine, dimethylethanolamine, triethanolamine,
Triethylamine, pyrrolidine, piperidine, 1-methylpiperidine, 2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-penta Examples include methylpiperidine, morpholine, tetramethylammonium ion, tetraethylammonium ion, and the like. Specific examples of phosphine include trimethylphosphine, triethylphosphine, tributylphosphine, dimethylphosphine, diethylphosphine, phenyldiethylphosphine, triphenylphosphine, tribenzylphosphine, and the like. Among these, tertiary amines are particularly preferred.

In the fluororesin of the present invention, (A)
The content of the unit is preferably selected depending on the expected modification effect, but it is usually selected from the range of 0.01 to 40 mol%. When the purpose is to improve adhesion with the base material or pigment dispersibility, it is about 0.01 to 15 mol%, and when the purpose is to increase the affinity for aqueous media (aqueous fluororesin) , a range of about 5 to 40 mol% is suitable.

In the fluororesin of the present invention, the vinyl monomer forming the unit (B) is represented by the formula (b).

0021
]

[Chemical formula 9]

The following expression is used. Specific examples of such vinyl monomers include, for example,

[0023]

[Chemical formula 10]

Fluoroethylene series such as [0024]

[0025]

[Chemical formula 11]

Fluoropropene series such as;

[0027]

[Chemical formula 12]

Among these, (b'
)formula

[0029]

[Chemical formula 13]

Fluoroethylene compounds and fluoropropene compounds represented by the following are preferred, and tetrafluoroethylene (CF2 = CF2), chlorotrifluoroethylene (CF2 = CFCl) and hexafluoropropene (CF2 = CFCF3) are particularly preferred. These fluoroolefins may be used alone or in combination of two or more.

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

[0032]

[Chemical formula 14]

The following expression is used. Such a vinyl monomer can be obtained by reacting a hydroxyl group-containing vinyl monomer represented by formula (d-1) with at least one cyclic hydrocarbon group-containing monoisocyanate.

[0034]

[Chemical formula 15]

Specific examples of these hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether,
Hydroxyalkyl vinyl ethers such as 4-hydroxybutyl vinyl ether and 4-hydroxycyclohexyl vinyl ether; hydroxyalkyl allyl ethers such as 2-hydroxyallyl vinyl ether and 4-hydroxybutyl allyl ether; 2-hydroxyethyl (
meth)acrylate, 4-hydroxypropyl(meth)
Hydroxyl group-containing (meth)acrylates such as acrylates,
Typical examples include crotonic acid esters containing hydroxyl groups such as 2-hydroxyethyl crotonate and 4-hydroxypropyl crotonate, allyl alcohol, etc. Among these, hydroxyalkyl vinyl ethers have the highest reactivity with fluoroolefins. Good and desirable. These hydroxyl group-containing vinyl monomers may be used alone or in combination of two or more.

The cyclic hydrocarbon group-containing monoisocyanate includes, for example, isocyanate groups of monoisocyanates such as cyclohexyl isocyanate, alkyl-substituted cyclohexyl isocyanate, benzyl isocyanate, isocyanatomethyl-cyclohexane, and the like. Furthermore, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate; (IPDI)
, 1,3-(or1,4)bis(isocyanatomethyl)
Cyclohexane; (hydrogenated XDI), 1,3-(or
1,4) Bis(isocyanatomethyl)benzene; (XD
I), 1,3-(or1,4)bis(α,αdimethylisocyanatomethyl)benzene (TMXDI), 1,
3-(or1,4)diisocyanatocyclohexane, 1
-Diisocyanate monomers containing cyclic hydrocarbon groups such as methyl-1,3-(or1,4) diisocyanatocyclohexane (hydrogenated TDI), bis(4-isocyanatocyclohexyl)methane; (hydrogenated MDI) Only one of the two isocyanate groups of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, hexanol, cyclohexanol, benzyl alcohol, 2-ethylhexyl alcohol, dipropylamine, dibutylamine, diisobutyl A monoisocyanate compound obtained by reacting with a monovalent active hydrogen compound such as amine or dicyclohexylamine,
Examples include so-called half block bodies.

[0037] These so-called half-block bodies are generally produced by reacting the corresponding diisocyanate monomer and an active hydrogen compound under diisocyanate excess conditions, preferably at an NCO/OH equivalent ratio of 6 or more. By removing excess isocyanate monomer and purifying it, a mixture containing half-block bodies as a main component is obtained.

As mentioned above, the isocyanates used in the present invention must have a cyclic saturated hydrocarbon group or an aromatic ring, and include, for example, phenyl isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, etc. Those in which an isocyanate group is directly bonded to an aromatic ring are not preferred because they cause defects in weather resistance as paints.

[0039] These monoisocyanates can be used as a mixture as appropriate, and aliphatic monoisocyanates such as butyl isocyanate, hexyl isocyanate, 2-ethylhexyl isocyanate, octadecyl isocyanate, etc. and/or hexamethylene diisocyanate, 3,3,5-(or3,5,5-)
It can also be used in combination with aliphatic diisocyanates such as trimethytrimethylhexamethylene diisocyanate, diisocyanates such as the above-mentioned cyclic hydrocarbon group-containing diisocyanates, and the like.

When the hydroxyl group-containing vinyl monomer and at least one cyclic hydrocarbon group-containing monoisocyanate are reacted to obtain the cyclic hydrocarbon group-containing vinyl monomer, the hydroxyl group-containing vinyl monomer may be reacted with the hydroxyl group-containing vinyl monomer. The desired cyclic hydrocarbon group-containing vinyl monomer may be obtained by reacting equal amounts of OH groups and NCO groups of isocyanates, and then subjected to copolymerization.
In addition, the NCO/OH equivalent ratio is 3/100 to 100/10
0, preferably in the range of 10/100 to 70/100 excess hydroxyl group-containing vinyl monomer, and if necessary in the presence of other copolymerizable vinyl monomers, and then the desired copolymerization reaction is carried out. You may also serve it. Furthermore, it is also possible to simultaneously charge desired vinyl monomers and isocyanate components into a reactor to carry out the polymerization reaction and the urethane group forming reaction simultaneously. A solvent may or may not be used during the reaction, but examples include toluene, xylene, ethyl acetate,
It is possible to use a solvent such as butyl acetate, cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. It is also possible to add a known urethanization reaction promoting catalyst such as dibutyltin dilaurate to accelerate the reaction. be.

[0041] The reaction temperature is usually selected from room temperature to about 120°C. The progress of the reaction is monitored by observing the decrease in NCO groups using, for example, infrared absorption spectroscopy or titration, and the reaction is usually terminated when the NCO groups disappear. In the fluororesin of the present invention, the content of the (B) units must be in the range of 3 to 80 mol%, preferably 5 to 50 mol%. If the content is less than 3 mol%, the compatibility with the curing agent and coating film hardness will be poor, and if it exceeds 80 mol%, the weather resistance will be reduced.

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

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

Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate, hydrogen peroxide, or redox initiators consisting of a combination of these with a reducing agent such as sodium bisulfite or sodium thiosulfate; ,
Inorganic initiators, such as systems in which a small amount of iron, ferrous salt, silver nitrate, etc. are coexisting with these, dibasic acid peroxides such as disuccinic acid peroxide, diglutaric acid peroxide, monosuccinic acid peroxide, and azovinic acid peroxides. Examples include organic initiators such as cysobutyramidine dibasic acid salt.

The amount of these polymerization initiators to be used is appropriately selected depending on the type thereof, copolymerization reaction conditions, etc., but is preferably 0.005 to 5% by weight, based on the total amount of monomers usually used. It is selected in a range of 0.05 to 0.5% by weight. There are no particular restrictions on the polymerization method, and for example, bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, etc. can be used, but from the standpoint of stability of the polymerization reaction, xylene, toluene, lower alkyl substituted benzenes, such as
Solution polymerization using esters such as butyl acetate, ketones such as methyl isobutyl ketone, alcohols such as t-butanol, saturated halogenated hydrocarbons having one or more fluorine atoms, etc., or in an aqueous medium. Emulsion polymerization methods, bulk polymerization methods that do not require separation from a solvent, and the like are preferably used.

When copolymerizing in an aqueous medium, a suspending agent or emulsifying agent is usually used as a dispersion stabilizer, and a basic buffer is added to adjust the pH value of the reaction solution during polymerization to 4, preferably It is desirable to set it to 6 or more. Also in the case of solution polymerization and bulk polymerization, addition of basic substances such as potassium carbonate and amine compounds is effective. Furthermore, there are no particular limitations on the polymerization format, and any of the batch, semi-continuous, and continuous methods can be used.

The reaction temperature in the copolymerization reaction is usually -
The temperature is appropriately selected within the range of 30 to +150°C depending on the type of polymerization initiation source and polymerization medium, and is usually selected within the range of 0 to 100°C, preferably 10 to 90°C. Further, the reaction pressure is not particularly limited, but is selected within the range of normal pressure to 100 kg/cm2. Furthermore, the copolymerization reaction can be carried out by adding a suitable chain transfer agent.

Subsequently, as a method for producing a fluororesin of the present invention, (b) at least a portion of the hydroxyl groups of the hydroxyl group-containing fluororesin containing (A), (B), and (D-1) as constituent components. and at least one type of cyclic hydrocarbon group-containing monoisocyanate will be described. (A) Formula;

[0049]

[Chemical formula 16]

Unit expressed by 0.
01-40 mol% (B) formula;

[0051]

[Chemical formula 17]

Unit expressed by 20
~80 mol% Formula (D-1);

[0053]

[Chemical formula 18]

Unit represented by 3~
The hydroxyl group-containing fluororesin containing 80 mol% (A), (B) and (D-1) as constituent components has vinyl monomers of formula (a), formula (b) and ( It is obtained by copolymerizing the formula d-1) in the same manner as in (a) above (copolymerizing vinyl monomers corresponding to each structural unit).

Formula (a);

[0056]

[Chemical formula 19]

Formula (b);

[0058]

[C20]

Formula (d-1);

[0060]

[C21]

Specific examples of these vinyl monomers are the same as those exemplified in (a). In the reaction between the thus obtained hydroxyl group-containing fluororesin and the cyclic hydrocarbon group-containing monoisocyanate, the OH of the hydroxyl group-containing fluororesin is
The equivalent ratio of the group to the NCO group of the isocyanate is usually 3
/100~100/100, preferably 10/100~
It is set in the range of 70/100. For information on reaction temperature, use of solvents and reaction-promoting catalysts, and how to confirm the end point of the reaction, etc.
This is similar to the reaction between the hydroxyl group-containing vinyl monomer and the cyclic hydrocarbon group-containing monoisocyanate described in (a).

Further, 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 each structural unit, or (b); at least a part of the hydroxyl groups of the hydroxyl group-containing fluororesin and at least one cyclic hydrocarbon group-containing monomer; The fluororesin of the present invention obtained by the method of reacting with isocyanate has the formula (A);

[0063]

[C22]

Unit expressed by 0.
01-40 mol% (B) formula;

[0065]

[C23]

Unit expressed by 20
~80 mol% Formula (C);

[0067]

[C24]

Unit represented by 3~
Although it is composed of 80 mol%, the above (A), (B),
(C) In addition to the units, each does not exceed 50 mol%,
(D) Copolymerized unit of functional group-containing vinyl monomer and/or
Or (E) it is desirable to include copolymerized units of other vinyl monomers. 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). mer, a hydrolyzable silyl group-containing vinyl monomer represented by formula (d-3), and the like.

[0069]

[C25]

[0070]

[C26]

[0071]

[C27]

Specific examples of the hydroxyl group-containing vinyl monomer (d-1) are the same as those exemplified in (a); (copolymerizing vinyl monomers corresponding to each structural unit). . Specific examples of the epoxy group-containing vinyl monomer (d-2) include, for example:

[0073]

[C28]

[0074] etc. Specific examples of the hydrolyzable silyl group-containing vinyl monomer (d-3) include, for example:
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, allyltrimethoxysilane, allyltriethoxysilane, allyldimethoxymethylsilane, vinyloxypropyltrimethylsiloxysilane, vinyloxyethoxypropyltrimethylsiloxysilane, 3-trimethoxysilyl Examples include propyl (meth)acrylate.

The functional group-containing vinyl monomers forming the unit (D) may be used alone or in combination of two or more. Further, other copolymerizable vinyl monomers forming the unit (E) include, for example, olefins such as ethylene, propylene, and isobutylene;
Haloolefins such as vinyl chloride and vinylidene chloride, vinyl acetate, vinyl n-butyrate, vinyl benzoate, pt-
Vinyl carboxylate esters such as vinyl butyl benzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate, vinyl laurate, isopropenyl carboxylate esters such as isopropenyl acetate and isopropenyl propionate, 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-perfluorooctyl ethyl 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, vinyl-9-aza-3-ethyl-8,8,9,10
,10-pentamethyl-1,5-dioxaspiro[5,
5]-3-Undecyl methyl ether, vinyl-9-aza-3-ethyl-8,8,10,10-tetramethyl-
Piperidinyl group-containing vinyl ethers such as 1,5-dioxaspiro[5,5]-3-undecyl methyl ether, aromatic vinyl compounds such as styrene and vinyltoluene, allyl formate, allyl acetate, allyl butyrate, allyl benzoate,
Allyl cyclohexanecarboxylate, Allyl cyclohexylpropionate, 4-allyloxy-2,2,6,6,
-tetramethylpiperidine, 4-allyloxy-1,2
, 2,6,6,-pentamethylpiperidine, allyl ethers such as allyl ethyl ether, allyl phenyl ether, butyl (meth)acrylate, methyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl ( meth)acrylate, 2-hydroxy-4-(2-methacryloxyethoxy)benzophenone, 4-(meth)acryloyloxy-
2,2,6,6,-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6,-pentamethylpiperidine, perfluoromethyl (meth)acrylate, perfluoropropyl (meth) Acrylate, perfluoropropyromethyl (meth)acrylate,
Perfluoromethylmethyl (meth)acrylate, 2-
Acrylic acid and methacrylic acid esters such as perfluorooctylethyl (meth)acrylate and perfluoroisononylmethyl (meth)acrylate; acrylamides such as acrylamide and N-methylolacrylamide; Examples include endocyclic vinyl ethers such as those described above.

These vinyl monomers may be used alone or in combination of two or more. In the fluororesin of the present invention, (D) copolymerized units of a functional group-containing vinyl monomer and/or (E) copolymerized units of other vinyl monomers, each within a range not exceeding 50 mol%. Those containing functional group-containing vinyl monomers forming the units (D) and/or other copolymerizable vinyl monomers forming the units (E) each do not exceed 50 mol%. It can be obtained by using it as a copolymerization component.

The molecular weight of the fluororesin of the present invention is the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and monodispersed polystyrene of 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
The temperature is 0 to 100°C.

The fluororesin of the present invention having such a composition, molecular weight, and glass transition temperature is soluble in organic solvents, has excellent compatibility with curing agents, and has good storage stability. A cured coating film containing a fluorine-containing resin as a main component is glossy, hard, and has excellent weather resistance. In the fluororesin of the present invention, when a hydroxyl group-containing vinyl monomer is used as the functional group-containing vinyl monomer forming the unit (D), the obtained fluororesin contains a hydroxyl group as a curing site. The curing agent used in ordinary thermosetting acrylic paints, such as polyvalent isocyanates, blocked isocyanate curing agents, melamine curing agents, urea resin curing agents, polybasic acid curing agents, etc., can be used to heat the coating. Can be hardened.

Furthermore, the hydroxyl group-containing fluororesin can also be cured at room temperature by using polyvalent isocyanates. As the polyvalent isocyanates,
For example, non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, their adducts, and polyvalent isocyanates having an isocyanurate ring are preferred, but among these, they are particularly compatible with fluororesins. Polyvalent isocyanates having an isocyanurate ring with good solubility are preferred. When curing at room temperature using these polyvalent isocyanates, curing can be accelerated by adding a known catalyst such as dibutyltin dilaurate.

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 unit (D), the obtained fluororesin has a cured site. By using polyaddition type curing agents such as polyamines, acid anhydrides, polyphenols, and polymercaptans, and catalyst type curing agents such as imidazoles and BF3 as curing agents, heating It can be cured or cured at room temperature.

[0081] Furthermore, in the fluororesin of the present invention, (
D) When using a hydrolyzable silyl group-containing vinyl monomer as the functional group-containing vinyl monomer forming the unit,
The obtained fluororesin contains a hydrolyzable silyl group as a curing site, and can be moisture-cured using an amine compound such as butylamine or a curing catalyst such as dibutyltin dilaurate.

[0082] The fluororesin of the present invention also has the above-mentioned (D
) If it does not contain units, it can be used as a lacquer-type coating material. The present invention provides a fluorine-based paint containing the above-mentioned new fluororesin as a main component, and various solvents can be used to make the fluororesin into a solution-type paint. 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, and glycols such as ethyl cellosolve. Examples include ethers and various commercially available thinners. To prepare this solution-type paint, mix the fluorine-containing resin and the solvent homogeneously using a mixer commonly used for preparing paints, such as a ball mill, paint shaker, sand mill, jet mill, three-roll mill, kneader, etc. This can be done by mixing. At this time, pigments, dispersion stabilizers, viscosity modifiers, leveling agents, gelling inhibitors, ultraviolet absorbers, etc. may be added as desired.

[0084]

[Example] Hereinafter, it will be explained in more detail with examples.
The present invention is not limited in any way by these examples. Note that all percentages in the examples indicate weight percentages. (2) Molecular weight of various resins: Determined from polystyrene standard calibration curve using gel permeation chromatography.

(Equipment used) Equipment: Shimadzu Corporation LC-3A column: Tosoh Corporation TSKgel G-5000 HXLTSKgel
G-4000 HXLTSKgel G-20
00 HXL detector: Shimadzu RID-6A Data processing: Shimadzu C-R4A Carrier: Tetrahydrofuran ■Glass transition temperature (Tg) of various resins; Measurement was performed using the following equipment and measurement conditions.

(Equipment used): Simultaneous differential thermogravimetric measurement device (manufactured by Seiko Electronics Co., Ltd.) SSC 5000
DSC 200 (measurement conditions): -40 to 120°C temperature increase (5°C/min) ■Hydroxyl value, acid value: Measured according to JIS K-0070. ■Gloss, flexibility, adhesion (Al); JIS K-54
Measured according to 00. (2) Infrared absorption spectrum (IR spectrum): Measured using FT-IR-5M model manufactured by JASCO Corporation. (2) Coating film hardness: Measured according to ISO-1522. (2) Weather resistance: Determined according to ASTM G-53.

[0087]

Example 1 The interior of a stainless steel autoclave with an internal volume of 1 liter and equipped with a stirrer was purged with nitrogen gas three times. Then, 49 g of 4-hydroxybutyl vinyl ether,
Cyclohexyl isocyanate 25g, xylene 74g
was charged and reacted at 80°C for 6 hours. Then, 1.7 g of crotonic acid, 4-methacryloyloxy-1,2,2
, 1.2 g of ,6,6,-pentamethylpiperidine, 56 g of isobutyl vinyl ether, 117 g of chlorotrifluoroethylene, 176 g of xylene, and 2.8 g of octanoyl peroxide as an initiator were charged at 73°C.
Time polymerization was performed. After the polymerization was completed, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the resulting copolymer solution was taken out. This copolymer solution was reprecipitated with n-hexane and dried. The yield of copolymer was 228 g.

The number average molecular weight of the obtained copolymer was 8.7.
00, the fluorine content is 22.8%, and the hydroxyl value is 51.
mgKOH/g, acid value was 5 mgKOH/g, and glass transition temperature was 28°C.

[0089]

Example 2 The interior of a stainless steel autoclave with an internal volume of 1 liter and equipped with a stirrer was purged with nitrogen gas three times. Then, 65 g of 4-hydroxybutyl vinyl ether,
Cyclohexyl isocyanate 38g, xylene 103
g was charged and reacted at 80°C for 6 hours. Then, 5.2 g of crotonic acid, 4-methacryloyloxy-2,2,
1.2 g of 6,6-tetramethylpiperidine, 38 g of isobutyl vinyl ether, 117 g of chlorotrifluoroethylene, 161 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 the polymerization was completed, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the resulting copolymer solution was taken out. This copolymer solution is
It was reprecipitated with n-hexane and dried. The yield of copolymer was 239 g.

The number average molecular weight of the obtained copolymer was 8.2
00, the fluorine content is 21.4%, and the hydroxyl value is 56.
mgKOH/g, acid value was 13 mgKOH/g, and glass transition temperature was 32°C.

[0091]

[Example 3] 7.7 g of potassium carbonate was charged into a stainless steel autoclave having an internal volume of 1 liter and equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times. Next, 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. Thereafter, 1.7 g of crotonic acid, 57 g of isobutyl vinyl ether, 117 g of chlorotrifluoroethylene, 176 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 the polymerization was completed, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the resulting copolymer solution was taken out. After removing potassium carbonate from this copolymer solution by filtration, it was reprecipitated with n-hexane and dried. The yield of copolymer was 238 g.

The number average molecular weight of the obtained copolymer was 9.4.
00, the fluorine content is 22.8%, and the hydroxyl value is 51.
mgKOH/g, acid value was 1.1 mgKOH/g, and glass transition temperature was 28°C.

[0093]

Example 4 222g of 3-isocyanamethyl-3,5
, 5-trimethylcyclohexyl isocyanate (IP
DI) and 7.4 g of isobutyl alcohol to 100
After reacting at .degree. C. for 3 hours, excess IPDI was removed and purified using a thin film evaporator to obtain a half block of IPDI with isobutyl alcohol having a purity of 93%.

Next, the inside of a stainless steel autoclave with an internal volume of 1 liter and equipped with a stirrer was purged with nitrogen gas three times. 54g of 4-hydroxybutyl vinyl ether
, 59 g of the above half block body and 113 g of xylene were charged and reacted at 80° C. for 6 hours. Then, 3.5 g of crotonic acid, 50 g of isobutyl vinyl ether, 117 g of chlorotrifluoroethylene, 2.2 g of triethylamine
g, 170 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 the polymerization was completed, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the resulting copolymer solution was taken out. The obtained fluorine-containing copolymer was reprecipitated with n-hexane and dried. The yield of copolymer was 266 g.

The number average molecular weight of the obtained copolymer was 9.2
00, the fluorine content is 19.8%, and the hydroxyl value is 51.
mgKOH/g, acid value was 7 mgKOH/g, and glass transition temperature was 33°C.

[0096]

Example 5 The interior of a stainless steel autoclave with an internal volume of 1 liter and equipped with a stirrer was purged with nitrogen gas three times. Then, 77 g of 4-hydroxybutyl vinyl ether,
Cyclohexyl isocyanate 50g, xylene 127
g was charged and reacted at 80°C for 6 hours. Then, 2.6 g of methyl maleate, 4-methacryloyloxy-1
,2,2,6,6,-pentamethylpiperidine 1.2g
, 32 g of isobutyl vinyl ether, 117 g of chlorotrifluoroethylene, 153 g of xylene, and 2.8 g of octanoyl peroxide as an initiator were charged.
Polymerization was carried out at ℃ for 8 hours. After the polymerization was completed, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the resulting copolymer solution was taken out. This copolymer solution was reprecipitated with n-hexane and dried. The yield of copolymer was 258 g.

The number average molecular weight of the obtained copolymer was 9.3
00, the fluorine content is 20.4%, and the hydroxyl value is 52.
mgKOH/g, acid value was 4 mgKOH/g, and glass transition temperature was 32°C.

[0098]

Example 6 A stainless steel autoclave with an internal volume of 1 liter and equipped with a stirrer was purged with nitrogen gas three times. Next, 74 g of 4-hydroxybutyl vinyl ether, 2.6 g of crotonic acid, and 4-methacryloyloxy-1,2
, 2 g of 2,6,6-pentamethylpiperidine, 84 g of isobutyl vinyl ether, 176 g of chlorotrifluoroethylene, 336 g of xylene, and 4.2 g of octanoyl peroxide as an initiator.
Time polymerization was performed. After the polymerization was completed, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the resulting copolymer solution was taken out. This copolymer solution was reprecipitated with n-hexane and dried. The yield of copolymer was 314 g.

The number average molecular weight of the obtained copolymer was 7.8.
00, the fluorine content is 25.4%, and the hydroxyl value is 10.
The acid value was 5 mmgKOH/g, and the glass transition temperature was 21°C. This is referred to as [Copolymer A]. 100 g of copolymer A dissolved in 111 g of xylene and 11 g of cyclohexyl isocyanate were added with 20 ppm of dibutyltin dilaurate (based on solid content) as a catalyst, and N
The reaction was continued at 80° C. for 4 hours until the disappearance of the CO group was confirmed.

The obtained fluororesin solution had a solid content of 50
%, number average molecular weight 9,500, resin hydroxyl value 51 mg
KOH/g, and the resin acid value was 4 mmgKOH/g.

[0101]

[Example 7] 100 g of the copolymer A obtained in Example 6 was dissolved in 126 g of xylene, and 26 g of a half block of IPDI obtained in Example 4 with isobutyl alcohol were mixed with 20 pp of dibutyltin dilaurate.
m (based on solid content) was added as a catalyst, and the mixture was heated for 80 minutes until the disappearance of NCO groups was confirmed by infrared absorption spectrum (IR).
The reaction was carried out at ℃ for 4 hours.

The obtained fluororesin solution had a solid content of 50
%, number average molecular weight 10,600, resin hydroxyl value 43m
gKOH/g, and the resin acid value was 3 mgKOH/g.

[0103]

Example 8 The inside of a stainless steel autoclave with an internal volume of 1 liter and equipped with a stirrer was purged with nitrogen gas three times. Then, 84 g of 4-hydroxybutyl vinyl ether,
38 g of cyclohexyl isocyanate, 187 g of xylene
g was charged and reacted at 80°C for 6 hours. Then, 17.2 g of crotonic acid, 4-methacryloyloxy-2,2
, 1.2 g of ,6,6,-tetramethylpiperidine, 8 g of isobutyl vinyl ether, 117 g of chlorotrifluoroethylene, 143 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. went. After the polymerization was completed, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the resulting copolymer solution was taken out. This copolymer solution was reprecipitated with n-hexane and dried. The yield of copolymer was 283 g.

The number average molecular weight of the obtained copolymer was 7.8.
00, the fluorine content is 17.3%, and the hydroxyl value is 72.
mgKOH/g, acid value was 26 mgKOH/g, and glass transition temperature was 32°C.

[0105]

[Examples 9 to 15] Each of the fluororesins obtained in Examples 1 to 5 was adjusted to a solid content of 50% with xylene, or the fluororesin solutions obtained in Examples 6 and 7 (solid content 50%) as the main ingredient, and "Duranate TPA" (manufactured by Asahi Kasei Industries, Ltd.) as the curing agent with NCO/OH = 1.
/1, and then painted using xylene as thinner with Ford Cup #4 for 15 seconds. After baking the obtained coating film at 120° C. for 1 hour, the physical properties of the coating film (coating film appearance, coating gloss, coating film hardness, flexibility, adhesion (Al), weather resistance) were evaluated.

In addition, each of the fluororesins obtained in Examples 1 to 5 was adjusted to have a solid content of 50% with xylene, or the fluororesin solutions obtained in Examples 6 and 7 (solid content was adjusted to 50%) ) and a pigment (quinacridone red) to a predetermined pigment weight concentration (PWC = 12%) and dispersed for 2 hours using a sand mill, each as a main ingredient,
The composition was formulated and painted as described above, and the degree of gloss and pigment aggregation was visually determined to evaluate pigment dispersibility.

[0107] The results are shown in Table 1.

[0108]

[Comparative Example 1] 7.7 g of potassium carbonate was charged into a stainless steel autoclave with an internal volume of 1 liter and equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times. Next, 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 the polymerization was completed, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the resulting copolymer solution was taken out. After removing potassium carbonate from this copolymer solution by filtration, it was reprecipitated with n-hexane and dried. The yield of 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, acid value was 0 mgKOH/g, and glass transition temperature was 21°C.

[0110]

[Comparative Example 2] 7.7 g of potassium carbonate was charged into a stainless steel autoclave with an internal volume of 1 liter and equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times. Next, 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
174 g of xylene (17 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 the polymerization was completed, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the resulting copolymer solution was taken out. After removing potassium carbonate from this copolymer solution by filtration, it was reprecipitated with n-hexane and dried. The yield of 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 46.
mgKOH/g, acid value was 0 mgKOH/g, and glass transition temperature was 28°C.

[0112]

[Comparative Example 3] 7.7 g of potassium carbonate was charged into a stainless steel autoclave with an internal volume of 1 liter and equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times. Next, 1.7 g of crotonic acid, 23 g of 4-hydroxybutyl vinyl ether, 78 g of isobutyl vinyl ether,
117g chlorotrifluoroethylene 220g xylene
and 2.8 g of octanoyl peroxide as an initiator.
was charged and polymerization was carried out at 73°C for 8 hours. After the polymerization was completed, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the resulting copolymer solution was taken out. After removing potassium carbonate from this copolymer solution by filtration, it was reprecipitated with n-hexane and dried. The yield of copolymer was 212 g.

The number average molecular weight of the obtained copolymer was 7.8.
00, the fluorine content is 25.9%, and the hydroxyl value is 51.
mgKOH/g, acid value was 1.2 mgKOH/g, and glass transition temperature was 21°C.

[0114]

[Comparative Examples 4 to 7] Each of the fluororesins obtained in Comparative Examples 1 to 3 was adjusted to a solid content of 50% with xylene, and Copolymer A was used as the main ingredient, and "Duranate TPA" was used as the curing agent. (manufactured by Asahi Kasei Industries, Ltd.) NCO/OH=1
/1, and then painted using xylene as a thinner with Ford Cup #4 for 15 seconds. After baking the obtained coating film at 120°C for 1 hour, the physical properties of the coating film (coating film appearance, coating film gloss, coating film hardness, flexibility,
Adhesion (Al), weather resistance) were evaluated.

In addition, each of the fluororesins obtained in Comparative Examples 1 to 3 was adjusted to a solid content of 50% with xylene, and copolymer A and pigment (quinacridone red) were mixed at a predetermined pigment weight concentration ( PWC = 12%).
Dispersion using a sand mill for 2 hours was used as the main ingredient, and the pigments were blended and painted as described above, and the degree of gloss and pigment aggregation was visually determined to evaluate pigment dispersibility.

[0116] The respective results are shown in Table 1.

[0117]

[Table 1]

[0118]

[Reference Example 1] Fluorine-containing resin obtained in Example 8 ((A)
When 80 g of the unit (17.2 g of crotonic acid) was dissolved in 20 g of ethyl cellosolve, 3.2 g of methyldiethanolamine was added, and 100 g of deionized water was added, a uniform fluorine-containing product with a resin content of 40% was obtained. A resin dispersion was obtained. In this way, the fluorine-containing copolymer of the present invention (
It can be seen that when the content of A) units is in the range of 5 to 40 mol %, good affinity is shown for the aqueous medium.

[0119]

Effects of the Invention As is clear from the above results, the present invention is soluble in organic solvents and has excellent compatibility with hardening agents and various fillers such as pigments and reinforcing agents. A fluororesin that can be cured at room temperature can be easily provided. In addition, the fluorine-based paint of the present invention, which contains the fluororesin as a main component, is glossy and hard, and can provide a coating film with excellent adhesion to the substrate and weather resistance under mild conditions. ,
For example, it is useful as a baking paint for colored rigid plates, colored aluminum plates, and aluminum sashes, or as an air-drying paint that can be applied on-site.

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

Furthermore, the fluororesin has a high affinity for aqueous media and is useful as a raw material for aqueous fluorine-based paints.

Claims (1)

[Claims] [Claim 1] A fluororesin comprising the following constituent components. (A) Units represented by formula [Chemical formula 1] 0.01 to 40 mol% (B) Units represented by formula [Chemical formula 2] 20 to 80 mol%
(C) Units represented by the formula [Chemical formula 3] 3 to 80 mol% [
2. A paint containing the fluororesin according to claim 1 as a main component.