JPS63161008A - Curable resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition curable by irradiation of heat or active energy rays such as ultraviolet light or electron beams, capable of giving cured products of high water resistance, comprising a specific prepolymer and fluorine-contg. aromatic dicarboxylic acid diallyl ester. CONSTITUTION:The objective composition comprising (A) a prepolymer having in one molecule at least one C=C double bond (e.g., unsaturated polybasic carboxylic acid polyester, unsaturated polyhydric alcohol polyester, unsaturated polyurethane) and (B) a fluorine-contg. aromatic dicarboxylic acid diallyl ester of formula I (X is 6-14C perfluoroalkenyl, e.g., of formula II, III). It is preferable that this composition contain such a reactive diluent as styrene or divinylbenzene. The compound of the formula I is novel one, which can be prepared, for example, by reaction of a perfluoroalkene of formula XF with a novel compound of formula IV made by esterification of hydroxyphthalic acid by allyl alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin composition that is cured by irradiation with heat or so-called active energy rays such as ultraviolet rays, electron beams, and gamma rays.

(Prior Art) A large number of curable resin compositions have been known in the past, including inks, festivals, paints, etc. *Used for various purposes such as adhesives, FRP, and cast products. However, for example, epoxy 7 acrylate resin has excellent adhesion to various base materials but is poor in water resistance, and resins used for unsaturated polyester also have the disadvantage of insufficient water resistance. There is.

(Problems to be Solved by the Invention) The purpose of the present invention is to eliminate the defects described in the 04 resin composition that is cured by heating or irradiating active energy rays, and to produce a cured product having excellent water resistance. The object of the present invention is to provide a curable resin composition that provides a curable resin composition.

(Means for Solving the Problems) The present invention provides a prepolymer having at least one carbon-carbon double bond in the molecule, and a formula (X represents a perfluoroalkenyl group of 6 to 14 at U element 11). It relates to a curable resin composition containing diallyl fluorine-containing aromatic dicarboxylic acid represented by:

A prepolymer is generally a polymer produced by stopping the polymerization reaction at an appropriate intermediate stage in order to facilitate molding, or a polymer produced by a reaction or under conditions that do not allow the polymerization reaction to proceed to a very high degree of polymerization. A polymer with a low degree of strength.

In the case of thermosetting resins, if the reaction is carried out sufficiently, a three-dimensional cross-linked structure will be generated, making the resin infusible and insoluble, making it impossible to mold it. Therefore, the polymerization reaction is carried out to the extent that it retains appropriate plasticity, and then molded. while curing. Further, unsaturated polyester resin, polyurethane resin, etc. are also cured while molding the prepolymer. In the production of polymers by bulk polymerization of methyl methacrylate, a prepolymer polymerized to an appropriate viscosity is placed in a mold and further heated to complete the polymerization reaction to produce a product. (For example, Chief Editor, Shoji Shida, Chemistry Dictionary, March 9, 1981, published by Morikita Publishing Co., Ltd.) The prepolymer that is a component of the composition of the present invention has at least one carbon-carbon double bond in the molecule. ing.

This is because, without this, in the composition, the compound (1) and the prepolymer would not react to form a cured product. The diallyl fluorine-containing aromatic dicarboxylic acid represented by the formula (1) reacts with all or a portion of this double bond to cause addition polymerization or to form a crosslink.

Diallyl fluorine-containing aromatic dicarboxylate represented by the formula (1), which is another component of the composition of the present invention, has addition polymerizability and crosslinking property itself, but carbon - It has a property (copolymerizability) of reacting with a carbon double bond to undergo rapid addition polymerization (copolymerizability) and a property of forming crosslinks between the prepolymers (crosslinkability). Furthermore, it has the property of imparting water resistance to the cured product of the composition of the present invention.

In the present invention, the perfluoroalkenyl group having 6 to 14 carbon atoms represented by -Yumeito l + Izuha h1 first one is F atom,
Others may represent a perfluoroalkyl group having 1 to 6 carbon atoms, and R4 represents a perfluorofurkyl group having 1 to 5 carbon atoms. fluoropropene dimer or trimer,
1 fluorine atom from tetrafluoroethylene tetramer to heptamer
Examples of groups formed by the elimination of these groups include the following structural formulas.

(CF,)2C=6C2F7, C.F.

The above compound (1) of the present invention is a new compound, for example, a hydroxy aromatic nocarboxylic acid derivative represented by the formula and XF
It is obtained by reacting a perfluoroalkene represented by (X represents perfluoroalkenyl having 6 to 14 carbon atoms).

The above-mentioned compound (2) is a new compound, and to produce it, for example, hydroxy 7-talic acid is usually esterified with 7-lyl alcohol in the presence of a catalyst.
It is preferable to use about 2 to 40 moles of 7lyl alcohol per 1 mole of tarric acid. Examples of the catalyst include concentrated sulfuric acid, para-toluenesulfonic acid, and boron trisulfide ethyl etherate. The reaction temperature is preferably about 50-2
00℃, the reaction time can be determined as appropriate, generally from about 30 minutes.
The reaction time is preferably about 20 hours, and the reaction pressure is not particularly limited.

This reaction is preferably carried out in a solvent. The solvent is preferably one that is azeotropic with water, such as benzene, toluene, xylene, or diallyl ether, and does not substantially form a solution when mixed with water. The generated compound (2) can be purified by known methods such as concentration, extraction, distillation, chromatography, etc., but it can also be reacted with a perfluoroalkene represented by XF in the next step without purification. .

The perfluoroalkene represented by the formula (indicating a group), particularly preferred are hexafluoropropene dimer and V3f1 form,
A tetrafluoroethylene heptamer can be mentioned, and the structural formula is as follows.

(CF3)2C=CF (02F%), The reaction is preferably carried out in a solvent in the presence of a base. Examples of the base include triethylamine, trimethylamine,
Amines such as tripropylamine, alkali metals or their hydroxides, etc., and aprotic polar solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, etc. can be suitably used as the solvent. The ratio of compound (2) and perfluoroalkene is usually about 1 to 10 moles of the latter per 1 mole of the former. The reaction temperature can be selected as appropriate, but is preferably in the range of about θ to 40°C, particularly about 0 to 20°C. The amount of base is about 2 to 1 mole of compound (2).
It is preferable to use it in a range of 20 mol. The target compound, Compound (1), can usually be separated and recovered by a known method used for separating an organic compound mixture system in which a solid is dissolved in a liquid. The resulting precipitate can be recovered by distilling it under reduced pressure.

(3) Some of the compounds represented by XF in the formula include and Compounds represented by are included.

From these, each is generated.

More specifically, for example is generated.

Compound (1) can also be obtained, for example, by reacting an aromatic dicarboxylic acid represented by the formula (X is the same as above) with 7lyl alcohol. Compound (4) is a known compound.

Preferably, the reaction is carried out in a solvent. As a solvent, it is preferable to use a solvent that is azeotropic with water and is substantially immiscible with water *L<, for example i? Examples include benzene, toluene, xylene, diallyl ether, and the like. The ratio of compound (4) and allyl alcohol is usually about 2 to 1 mole of the former to about 1 mole of the latter.
Preferably, 0 mol is used. The reaction temperature can be selected as appropriate, but it is preferably in the range of about 50 to 200°C, particularly about 70 to 160°C. Compound (1), which is the target compound, is usually used for the separation of a mixed organic compound system in which a solid is dissolved in a liquid. It can be separated and recovered by known methods, such as concentration, distillation, chromatography, etc.

In the present invention, prepolymers having at least one double bond in the molecule include, but are not limited to, the following.

(i) Unsaturated polybasic carboxylic acid polyester or unsaturated polyhydric alcohol polyester A condensate of a polybasic carboxylic acid and a polyhydric alcohol, in which at least some or all of them are unsaturated polybasic carboxylic acids. It is an acid or an unsaturated polyhydric alcohol.

Polybasic carboxylic acids include unsaturated polybasic carboxylic acids and saturated polybasic carboxylic acids, and examples of the former include maleic anhydride, hexamaric acid, citraconic acid, and itaconic acid, and the latter include , 7-talic anhydride, isophthalic acid, terephthalic acid, 7-dipic acid, azelaic acid, sebacic acid, dodecanniic acid and the like. For details, please refer to Polymer Data [Polymer Data Handbook Basic II Edition No. 259-
page 275 (nocarboxylic acid)] (January 30, 1985,
Published by Baifukan Co., Ltd.).

Polyhydric alcohols include saturated polyhydric alcohols and unsaturated polyhydric alcohols, and the former include ethylene glycol,
Examples include flukanediol having 2 to 8 carbon atoms such as propylene glycol, and the latter include butynediol, 3,4-
Examples include dihydroxy-1,5-hexadiene and pentaerythritol noallyl ether. For details, please refer to the above-mentioned “Polymer Data Handbook Basic Edition No. 283”.
- pages 322 (Diols and Polyhydric Alcohols).

Generally, it is an unsaturated polybasic carboxylic acid or a condensate of a saturated polybasic carboxylic acid and a saturated polyhydric alcohol.

(ii) Unsaturated monocarboxylic acid polyester A condensate of an unsaturated monocarboxylic acid, a polybasic carboxylic acid, and a polyhydric alcohol.

Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid.
It also includes halfesters of unsaturated nocarboxylic acids such as alkyl (R element a1-8 of alkyl), monoalkyl 7malate (alkyl has 1-8 carbon atoms), and monoalkyl itaconate (alkyl has 1-8 carbon atoms). Ru.

For polybasic carboxylic acids and polyhydric alcohols,
As already stated in (i).

Generally, it is a condensate of an unsaturated monocarboxylic acid, a saturated polybasic carboxylic acid, and a saturated polyhydric flucol.

(iii) Adduct of polyvalent epoxy compound and unsaturated monocarboxylic acid This is an adduct of unsaturated monocarboxylic acid to a polyvalent epoxy compound.

Polyvalent epoxy compounds include polyepoxy hydrocarbons, polyepoxyhalodenohydrocarbons, polyepoxyalcohols, polyepoxyaldehydes, polyepoxycarboxylic acids, etc., and include both saturated and unsaturated compounds, with two or more compounds in one molecule. These polymers, so-called epoxy resins, are also included as long as they have epoxy groups. Examples of polyvalent epoxy compounds include Tosu72/-L-A-diglycidyl ether, neopentyl glycol diglycidyl ether, vinylcyclohexene dieboxide, and epoxidized soybean oil. As for unsaturated monocarboxylic acids, the compounds mentioned in (ii) can be exemplified.

(1v) Polyether polyol Unsaturated monocarboxylic acid ester This is an ester of an adduct of fullylene oxide to a polyhydric alcohol (polyether polyol) and an unsaturated monocarboxylic acid.

Alkylene oxides include those having 2 to 8 carbon atoms, such as ethylene oxide and propylene oxide, and those in which some hydrogen atoms are replaced with halogen atoms, such as chlorine atoms.

For polyhydric alcohols and unsaturated moacarboxylic acids,
As already stated in (i) and (7(ii)).

(v) Unsaturated polyurethane A soluble and fusible compound having free isocyanate groups (
It is an adduct of an unsaturated monocarboxylic acid partial ester of a polyhydric alcohol to a polyhydric alcohol (forming a linear or branched structure and not forming a network structure).

As those having uni and free incyanate groups, mention may be made of polyhydric isocyanates and adducts of polyhydric incyane Y to polyhydric alcohols and V/or polyether polyols.

Polyvalent incyanates include tolylene diisocyanate,
Dimethylene benzene diisocyanate, diphenylmethane diisocyanate, hexahydrotolylene diisocyanate, di/ethylene cyclohexane noisocyanate,
Dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, inholone noisocyanate,
Tri-7enyl/tan triisocyanate, C 1 ""-( == ( ○Q ( As described in (i) for polyhydric alcohols and (iv) for polyether polyols.

Examples of unsaturated monocarboxylic acid partial esters of polyhydric alcohols include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and glycerin di(meth)acrylate.

These compounds (i) to (v) can be used alone or in combination of two or more.

In the composition of the present invention, the compounding ratio of compound (1) is approximately 1
It is preferably in the range of ~99% (wt%, hereinafter the same), and particularly preferably in the range of about 20 to 60%.

In the present invention, an ethylenically unsaturated compound can be used as a reactive diluent if necessary when curing the resin composition. Various known compounds can be used as the ethylenically unsaturated compound, but representative examples include styrene, vinyltoluene, chlorostyrene, t-butylstyrene, a-methylstyrene, novinylbenzene, acrylic acid, and methacrylic acid. , methyl, ethyl, isopropyl, n-butyl, t-butyl, a-ethylhexyl, n-/nyl, n- of acrylic or methacrylic acid
Decyl, lauryl, ste7lyl ester, etc., n-butoxyethyl acrylic acid or methacrylic acid, cyclohexyl, 7ethyl/xyethyl, tetrahydropurfuryl,
glycitur, allyl, pencil, tribromophenyl,
2.3-dichloropropyl, 3-chloro-2-human axypyl ester, etc., ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, diethylene glycol 7/(meth)acrylate, dipropylene glycol mono( meth)acrylate, polyprolene glycol mo/(meth)acrylate) with a molecular weight (hereinafter referred to as MW) of 200 to 1000, M
Polyethylene glyfur monomethyl ether mono(meth)acrylate with W200-1000, MW200-1
M
Polyethylene glycol monoethyl nythermo/(meth)acrylate with W200-1000, MW200-1
000 polypropylene glycol monoethyl ether mono(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate ) acrylate, neobentyl glycol no(meth)acrylate, 1,6-hexanethiol di(meth)acrylate,
Polyprolene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate
Acrylate, trinotylolethane di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolethane tri(meth)acrylate,
The amount of the zero-reactive diluent, which includes diallyl 7-talate, dibutyl 7-malate, vinyl acetate, etc., is about 1 to 95% by weight, preferably about 5 to 8% by weight, based on the total amount with the prepyrimer.
Good I1% is 0% by weight.

For the purpose of stably storing the composition of the present invention, a known polymerization inhibitor can be added.

The amount added is 0.001 to 2.5 based on the total amount of the composition.
% by weight, preferably in the range of o, oos to 1% by weight.Furthermore, in the present invention, commonly used additives such as colorants and dispersants can be added as necessary.

The composition of the present invention can be obtained by mixing the above-mentioned components by various known methods, and for example, a mixer, roll mill, ball mill, sand mill, high-speed impeller, etc. can be used.

The composition of the present invention can be cured by known methods for prepolymers having at least 61 double bonds in the molecule, such as heat or ultraviolet light, electron beams, X-rays, gamma rays, etc.
It can be cured by irradiating active energy such as radiation.

In the present invention, when using high-energy ionizing radiation such as electron beams, X-rays, and γ-rays, which have the effect of being absorbed by substances and emitting secondary electrons, it is not necessary to add a polymerization initiator. However, when curing by other heating or ultraviolet rays, it is preferable to add a thermal polymerization initiator or a photopolymerization initiator.

Examples of thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, t-butyl perbenzoate, and t-butyl perbenzoate.
Peresters such as butyl peroxy-2-ethylhexoate, hydroperoxides and oxides such as t-butyl hydroperoxide and cumene hydroperoxide, and photopolymerization initiators such as 2.2 - benzoinfurkyl ethers such as jetoxyaceto7ene/2,2-dimethoxy-2-phenyl7cetophenone, aceto7enes such as jetoxyacetophenone, ketones such as benzophenone, thioxanthone such as 2-chlorothioxanthone Examples include the following. The amount of initiator added is about 0.001 to 20% by weight, preferably about 0.1 to 20% by weight based on the total amount of prepolymer and diluent.
It is best to set the first part to %.

Regardless of heat, light, or active energy rays, the curing temperature ranges from room temperature to 250°C, preferably from room temperature to 180°C. The amount of the rfR initiator added is preferably about 0.001 to 20% by weight, preferably about 0.1 to 10% by weight, based on the total weight of the prepolymer and diluent.

(Example) In the following reference examples, examples, and comparative examples, 0 parts means 0 parts unless otherwise specified.

Reference Example 1 0.2 mole of 5-hydroxyisophthalic acid was placed in a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and 0.6 mole of allyl alcohol, toluene Booml, and 1.3 g of sulfuric acid were added.

0.2 g of p-methoxyphenol was added and the mixture was heated to reflux. The distilled water was condensed in a cooling tube and separated from toluene, which was continuously returned to the reaction vessel. After 8 hours, heating was stopped and the mixture was allowed to cool.

The total amount of water distilled out at this point was 71.

After washing the reaction solution with saturated brine until the aqueous layer no longer showed acidity, toluene was distilled off under reduced pressure. This concentrated solution was distilled under reduced pressure to obtain 27 g (yield 52%) of diallyl 5-hydroxyisophthalate.

b, p, 202-205°C 15 mmHg 28 g of diallyl 5-hydroxyisophthalate thus obtained was dissolved in 90 ml of dimethylformamide, 31 g of triethylamine was added, and 45 g of hexafluoropropene trimer was added in one portion at room temperature with stirring. and continued stirring. After 2 hours, the reaction solution was poured into a large amount of diluted hydrochloric acid, and the precipitated oil was separated, washed with water, and distilled under reduced pressure to obtain diallyl 5-(perfluorononenyloxy)isophthalate (compound A).
) 41g (yield 59%) was obtained.

b@p, 150-152℃ / 4 III
Hg Reference Example 2 4-(t<-Fluorononenyloxy)7tallic diallyl ( Compound B) was obtained.

b@p, 160~b Reference Example 3 Reference Example except that 30 g of 2fi form was used instead of the hexafluoropropene 3 form in Reference Example 1, and the reaction temperature with diallyl 5-hydroxyisophthalate was 0 to 4°C. 1
In the same manner as above, 39 g of diallyl 5-(perfluorohexenyloxy)isophthalate (compound C) was obtained.

b, p, 128-131°C 15+ma+Hg Reference Example 4 4-(perfluorodecetate) was prepared in the same manner as in Reference Example 2 except that 50 g of tetrafluoroethylene pentamer was used instead of the hexafluoropropene trimer in Reference Example 2. Diallyl(oxy)7talate (Compound D) was obtained.

b, p, 165-b Example 1 An ultraviolet curable resin composition (1) was produced with the following formulation.

This oligoester 7 acrylate [Product name Arrowex M-6420X, viscosity 4 x 10'cps/50
°C, manufactured by Toagosei Kagaku Kogyo Co., Ltd.] 50 Compound (A) 35 units Trimethylolpropane triacrylate 5 units 2-hydroxyethyl acrylate 3*0-Methyl benzoylbenzoate 5 units Diethylaminoethyl methacrylate 100 parts Composition Coat material (1) on a glass plate using a bar coater to 20μ
Coat it to the desired thickness and use a high pressure mercury lamp (80W/e1m).
) on a conveyor running at 5 m/min.
After several passes, the coating film was completely cured.

Example 2 An ultraviolet curable resin composition (If) was produced with the following formulation.

This unsaturated epoxy resin [Product name Dicklite UE-8]
200, manufactured by Dainippon Ink and Chemicals Co., Ltd.] This compound (B) 30 units 1,6-hexanesiol cyacrylate 10 units 2-hydroxyethyl acryloyl phos7ate car 0-benzoylbenzoate 5 units Triethanolamine 2,100 parts of composition (II) was applied to a degreased soft steel plate using a bar coater to a thickness of 20 μm, and the following operations were carried out in the same manner as in Example 1.

Example 3 COOCH2CH=CH2 A thermosetting resin composition (III) was produced with the following formulation.

This maleic acid-propylene glycol-based unsaturated compound +)
x x f rutJ1m (acid value 1B, 5mgK O
H/g) 40 compounds (C)
35 pieces 7
2 0 methyl ethyl ketone peroxide 3 methyl aniline (0.5%
Solution) 1 quintillion s 7 ten Cobalt Co 5'
1,100 parts of composition (III) was applied to a degreased soft steel plate to a thickness of 100 μm using a bar coater, and left at 30° C. for 10 hours in a desiccator purged with nitrogen.

Example 4 Present urethane acrylate [Product name Aronix M-11
00, viscosity 8-12X 10'cps/50'C.

Manufactured by Toagosei Kagaku Kogyo Co., Ltd.] 45 Compound (A) 25 units Trimethylolpropane triacrylate 2-hydroxyethyl acryloyl 3-phosphate 7-ethyl methyl 0-benzoylbenzoate 5 units Triethanolamine 2100 parts of the above An ultraviolet curable resin composition (■) was produced by blending. The same procedure as in Example 1 was carried out using composition (IV).

Example 5 The present polyether acrylate [trade name Aronix M-
220. Viscosity 10-20 cps/25°C, manufactured by Toagosei Chemical Industry Co., Ltd.] 30 This compound (B) s.

Trinotylolpropane triacrylate Notyl 0-benzoylbenzoate 50 Diethylaminoethyl methacrylate 100 parts An ultraviolet curable resin composition (V) was prepared using the above formulation. Composition (V) was coated on a glass plate using a percoater.
The coating was applied to a thickness of 0 μm, and the following operations were carried out in the same manner as in Example 1.

Comparative Example 1 The composition of Example 1 was operated in the same manner as in Example 1 except that compound (A) was replaced with diallyl isophthalate.

Comparative Example 2 The composition of Example 2 was operated in the same manner as in Example 2, except that noallyl heptatalate was used instead of compound (B).

Comparative Example 3 The composition of Example 3 was operated in the same manner as in Example 3 except that diallyl isophthalate was used instead of compound (C).

Comparative Example 4 The same procedure as in Example 4 was carried out except that diallyl isophthalate was used instead of compound (A) in the composition of Example 4.

Comparative Example 5 The same procedure as in Example 5 was carried out except that diallyl isophthalate was used in place of compound (B) in the composition of Example 5.

Example 6 An ultraviolet curable resin composition (VI) was produced with the following formulation and operated in the same manner as in Example 1.

This polyethylene glycol diacrylate (average molecular weight 510) 40 car compound (A)
20 car trimethylolpropane triacrylate methyl 0-benzoylbenzoate
6 bottles 100 parts of diethylaminoethyl methacrylate Example 7 1 mole of maleic anhydride, 1 mole of talic anhydride and 2.16 moles of diethylene glycol were added to 1 mole of diethylene glycol while passing nitrogen through it.
The temperature was raised to 150°C over an hour, then held at that temperature for 2 hours, and then heating continued at 190°C for 3 hours. The residue was an unsaturated polyester with an acid value of 55.7 mg K OH/g and a hydroxyl value of 84.9 mg K OH/g. The thermosetting resin composition (■
) and a cured product were obtained.

Example 8 An ultraviolet curable resin composition (■) was produced with the following formulation,
The following operations were carried out in the same manner as in Example 1.

Urethane acrylate 40 Compound (A) 20 Trinotyrolpropane triacrylate Tetrahydro-7-rufuryl acrylate 20 Wood benzyl dimethyl ketal 100 parts Example 9 Oligoester acrylate represented by the following structural formula [trade name Bishuto #3) 00, Osaka Organic Chemical Industry Co., Ltd.
An ultraviolet curable resin composition OX) was prepared using 50 parts of the UV-curable resin composition OX) as a base resin, and the following operations were carried out in the same manner as in Example 1.

(Viscosity 400-600 cps 150°C) Example 10 An ultraviolet curable resin composition (X) was produced with the following formulation,
The following operation was carried out in the same manner as in Example 2.

This epoxy acrylate [Product name Bishoot #540]
, manufactured by Osaka Organic Chemical Industry Co., Ltd.]40C)12=CHC0
0CH2CH(01()C)12-(viscosity 2 X10'
cps150℃) This compound (B) 30*1f6
-Hexaneshiolnoacrylate) 20 Kyo 2-Hydroxyethyl 7Cryloyl 3Phos 7Eight Wood 0-Methyl benzoylbenzoate 5 units Triethanolamine 2100 parts/Resistance and resistance amount Adhesion to the substrate before boiling by the following method The water resistance was tested by checking the condition of the coating film after boiling. The results are shown in Table 1. From the table, water resistance was improved by blending compound (1), and the effect of the present invention is clear.

Adhesion: Tested using a goblin peel test. That is, one square of I x 1 mm is placed on the coating film to reach the substrate.
00 squares, pressed cellophane tape on top of it to adhere it and peeled it off, and counted the number of remaining squares. The display is the number of remaining square holes.

Water resistance: Condition of paint film after 2 hours of boiling ○ No change at all Δ　Whitening, 7 creases are partially observed. X Peeling from the base material Table 1 (that's all)

Claims (3)

[Claims] (1) Prepolymers having at least one carbon-carbon double bond in the molecule, and formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (X represents a perfluoroalkenyl group having 6 to 14 carbon atoms) ) A curable resin composition containing diallyl fluorine-containing aromatic dicarboxylic acid represented by: (2) Prepolymer is unsaturated polybasic carboxylic acid polyester, unsaturated polyhydric alcohol polyester, unsaturated monocarboxylic acid polyester, adduct of polyvalent epoxy compound and unsaturated monocarboxylic acid, polyether polyol unsaturated monocarboxylic acid The composition according to claim 1, which is an acid ester or an unsaturated polyurethane. (3) Claim 1 further containing a reactive diluent
Compositions as described in Section.