JPS63113010A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition useful as coating compound, adhesive, cast article, etc., having improved adhesivity, water resistance, chemical resistance, mechanical strength and curing properties, by blending a specific resin of side chain unsaturated bond type with a specific unsaturated alkyd. CONSTITUTION:A composition obtained by blending (A) a resin of side chain unsaturated bond type shown by formula [A is main chain consisting of vinyl monomer and (meth)acryloyl group; R is H or CH3; Y is epoxy resin residue after removal of ester bond from compound having the ester bond which is formed by subjecting epoxy group in molecule to ring formation and addition reaction with carboxyl group] with (B) an unsaturated alkyd prepared by esterifying an alpha,beta-unsaturated polybasic acid (acid anhydride thereof) or a mixture of the acid and a saturated polybasic acid (acid anhydride thereof) with a polyhydric alcohol and, if necessary, (C) a polymerizable monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a curable resin composition having excellent adhesion, water resistance, chemical resistance and mechanical strength.

[Conventional technology]

In recent years, as the uses of radical curable resins such as unsaturated polyester resins and vinyl ester resins have expanded, the performance required of these radical curable resins has become increasingly sophisticated. For example, hot water storage tanks are now required to have better water resistance and chemical resistance than existing radical curable resins.

Water resistance and chemical resistance naturally depend on the structure of the polymer, and with existing radical curing resins such as unsaturated polyester resin and vinyl ester resin,
All of them have ester bonds in the constituent molecules of the main chain polymer or main chain oligomer, and it is known that the concentration of these ester bonds is a factor that influences performance.

Therefore, even if we try to improve the physical properties of these existing radical-curing resins beyond a certain level, there are factors such as ester bonds in the main chain that impair the physical properties, so it is difficult to improve the physical properties beyond a certain level. It is virtually impossible to do so.

[Problem that the invention seeks to solve]

As a result of various studies on curable resins that eliminate the drawbacks of existing radical curable resins and can be used in a wider range of applications, the present inventors discovered that the main chain contains factors that impair physical properties such as ester bonds. The main chain polymer is a polymer obtained by polymerization of vinyl monomers with no vinyl monomer, and the side chain unsaturated bond type resin has an acryloyl group or methacryloyl group as a crosslinking point by radical curing in the side chain via an epoxy resin residue. Headline found to be valid.

Already suggested.

However, when this side chain unsaturated bond type resin is used alone,
The problem with this method is that it cures slowly and takes a relatively long time to completely cure.

From this point of view, the present inventors further investigated and found that a curable resin m is prepared by blending a side chain unsaturated bond type resin, an unsaturated alkyd, and, if necessary, a polymerizable monomer.
The present invention was completed by discovering that a paraboloid can solve the above-mentioned drawbacks.

[Means for solving problems]

That is, the present invention is based on the general formula [where A is a main chain consisting of a copolymer resin of a vinyl monomer and an acryloyl group or a methacryloyl group,
R is hydrogen or a methyl group, and Y is the residue of an epoxy resin in which the epoxy group in the molecule forms an ester bond through a ring-opening addition reaction with a carboxyl group, from which the ester bond is removed. A resin obtained by esterifying a chain-unsaturated bond type resin and (B) an α, β-unsaturated polybasic acid or its acid anhydride, or a mixture of this and a saturated polybasic acid or its acid anhydride, and a polyhydric alcohol. The present invention relates to a curable resin composition comprising an unsaturated alkyd and C) a polymerizable monomer as required.

[Effect]

In the present invention, the effect of blending the side chain unsaturated bond type resin and the unsaturated alkyd is extremely remarkable.

That is, side chain unsaturated bond type resins have the disadvantage of slow curing and require a relatively long time for complete curing, while unsaturated alkyds are water resistant.

Although it has drawbacks such as insufficient chemical resistance and adhesion, these component defects can be resolved by mixing a high molecular weight (molecular weight of approximately 10,000 or more) side chain unsaturated bond type resin and unsaturated alkyd. This provides a curable resin composition that is completely cured, has excellent curability, and has extremely excellent adhesion, water resistance, and mechanical strength.

As a first method, the side chain unsaturated bond type resin used in the present invention is prepared by: (1) about 0.1 to 0.5 equivalents of acrylic acid or methacrylic acid per 1 equivalent of the epoxy group of the epoxy resin; At least one unsaturated epoxy resin has an acryloyl group or a methacryloyl group [hereinafter abbreviated as a (meth)acryloyl group] and an epoxy group in the molecule obtained by reacting [hereinafter abbreviated as (meth)acrylic acid]. A polymer-containing reaction mixture having an epoxy resin group in the side chain of the resulting polymer is produced by total copolymerization of the component contained as a fraction and (2) a vinyl monomer, and then the epoxy resin remaining in the resulting reaction mixture is It is prepared by adding a substantially equivalent amount of (meth)acrylic acid to the epoxy group and reacting the epoxy group with the carboxyl group.

In addition, as a second method, (1) a vinyl copolymer having a carboxyl group in the side chain obtained by copolymerizing (meth)acrylic acid and a vinyl monomer, and (2) an epoxy group 1 of an epoxy resin. 0.5-0. In the molecule obtained by reacting g equivalent of (meth)acrylic acid, (
meth) acryloyl group and an unsaturated epoxy resin having 72 poquine groups. Agricultural production is also possible by reacting in substantially equivalent amounts.

A typical example of the unsaturated epoxy resin produced in (1) of the first method of the present invention is as shown in the following formula (4): CH
5CI (3 unsaturated epoxy resin, (A)) However, in the reaction of the epoxy resin and (meth)acrylic acid in an equal equivalent ratio, the following di(meth)acrylate is produced, instead of forming 1004 particles even in small amounts. At the same time, unreacted epoxy resin remains] A mixture of primary components (B), (C) and (4) is obtained.

H30 Vinyl ester resin (B) Hs Epoxy resin (C) If even a small amount of vinyl ester (B) is formed among these components, it will appear as crosslinking during polymerization, resulting in a side chain unsaturated bond type resin. It will no longer be possible to equip it.

Therefore, in order to prevent the formation of vinyl ester resin), it is necessary to increase the proportion of epoxy resin used in an equimolar amount to that of (meth)acrylic acid. The resin has the above-mentioned structure (A) and structure (
It becomes a mixture of C).

The presence of the residual epoxy resin (C), which does not initially participate in the reaction with (meth)acrylic acid, becomes useful for improving properties by later attaching a (meth)acryloyl group depending on the application.

The first method of the present invention is schematically shown as follows.

(1) First, a desired amount of (meth)acrylic acid and (meth)
An unsaturated epoxy resin is produced by reacting an epoxy resin in an excess equivalent ratio with respect to acryloyl groups using a necessary reaction catalyst such as a tertiary amine, amine salt, quaternary ammonium salt, or metal salt.

(11) Next, after adding the required type and amount of vinyl monomer, the acryloyl group of the unsaturated epoxy resin and the vinyl monomer are radically polymerized in the presence of an initiator such as azobisin butyronitrile. A reaction mixture containing a polymer having epoxy groups in the side chain is obtained.

010 Furthermore, add the required amount of (meth)acrylic acid,
By reacting the epoxy group remaining in the reaction mixture of (11) with the carzaxyl group, the desired polymer having a vinyl ester group in the side chain can be obtained.

There are no particular limitations on the epoxy resin used in the present invention.

For example, as a diglycidyl ether type of bisphenol A, 2pico) 827 from Yuka Shell Co., Ltd. is used.

828.834.1001, Dow ODER-330
.

331.332, GY-257 from Chipa Co., Ebikuron #840.850.810° from Dainippon Ink & Chemical Co., Ltd. Tobu Kasei Co., Ltd. Fu Epototo VD-115, -127, A, E, R330, 331 from Asahi Kasei Co., etc. can give.

A typical example of Nozarac's glycidyl ether type epoxy resin is DEN-431, 438 from Dow Company.

There are many types of cycloaliphatic epoxy resins in the literature, but in reality, Union Carbide's ERL
-4221 is commercially available and can also be used in the present invention.

In addition, as a special epoxy resin, Yuka Shell Co., Ltd.'s Y
A biphenyl type called X-4000 is also available.

A diglycidyl ether-coated I xy resin using bisphenol F and bisphenol S instead of bisphenol A, such as Epicor 807 type manufactured by Yuka Shell Co., Ltd., can also be used.

There is also a type in which alkylene oxide is added to bisphenol A and the terminal hydroxyl group is epoxidized with shrimp chlorohydrin.

(The following is a blank space) Among these, preferred epoxy resins are phenyl glycidyl ether type polyaddition homologs synthesized from bisphenol and shrimp chlorohydrin. Its general formula is shown, for example, as follows: (where n = O~5,
(R, , R2 are hydrogen or methyl groups) The most suitable type for the present invention is one in which n is about θ to 3 in both formulas.

The ratio of (meth)acrylic acid and epoxy resin when synthesizing the unsaturated epoxy resin (A) is 1:1 (meth)acrylic acid
Per mole (i.e. per equivalent of carboxylic group),
An epoxy resin having 2 or 3 or more glycidyl ether type epoxy groups in one molecule is used if there are 2 epoxy groups, 1 mol or more, and if there are more than 2 epoxy groups, 1 mol or more is used. However, it is necessary that the epoxy group has more than 2 equivalents. Preferably, (meth)acrylic acid is used in an amount of po, i to 0.5 equivalents per equivalent of epoxy group.

As the vinyl monomer used in combination with the unsaturated epoxy resin to form the polymer bone core, any vinyl monomer that can be copolymerized with a (meth)acryloyl group can be used.

Typical examples of these include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, inbutyl acrylate, tertiary butyl acrylate, and 2-acrylate.
Ethylhexyl, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, tetrahydrofurfuryl methacrylate, Examples include acrylonitrile, vinyl acetate, vinyl globionate, vinylidene chloride, and vinyl chloride. Copolymerization can be carried out by bulk polymerization, solution polymerization, alcohol polymerization, etc. In the case of bulk polymerization or solution polymerization, the polymer is used as it is in the next reaction with (meth)acrylic acid.

In the case of pearl polymerization, the resulting copolymer is dissolved in a monomer or solvent and then reacted with (meth)acrylic acid with the epoxy groups in the polymer.

When radical copolymerizing a mixture of an unsaturated epoxy resin and a vinyl monomer, known radical polymerization catalysts such as organic peroxides and azo compounds are used in combination.

Furthermore, the ratio of the (meth)acryloyl group to the vinyl monomer of the unsaturated epoxy resin is such that the ratio of the vinyl monomer is 99.
It can be varied over a wide range, such as 9 moles, and varies depending on the application, but generally between 95 moles and 96 to 50 moles is suitable.

In order to react the epoxy groups remaining in the polymer which has an epoxy resin group in the side chain obtained from the copolymerization reaction with the carboxyl group, the amount of (meth)acrylic acid added to the polymer depends on the epoxy component used in the previous step. Although it varies depending on the amount, it is preferable to use an amount that will cause substantially all of the remaining epoxy groups to react. That is, the amount of meth)acrylic acid per equivalent of remaining niboxy group is 0.9 to 1.
It is preferred to use 1 equivalent, preferably 0.95 to 1.05 equivalents.

The second method for producing the curable resin of the present invention is to use an unsaturated epoxy resin obtained by reacting an epoxy resin with (meth)acrylic acid and a copolymer of (meth)acrylic acid and a vinyl monomer. This is a method of causing a reaction.

What should be noted in the second method is that when producing the unsaturated epoxy resin, it is preferable to minimize the remaining amount of unreacted epoxy resin. If a large amount remains, it will cause dulling during the esterification reaction with the vinyl copolymer.

Therefore, the ratio of (meth)acrylic acid used needs to be as close to the epoxy equivalent as possible, but since unsaturated epoxy resins are used for esterification reactions rather than copolymerization reactions, one epoxy group remains in the molecule. Therefore, 0.5 to 0.1 g per equivalent of epoxy group in epoxy resin.
It is preferable to react an equivalent amount of (meth)acrylic acid.

In the second method, di(meth)acrylate resin is inevitably included, but since the original resin has excellent basic performance, it does not impair the performance of the resin of the present invention.

The second method of the present invention is schematically illustrated as follows.

(f) ffiffljLo epoxy resin and 0.5 to 09 g equivalent of (meth)acrylic acid to the epoxy resin are reacted using the reaction catalyst described in (1) above to produce an unsaturated epoxy resin. let The epoxy resin used here is the same as that described in the first method.

(b) A copolymer of vinyl monomer and (meth)acrylic acid is produced according to a conventional radical polymerization recipe. Examples of vinyl monomers include those exemplified in the first method. The ratio of vinyl monomer to (meth)acrylic acid can be varied widely within the range of 99 to 1 mole, but 99 to 50 mole is suitable.

(c) The unsaturated epoxy resin produced in (a) and the copolymer of (←) are reacted so that the epoxy groups and carboxyl groups are substantially equivalent. The reaction is similar to the first method.

The unsaturated alkyd used in the present invention is α・β
- An α/β-unsaturated polybasic product obtained by esterifying an unsaturated polybasic acid or its acid anhydride, or a mixture of this with a saturated polybasic acid or its acid anhydride, and a polyhydric alcohol. Examples of the acid or its acid anhydride include maleic anhydride, maleic acid, fumaric acid, and itaconic acid.

Examples of the saturated polybasic acid or its acid anhydride include phthalic anhydride, isophthalic acid, terephthalic acid, hexahydroheptalic anhydride, succinic acid, adipic acid, cepacic acid, and tetrachlorophthalic anhydride.

Although it has unsaturated bonds, it is not an unsaturated acid in the sense of α/β-unsaturated polybasic acids, but is a polybasic acid that is conventionally treated like a saturated acid. Examples include phthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and Hett's acid.

As the polyhydric alcohol, divalent to trivalent alcohols are used, and divalent glycol is usually preferably used. Typical examples include propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol,
1,6-hexanediol, hydrogenated bisphenol A,
Examples include bisphenol A-ethylene oxide adduct, bisphenol A-propylene oxide adduct, 1,4-cyclohexane dimetatool, trimethylolgulon, glycerin, and the like.

Esterification is carried out according to conventional methods.

The type of unsaturated alkyd cannot be determined simply because it depends on the physical properties required for the product.

Unsaturated alkyds can be used in combination with copolymerizable monomers if necessary, and for most applications it is preferable to use monomers in combination, but for applications such as molding materials and decorative laminates, Monomers may not be used together. Examples of copolymerizable monomers include styrene, vinyltoluene, methyl methacrylate, diallyl phthalate, and the like.

The mixing ratio of the side chain unsaturated bond type resin and the unsaturated alkyd cannot be determined unconditionally as it varies depending on the performance required for the product, but in general, the side chain unsaturated bond type resin is 5 to 95%.
% by weight, preferably 20-80% by weight, and 95-5% by weight, preferably 80-20% by weight of unsaturated alkyd. Outside this range, the remarkable effects of the present invention cannot be obtained.

In the present invention, a polymerizable monomer may be further added to the composition consisting of the side chain unsaturated bond type resin and the unsaturated alkyd, if necessary.

Examples of polymerizable monomers include styrene, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, and polypropylene glycol diacrylate. , propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane diacrylate.

Examples include trimethylolpropane diacrylate, trimethylolpropane trimethacrylate, pentaerythrit triacrylate, pentaerythrittetraacrylate, pentaerythritol trimethacrylate, four-tentaerythrittetramethacrylate, and these may be used in combination. good. The blending amount of the polymerizable monomer is a mixture of side chain unsaturated bond type resin and unsaturated alkyd.
The amount is preferably 10 to 60 parts by weight per 00 parts by weight.

The curable resin composition of the present invention can be cured by a conventionally known method.

That is, in order to cure the curable resin composition of the present invention, an organic peroxide such as benzoyl peroxide, methyl ethyl ketone monooxide, cumene hydrochloride, monooxide, etc. is added and the composition is heated and cured. You can also
Alternatively, a photosensitizer such as benzoin, benzyl, benzophenone, 2-hydroxy-3-benzoylpropane, benzoin methyl ether, etc. may be added for ultraviolet curing. In addition, organic peroxides and organic acid salts of cobalt (e.g. cobalt naphthenate), aromatic tertiary amines (
For example, it may be cured at room temperature using an accelerator such as trimethylaniline).

A reinforcing material, a filler, a coloring agent, a mold release agent, etc. may be added to the curable resin composition as necessary.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, "part" and "chi" in the examples mean "part by weight" and "weight jltsJ", respectively, unless otherwise specified.

Example 1 (1) Synthesis of side chain unsaturated bond type resin (4) Production of unsaturated epoxy resin (&) IJI-t with a stirrer, a thermometer with a gas introduction tube, a reflux condenser, and a dropping funnel. In a flask, 3607-(1 liter) of Mitsubishi Yuka-Ciel's Epicote 827 was added as an epoxy resin, and methacrylic acid 43iP (0,5 liter) was added.
%), benzyldimethylamine 1,2? , prepared with benzoquinone O,OS iP, 120-130
After reacting for 3 hours under air blowing conditions at °C, the acid value was almost zero, and unsaturated epoxy resin (a) was obtained in the form of pale reddish brown silag.

For resin (&), the following formula (1) is calculated as 223? And free engineering resin 180? It is a mixture of

Side chain worker? Synthesis of methyl ethyl keto 7250t1 unsaturated epoxy resin (a) 173j' (0.2 mol), styrene 100P, azobisisobutyronitrile 3,5 I
Styrene 87P (total styrene amount: 1.8 mol) was added dropwise at 75° C. in a nitrogen stream.

After 6 hours, add 2 more azobisisobutyronitrile? was added, and the polymerization was further continued for 10 hours.

When the polymerization rate reached 961, hydroquinone 0.27
was added to stop the polymerization.

A methyl ethyl ketone solution (solid content: 40%) of the side chain epoxy resin was obtained in the form of a pale yellowish brown liquid.

As a result of the APC analysis, a polymer having a peak at a molecular weight of approximately 50,000 and a resin which is a mixture of unreacted Nixi resin were confirmed.

Synthesis of side chain unsaturated bond type resin) Methacrylic acid 52/- (0.60 mol) was added to the entire amount of the methyl ethyl ketone solution of the above-mentioned side chain unsaturated bond type resin.

When triphenylphosphine is charged with 0.8 Pt and reacted for 16 hours at the boiling point of methyl ethyl ketone, the acid value is 1.0.
．． After adding 420 iP of styrene monomer, the mixture was heated under reduced pressure of 400 to 450 lHg to remove methyl ethyl ketone.

After about 6 hours, gas chromatography analysis showed that the concentration of methyl ethyl ketone was 0.3, so when heating was stopped, the side chain unsaturated bond type resin (A) was yellowish brown and had a viscosity of 1.9.
Obtained with Poise.

(2) Synthesis stirrer for unsaturated polyester resin,
Bisphenol A-fa pyrene oxide adduct (1 mole of propylene oxide added to both ends) was placed in a 1-size four-tube flask equipped with a fractionating condenser, thermometer, and gas inlet tube. .

Prepare fumaric acid 116P, 210-2 in nitrogen gas stream
Esterification was carried out at 20°C. Hydroquinone 0.05 when the acid value reaches 35.4? was poured into a metal vat and cooled to obtain an unsaturated alkyd with a yellowish brown color and a melting point of about 80°C.

300 parts of pulverized unsaturated alkyd and 300 parts of styrene were heated at 50 to 60°C while stirring in a Mitsuro flask.
By heating and dissolving the resin, an unsaturated polyester resin (B) having a yellowish brown color and a viscosity of 4.7 poise was obtained.

Add 2 parts of methyl ethyl ketone peroxide, 1 part of cobalt naphthenate, and 0.1 part of dimethylaniline O to 100 parts of the side chain unsaturated bond type resin (4), the unsaturated I-lyester resin (B), or a mixture thereof. 300 parts mX 300ffl! ×
The physical properties of the cast product obtained from the composition of the present invention are as shown in Table 1, and the physical properties of the cast product obtained from the composition of the present invention are as follows: The physical properties were well balanced and superior to those of cast products made of , or unsaturated polyester resin (B) alone.

The coating film hardness is the value obtained by coating the composition on a glass plate with a bar coulter to a thickness of 0.2 and curing it.

Example 2 (1) Synthesis of side chain unsaturated bond type resin (Q) Acrylic acid 72?
, bisphenol A228P (1 mol), 85 (1' (2.5 mol)) of φ332 manufactured by Asahitsu Co., Ltd. as an epoxy resin, triphenylphosphine 4j', and 0.4 P of t-butylhydroquinone, 120 ~ 4 at 130℃
After reacting for a period of time, a resinous unsaturated IdP resin (c) having an acid value of 8.1, a pale yellowish brown color, and a softening point of 40° C. was obtained.

600 J' of unsaturated engineering I xy resin (,), 200 J' of ethyl acrylate, 26 M' of styrene, 10 JF of azobisisobutyronitrile, 800 J' of methyl ethyl ketone in a 3 J' equipped with a stirrer, a reflux condenser, a thermometer, and a gas introduction pipe. The mixture was charged into a Yotsuro flask and polymerization was continued for 16 hours under reflux of methyl ethyl ketone in a nitrogen stream, and the polymerization rate reached 94.

Polymerization was stopped by adding 0.51 P of hydroquinone, and a side chain epoxy resin (j) was obtained in the form of a brown liquid.

Acrylic acid 72f (1 mol) was added to the entire amount of the side chain epoxy resin (d) described above, and triphenylphosphine was added to 2
When the mixture was reacted for 26 hours at the boiling point of methyl ethyl ketone, the acid value was 1.4, and infrared analysis confirmed that the nixyl group had disappeared. The obtained methyl ethyl ketone solution of the side chain unsaturated bond type resin (B) was yellowish brown and had a viscosity of about 30 poise.

(2) Synthesis of unsaturated I-lyester resin (b) In a four-cylinder flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas inlet tube, Neopear f glycol 230j',
Charge 23 LP of isophthalic acid and heat under nitrogen gas flow for 20 LP.
Esterification was carried out at 0-210°C. Acid value is 21.7
When it reaches 78 itaconic acid? was added, further esterification was carried out until the acid value reached 39.7, and the temperature was increased to 150.
After lowering the temperature to ℃, 0.08P of hydroquinone and 200/- of trimethylolpropane triacrylate were added, followed by 132P of methyl methacrylate, which was uniformly dissolved to form an unsaturated polyester with a Gardner color number of 2 and a viscosity of 24.9 poise. Resin (2) was synthesized.

1 part of a photoinitiator (Irugaki Eana 651 manufactured by Chipa) was added to 100 parts of a resin in which side chain unsaturated bond type resin (C) and unsaturated polyester resin were mixed in the ratio shown in Table 2. Masking tape was applied to both ends of a bonderite-treated steel plate with the composition applied, and then a polyethylene terephthalate film having a thickness of 100 μm was adhered and defoamed using a roll.

The thickness of the coating film was determined by the thickness of the masking tape, and in this case was 70μ.

This was cured by passing through 20 cIrL under the rung at a speed of 15 m/min using an ultraviolet irradiation device with an output of 30 kW.

The physical properties of the obtained coating film are shown in Table 2, and the physical properties of the resin composition of the present invention are those of the side chain unsaturated bond type resin (C).
It was found that the physical properties were better than those of the unsaturated polyester resin ρ) alone or the unsaturated polyester resin ρ) alone.

Example 3 (1) Synthesis of side chain unsaturated bond type resin (g)) 3L of methacrylic acid 48P (0.55 mol) and styrene monomer 600? .

Methyl ethyl ketone 4007. t-dodecyl mercaptan 2. P, azobisisobutyronitrile 4? Prepare
Polymerization was carried out at 75°C for 15 hours. Hydroquinone 0.2
1 was added to inhibit polymerization. The polymerization rate of styrene monomer was 88%, and the polymerization rate of methacrylic acid was 98%.

An evaporation operation was performed while adding styrene monomer to remove methyl ethyl ketone at 60° C. under reduced pressure.

Methyl ethyl ketone was removed until it became 0.1% by weight or less in the evaporation distillate. The resulting liquid had a non-volatile content of about 60% by weight.

Synthesis of unsaturated epoxy resin (f) Novolac type epoxy resin DEN-431 (manufactured by Dow Chemical Company) 356? in an IL glass autoclave. (2 epoxy equivalents), 130 t (1.5 mol) of methacrylic acid,
1.27-pendel dimethylamine and 0.1' 6 P of parabenzoquinone were charged, and the mixture was reacted at 110°C for 90 minutes. The acid value was approximately 2. The general composition of the obtained unsaturated epoxy resin (f) was as follows.

Unsaturated epoxy resin 218P divinyl ester resin 266P methacrylic acid
2P and others 1? Styrene monomer 300 in the above liquid? was added to prepare it for the next reaction.

Synthesis of side chain unsaturated bond type resin (f) Diluted with styrene monomer to obtain unsaturated resin solution (f)
) was washed with styrene in a 3L glass autoclave containing the side chain caldic acid polymer (, ), and the entire amount was transferred to 7'.
j. Triphenylphosphine 5i! '', 0.54 P of rosebenzoquinone was added, and the mixture was reacted at 120° C. for 90 minutes.

Styrene monomer 880P side chain unsaturated bond type resin 870? vinyl ester resin
266 The resin liquid with the above composition has a temperature of 15.9r (25°C).
) was a yellow-brown transparent liquid.

(2) Synthesis stirrer for unsaturated polyester resin (F'),
Into 11 four-eye flasks equipped with a fractionating condenser, a gas inlet tube, and a thermometer, 250 g of propylene glycol, 291 g of trimethyl terephthalate, and 2.5 g of zinc acetate were charged, and methanol was added at 180 to 200°C. Transesterification reaction was carried out while distilling. At the stage when about 99 cc of methanol was distilled off, 147 m of maleic anhydride was added, and esterification was continued at 190 to 200°C in a nitrogen gas stream, and the reaction was stopped when the acid value reached 34.4. did. After lowering the temperature to 150 °C, hydroquinone 0,0
6y-, poured into a stainless steel vat, and cooled.

The unsaturated alkyd obtained is pale yellowish brown and has a softening point of about 75.
It was ℃.

100 parts of unsaturated alkyd and 100 parts of ethyl acetate were obtained.

To 100 parts of resin mixed with side chain unsaturated bond type resin (odor and unsaturated ester resin solution V) in the proportions shown in Table 3, 3 parts of titanium white and 0.5 parts of tertiary butylhydride or monooxide were added. 0.05 parts of naphthenic acid conoglu) and 5 ppm of silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., KF-9610 centistokes). After applying it to a steel plate treated with Ndellite so as to have a coating thickness of 0.2 rnttr, it was baked at 80° C. for 30 minutes and at 120° C. for 30 minutes to form a coating film.

The physical properties of the obtained coating film are as shown in Table 3, and the physical properties of the resin composition of the present invention are as follows: The physical properties of solution 1'F') were superior to those used alone.

〔Effect of the invention〕

Since the curable resin composition of the present invention uses a side chain unsaturated bond type resin having a (meth)acryloyl group at the end of the side chain via an epoxy resin residue, it has heat resistance, water resistance,
It has excellent adhesion and mechanical strength, and has good curing properties, making it extremely useful for various uses such as paints, adhesives, molding materials, cast products, and FRP.

Claims (1)

[Claims] 1. (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, A is a main chain consisting of a copolymer resin of a vinyl monomer and an acryloyl group or a methacryloyl group,
R is hydrogen or a methyl group, and Y is the residue of an epoxy resin in which the epoxy group in the molecule forms an ester bond through a ring-opening addition reaction with a carboxyl group, from which the ester bond is removed. a chain unsaturated bond type resin and (B) an α,β-unsaturated polybasic acid or its acid anhydride;
Alternatively, a curable resin composition containing an unsaturated alkyd obtained by esterifying a mixture of this and a saturated polybasic acid or its acid anhydride with a polyhydric alcohol. 2. The curable resin composition according to claim 1, further comprising a polymerizable monomer added to the curable resin composition.