JPS62209121A - Production of curable resin - Google Patents

Abstract

PURPOSE:To obtain the titled novel resin useful as coating compounds, etc., having improved heat resistance and mechanical strength safely and readily, by reacting an epoxy resin-phenol addition product with a diisocyanate and reacting the resultant compound with an unsaturated hydroxyl compound. CONSTITUTION:(A) (i) An epoxy resin-phenol addition product containing two or more hydroxyl groups and two or more allyloxymethylene groups obtained by adding monohydric phenols to the epoxy groups of an epoxy resin containing two or more epoxy group and (ii) a diisocyanate are subjected to addition reaction in the presence of (iii) both a radically polymerizable monomer and a polymerization inhibitor in such a way that the amount of the isocyanate group of the component ii is substantially 2 equivalents based on 1 equivalent hydroxyl group of the component i to give an isocyanate addition resin and the component A is reacted with (B) an unsaturated hydroxyl compound containing one or more unsaturated group and one or more hydroxyl groups in one molecule or a resin to give the aimed compound shown by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a radically curable resin having a novel structure useful for various uses such as paints, adhesives, molding materials, and F'RP.

[Conventional technology]

Currently, as radical-curing resins that can be cured at room temperature, unsaturated polyester resins and vinyl ester resins (
Epoxy acrylate resins) are the most representative, and they are used in a wide variety of fields, taking advantage of their respective characteristics.

However, as the applications expand, the performance required of the resin becomes more detailed and sophisticated, and it may be difficult to satisfy these demands with conventional resins.

For example, taking heat resistance as an example, as long as styrene is used as a crosslinking agent, its practical range in terms of heat distortion temperature is at most 120°C, and it cannot be used for applications that require higher temperatures. Can not.

Although there are special highly reactive resins that are heat resistant and have a heat distortion temperature of 130 to 150°C, they do not have sufficient properties such as mechanical strength and pose problems for practical use. Sometimes it happened.

[Problem that the invention seeks to solve]

In view of the above situation, the inventors of the present invention have conducted various studies in order to industrially easily produce high-performance resins that exceed the physical properties of existing resins, particularly vinyl ester resins, and have discovered a new resin with excellent heat resistance and mechanical strength. Structure [Another means to solve the problem] That is, the method for producing a curable resin of the present invention involves an addition reaction of monohydric phenols to the epoxy group of an epoxy resin having two or more epoxy groups in one molecule. An epoxy resin-phenol adduct each having two or more hydroxyl groups and allyloxymethylene groups in one molecule obtained by this process and a diisocyanate are combined in the presence of a radically polymerizable monomer and a polymerization inhibitor. , the addition reaction is carried out so that the isocyanate groups of the diisocyanate are substantially 2 equivalents per 1 equivalent of hydroxyl groups of the adduct, so that two or more isocyanate groups and allyloxymethylene groups are each produced in one molecule. A covalent isocyanate addition resin is produced, and then the addition resin is reacted with an unsaturated hydroxyl compound or resin that shares one or more unsaturated groups and hydroxyl groups in each molecule. It is.

[Effect]

First, in order to facilitate understanding of the present invention, the flow of the method for producing the curable resin of the present invention using representative examples will be shown using chemical structural formulas.

Epoxy resin-phenol adduct containing two or more hydroxyl groups and allyloxymethylene groups each in one molecule (blank below). Incyananito addition renon (B) An unsaturated hydroxyl compound that shares one or more unsaturated groups and a hydroxyl group in each molecule (blank below) Self 8=8 By reacting a vinyl ester resin with a twisocyanate,
It is known to link vinyl esters together.

Compared to this method, the advantages of the present invention can be summarized as follows.

(a) Resin synthesis can be performed safely.

When a small amount (several positions) of diisocyanate is reacted with a vinyl ester, it is difficult to react, and when there is a large amount of diisocyanate as a whole, such as when one molecule of vinyl ester is reacted with 0.5 to 1 molecule of diisocyanate. Although the reason is not clear, it becomes dull and cannot be successfully synthesized into a resin.

However, according to the present invention, resins can be synthesized safely even with the same diisocyanate usage ratio.

(b) Physical properties are improved.

Compared to the case where vinyl ester resins are directly reacted with diisocyanate, physical properties are improved in almost all respects. In particular, in the curable resin of the present invention, a hard, bulky group such as an allyloxymethylene group is introduced into the side chain, so physical properties such as heat resistance and hardness are significantly improved.

(c) The raw materials can be varied widely and the properties can be changed accordingly.

For example, the structure can be changed by changing the type of phenol.

Epoxy resin-phenol adducts (hereinafter referred to as (
4) The component (sometimes referred to as component) is made by reacting monohydric phenols with an epoxy resin having two or more epoxy groups in one molecule so that the epoxy groups and phenolic hydroxyl groups are substantially equimolar; It is produced by converting an epoxy group into an alcoholic hydroxyl group and introducing an allyloxymethylene group.

At this time, reaction catalysts such as quaternary ammonium salts, aliphatic tertiary amines, trisdimethylaminophenol, salts of secondary amines, sulfonium salts, phosphorium salts, and triphenylphosphine are used for the reaction between epoxy groups and phenolic hydroxyl groups. The necessary amount (generally 0.1 to 1
phr) Must be used together.

The reaction is smoothly carried out at 120-160°C. The end point of the reaction is determined by infrared analysis based on the disappearance of epoxy groups.

As an example of the epoxy resin used, it is desirable to use a type that does not have many free hydroxyl groups.

Examples include Eva, diglycidyl ether type of bisphenol A, such as Epicor 827゜828 from Yuka Shell, DER-330, 331, 332 from Dow, and GY-2 from Chipatsuji.
57 etc.

Representative examples of the novolak glycidyl ether type epoxy resins include DOW's DEN-431 and 438.

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 diglycyl sol ether type epoxy resin using bisphenol F instead of bisphenol A, ie, Epicoat 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 phenol to be reacted with the epoxy resin is not particularly limited, except that it is a monohydric phenol. An example is the following.

Phenol so-cresol, m-cresol, p-
Cresol, 2,3 xylenol, 2,4 xylenol, 2,5 xylenol, 2,6 xylenol, 3.4 xylenol, 3,5 xylenol, noliisozorobylphenol, noglatt-butylphenol, noj
laoctylphenol, paranonylphenol, paraphenylphenol, noclacumylphenol, α-naphthol, β-naphthol, 2.5-・sibromophenol, 2,6-di-t-butyl-1-hydroxytoluene, 2.6- - Sheet-t-butyl-1-hydroxyanisole.

It is desirable that the reaction ratio between the epoxy group and the phenolic hydroxyl group is substantially 1:1.

Examples of the diisocyanate (hereinafter sometimes referred to as component (B)) used as the second component in the method of the present invention include the following types.

2.4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, ・diphenylmethane diisocyanate, norya-phenylene diisocyanate, 1,5-naphthylene diisocyanate , 1,6 hexamethylene diisocyanate, inphorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate.

The addition reaction between component (A) and component (B), that is, the reaction between the epoxy resin-phenol adduct and the diisocyanate, is as follows:
By carrying out the reaction in the presence of a radically polymerizable monomer and a polymerization inhibitor, there are advantages in that gelling, which tends to occur when diisocyanates are used, is prevented and the reaction can be easily controlled. Furthermore, the use of a polymerizable monomer has the advantage that it can be directly used for curing without problems such as solvent recovery when using a solvent.

The radically polymerizable monomers that can be used in the present invention include component (4), component (B), component (A), and (
B) Addition reactant with component (isocyanate addition resin)
It is selected from the viewpoint of improving the hardness and heat resistance of the cured product after curing, but at the same time, since the curable resin of the present invention is solid, it is inconvenient to mold and cure it as it is. Therefore, it is used for the purpose of dissolving it and making it easier to handle.

Practically preferable radically polymerizable monomers include methyl methacrylate, ethyl methacrylate, inbutyl methacrylate, n-butyl methacrylate, inbutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, benzyl methacrylate, and cyclohexyl. Methacrylate, phenoxyethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hensyl acrylate, phenoxyethyl acrylate, ethylene glycol no methacrylate, no ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neonin Examples include (meth)acrylic acid esters such as tylglycol dimethacrylate, 1,6-hexanesiol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate, and aromatic vinyl compounds such as styrene and vinyltoluene. It will be done. Two or more of these monomers may be used in combination.

Among these radically polymerizable monomers, styrene and methyl methacrylate are most preferably used.

The amount of radically polymerizable monomer to be used requires a place to dissolve the three components mentioned above, and the amount varies depending on the type of individual monomer, but it is usually about 100 parts by weight of the solid resin. It is used in a range of 0.1 to 2 times.

The polymerization inhibitor used in the present invention is used to prevent the radically polymerizable monomer from polymerizing during the reaction between the component (4) and the component (B). Examples include hydroquinone, benzoquinone, toluhydroquinone, trimethylhydroquinone, and tolbenzoquinone. It is usually used in an amount of 0.005 to 0.5 parts per 100 parts by weight of the monomer-dissolved resin.

Component (4) and component (B) are reacted at a ratio such that the amount of isocyanate groups in component B is substantially 2 equivalents per 1 equivalent of hydroxyl group in component (4), so (B) One of the isocyanate groups in the component undergoes an addition reaction with a hydroxyl group to form a urethane bond, but the other isocyanate group remains unreacted. Therefore, the produced isocyanate-added resin shares two or more allyloxymethylene groups and isocyanate groups via urethane bonds in each molecule.

Unsaturated hydroxyl compounds or resins (hereinafter referred to as (C
) component) is a saturated or unsaturated monoepoxy compound or epoxy resin having one epoxy group in one molecule, and acrylic acid or methacrylic acid (hereinafter referred to as (meth)acrylic acid). It is produced by reacting an epoxy group and a carboxyl group so that they have substantially equivalent weights.

Examples of saturated monoepoxy compounds include, for example, phenyl glycidyl ether, cresyl glycidyl ether, 2
, 5-dibromucresylglycidyl sol ether, styrene oxide, propylene oxide, ethylene oxide, butylene oxide, butylglycidyl ether, and the like.

Examples of the unsaturated monoepoxy compound include glycysol methacrylate, glycidyl acrylate, allyl glycidyl ether, and the like.

As for the epoxy resin used in the production of component (C), the types mentioned above are of course suitable, but it is also possible to expand the range of types and use types having one or more hydroxyl groups, that is, types with a molecular weight in the range of 350 to 2,500. It is.

For the reaction between the saturated or unsaturated monoepoxy compound or epoxy resin and (meth)acrylic acid, the reaction catalyst used in the reaction system of the phenol and the epoxy resin described above is used as a catalyst.

At this time, it is necessary to use a polymerization inhibitor typified by polyhydric phenols to prevent the reaction from occurring during the reaction.

Of course, commercial products such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, which are reaction products of a monoepoxy compound and (meth)acrylic acid, can also be used as component (C') of the present invention. Furthermore, commercial vinyl ester resin (epoxy acrylate), which is a reaction product of epoxy resin and (meth)acrylic acid, is also available (C).
Of course, it can be used as a component.

In the reaction between the isocyanate-added resin and component (C), 1 hydroxyl group in component (C) per 1 equivalent of isocyanate group.
The amount is equivalent or more and is selected as necessary.

A proportion of hydroxyl groups of 2 equivalents or more means that there may be a free component (C) that does not participate in the reaction, but it is included in the present invention as long as this amount does not account for the main component.

The reaction between the isocyanate-added resin and the component (0) can be smoothly carried out in the radically polymerizable monomer used in the above reaction. In addition, component (C) may be used alone, or two or more compounds or resins may be used in combination.When component (C) is used in combination, it may be saturated or unsaturated. When a saturated monoepoxy compound or epoxy resin is reacted with (meth)acrylic acid, 2
Can be produced simultaneously by using more than one species,
By using it, it is possible to obtain a curable resin having excellent physical properties such as heat resistance and strength.

It goes without saying that the resin curable by the method of the present invention may contain fillers, reinforcing materials, colorants, mold release agents, polymers, etc., if necessary.

〔Example〕

Next, in order to assist in understanding the present invention, examples are shown below.

Example 1 Production of epoxy resin-phenol adduct CI) Stirrer,
In a No. 11 Mitsuro flask equipped with a reflux condenser and a thermometer, 360 g of Epicoat 827 from Yuka Shell Epoxy Co., Ltd. as an epoxy resin and 188 g of phenol were added. ! When 1.5 g of trimethylbennolammonium chloride (i+) was charged and the temperature was raised, heat rapidly generated when the temperature exceeded 120°C.

Cool and keep at 150-160℃, then reheat for 15 minutes.
After reacting at 0 to 160°C for 5 hours, infrared analysis showed that free epoxy groups had completely disappeared.

Epoxy resin-phenol mixture cooled to room temperature
It was light yellowish brown and sill-like.

Production of isocyanate adduct [■] In a similar apparatus, add 550 g of adduct [■] and Styrene Y25.
Weigh out 0.9-”labenzoquinone 0.01.!i′,
After heating and dissolving at 60-70°C, 350 g of 2.4-) rylennoinquanate was added and reacted at 60°C for 5 hours. As a result of analysis by di-n-butylamine-hydrochloric acid titration, the isocyanate group was dissolved. It was observed that the content of the system was reduced by almost half from 4% to 1.8%.

Add 250p of styrene and add isocyanate adduct Cl
1) was obtained as a pale yellowish brown liquid.

Production of unsaturated hydroxyl compound [■] In an IJE Tulo flask equipped with a stirrer, reflux condenser, and thermometer, 300 g of phenyl glycidyl ether and 17 g of methacrylic acid were added.
21 Triphenylphosphine 2g, -hydroquinone 0.2. ! After heating and reacting at 120-130℃ for 3 hours, the acid value was 4.1, so styrene 26
0y was added to produce an unsaturated monohydroxyl compound [■] (styrene solution).

Preparation of curable resin [A] The entire amount of the isocyanate adduct [■] and 730 I of the unsaturated monohydroxyl compound (In) (styrene solution) are transferred to a 31-meter flask equipped with a stirrer, a reflux condenser, and a thermometer.

After raising the temperature to 60°C, 4 g of dibutyltin dilaurate was added and the mixture was reacted at 60°C for 3 hours. As a result of infrared analysis, it was confirmed that the isocyanate group had disappeared.

Furthermore, 585g of styrene was added to make a curable resin [A]
was obtained with a reddish brown color and a viscosity of 5.4 poise.

A system in which 100 parts of resin [A] was mixed with 1.5 parts of Su 328E from Kayaku Nouri Co., Ltd. as a hardening agent and 0.3 parts of naphthi/cobalt acid was glued in 22 minutes, rapidly generating heat and reaching the maximum temperature. reached 160°C.

The physical properties of the cured resin were as follows.

Bending strength 16.7 kll/mtr2
Heat distortion temperature 121°C Rockwell hardness M-113 Charpy impact value 3 kgc5m2 Example 2 Production of unsaturated hydroxyl compound CIV) 1 equipped with a stirrer, reflux condenser, and thermometer! In the Mitsuro flask,
Glycidyl methacrylate 284g, methacrylic acid 17
2g, triphenylphosphine 2g, hydroquinone 0
．． 29 was charged and heated and stirred at 120 to 130°C for 5 hours, the acid value became 11, so styrene 244y was added to produce unsaturated monohydroxyl compound (IV) (styrene solution).

Production of curable resin CB] To the entire amount of isocyanate adduct [11], add 700 J of unsaturated hydroxyl compound CIV:] (styrene solution),
Transfer to a 31-meter flask equipped with a stirrer, reflux condenser, and thermometer.

After raising the temperature to 60°C, 4 g of dibutyltin dilaurate was added and the mixture was reacted at 60°C for 3 hours. As a result of infrared analysis, it was confirmed that the isocyanate group had disappeared.

Furthermore, add 600g of styrene to make a curable resin [B]
was obtained with a reddish brown color and a viscosity of 3 voids.

A system in which 100 parts of resin CB was mixed with 1.5 parts of φ328E from Kayaku Nouri Co., Ltd. as a curing agent and 0.3 parts of cobalt naphthenate was cured in 15 minutes and rapidly generated heat, reaching a maximum temperature of 161°C. reached.

The physical properties of the molded resin are: bending strength: 14.6 kg7m2; heat distortion temperature: 131°C; Rockwell hardness: M-115; Charpy impact value: 2.7 mm et al.2; it is hard, but has high heat resistance and strength. revealed.

The epoxy resin-phenol adduct [I] was produced in a similar device to the production of the isocyanate adduct [v].
350g, styrene 150g, rosebenzoquinone 0.
After weighing 01g and dissolving it by heating at 60 to 70°C, 2,
Add 220g of 4-tolylene diisocyanate and heat to 60°C.
After reacting for 5 hours at
．． It was observed that the number had decreased by almost half to 6%.

Add styrene 130.9 and add isocyanate adduct [
(2)] was obtained in the form of a pale yellowish brown liquid.

Production of vinyl ester m [M”] In a 11-three flask equipped with a stirrer, a reflux condenser, and a thermometer, the above-mentioned Epicoat 82 was added as an epoxy resin.
7, 172y of methacrylic acid, 0.2g of hydroquinone, and 1.5g of )limethylbenzolammonium chloride were charged and reacted for 3 hours with vigorous stirring at 120 to 130°C, resulting in an acid value of 5.9.

Added 230 g'e of styrene, vinyl ester resin CVD
was obtained as a reddish brown liquid.

Production of curable resin CC''l 430 g of isocyanate adduct [■] and vinyl ester resin CM) 760.9 were charged into a 2!3 flask equipped with a stirrer, a reflux condenser, and a thermometer, and the temperature was 60.
℃, dibutyltin dilaurate 2. ! i'
? In addition, when reacting at 60°C for 3 hours, as a result of infrared analysis,
Free isocyanate groups had completely disappeared.

410 g of styrene was added to obtain a curable resin with a reddish brown color and a viscosity of 9.7 poise.

A system in which 100 parts of resin [C], 1.5 parts of ÷328E from Kayaku Nouri Co., Ltd. as a curing agent and 0.5 parts of cobalt naphthenate was added was cured in 29 minutes and rapidly generated heat after being cured. Gave.

Its properties are: Bending strength: 16.7 Yu/+2 Flexural modulus: 460 Yu/Bleaching: 2 Charpy impact value
3.7 Yu・cm/cm2m/form temperature
127°C Rockwell hardness was M-113.

Comparative Example 1 Vinyl ester resin [: ■] 760 in the same packaging ff
174 g of 2,4-tolylene diisocyanate (containing equimolar isocyanate groups as the isocyanate adduct [■]) was added to 1.
When 6 g of the resin was added, the resin was converted into a resin after about 3 minutes, and a practically usable resin was not obtained.

Example 4 2j Seno! equipped with a stirrer, reflux condenser, and thermometer.
The epoxy resin produced in Example 1 was placed in a rubble flask.
550 g of phenol adduct CD, 330.9 g of hexamethylene diisocyanate. Styrene 420g, Cerabenzoquinone 0.2g, Diptyltin dilaurate 4.5g
After preparing a homogeneous solution, it was reacted at 60°C for 5 hours.

As a result of infrared analysis, it was estimated that the absorption of isocyanate was reduced by almost half.

The obtained isocyanate adduct [■] was obtained in the form of a reddish brown liquid.

Preparation of unsaturated hydroxy compound [■] Into a separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 150.
p, 86 g of methacrylic acid, 70 g of triphenylphosphine.
Add 5/i and 0.051 hydroquinone, 12
When reacted at 0-130°C for 3 hours.

The acid value was 8.1, so styrene/164. Add ji+ and unsaturated hydroxy compound [■] (styrene solution)
was obtained as a light reddish brown liquid.

Production of curable resin (D) In a 3J Mitsuro flask equipped with a stirrer, reflux condenser, and thermometer, add isocyanate adduct [■] 1,300
g, 760 g of vinyl ester resin [■], 400 g of unsaturated monohydroxy compound [■], 0.2 g of rosebenzoquinone, dibutyltin dilaure (5.9) were added, and when reacted at 60°C for 8 hours, infrared As a result of analysis, it was confirmed that free isocyanate groups had completely disappeared.

500 g of styrene was added to obtain a curable resin (D) having a reddish brown color and a viscosity of 7.1 voids.

A mixed system in which 1.5 parts of 328E and 0.3 parts of copal naphthenate were added to 100 parts of resin glued in 14 minutes and rapidly generated heat, reaching a maximum exothermic temperature of 162°C.

The main physical properties of the cast product were as follows, and a hard and tough resin was obtained.

Bending strength 16.9 ψj2 Shalpy @ Impact value 3.9 'K1cm/cm2 Heat distortion temperature 119℃ Rockwell hardness M-113 Example 5 Production of unsaturated hydroxyl resin CIX) Equipped with a stirrer, reflux condenser, and thermometer 11 In a three-piece flask, as an epoxy resin, 370 g of bisphenol A-)glycidyl ether with an epoxy equivalent of 185, glycysol methacrylate 1429, 258 g of methacrylic acid, 2.5 g of pennoldimethylamine, and 0.0 g of hydroquinone were added.
Styrene 230 was charged and reacted for 4 hours at 125-130°C in an air stream, and the acid value became 8.1.
g and reddish brown liquid unsaturated hydroxyl resin (I
X) was obtained.

Production of isocyanate adduct [X] Epoxy resin-phenol adduct C was placed in a 31-cell rubble flask equipped with a stirrer, a reflux condenser, and a heating device.
540g of D, 260g of styrene, rosebenzoquinone o
, oig, were weighed and made into a homogeneous solution, 2. When 350 g of '4-tolylene diisocyanate was added and reacted at 60°C for 5 hours, it was estimated that the isocyanate concentration was reduced by approximately half as a result of infrared analysis.

The obtained isocyanate adduct [X] was a yellowish brown liquid.

Preparation of curable resin [E] To this, add the entire amount of unsaturated hydroxyl resin [■] (styrene solution), and further add 5 g of dibutyltin dilaurate and 0.3 g of grabenzoquinone.
After reacting at ℃ for 5 hours, infrared analysis showed that free isocyanate groups completely disappeared. 1170 g of styrene was added, and the curable resin [E] was reddish brown and had a viscosity of 5.9 poise. Obtained.

To 100 parts by weight of resin (E), 328 from Kayaku Nury Co., Ltd.
The system to which 1 part of E and 0.2 part of cobalt naphthenate was added was glued in 6 minutes and rapidly generated heat, reaching a maximum temperature of 166°C.

The physical properties of the cured resin were as follows.

Bending strength 15.9kg/+2 Heat deformation temperature 136℃ Rockwell hardness M-116 Shall-Impact value 2.4 kgcIn/crn
2 Example 6 Production of epoxy resin-xylenol adduct (XI) A novolak type epoxy resin was prepared using 1) EN -
431 to 36 (add 270 g of 1,2,6-xylenol and 2 g of benzyldimethylamine, and heat at 150 to 160°C.
After reacting for 3 hours, infrared analysis confirmed that free epoxy groups had disappeared.

Further, 0.1 g of styrene 37051, )/hydroquinone was added to obtain an epoxy resin-xylenol adduct [X] in the form of a pale reddish brown liquid.

Production of isocyanate adduct [Kari] Panoramic view of adduct [X] cooled to around room temperature, further diphenylmethane diincyaner) 500J, styrene 330
When the temperature was raised to 60° C. for 5 hours, the same analysis as in Example 1 revealed that the isocyanate value was reduced by almost half.

The isocyanate adduct [X] was obtained in a pale reddish brown liquid state.

Preparation of curable resin [F] Transfer the entire amount of isocyanate adduct CXI) to a 31-meter flask equipped with a stirrer, reflux condenser, and thermometer, and then add 288 g of 2-hydroxyglobyl methacrylate.
, dibutyltin dilaurate 3g pescizoquinone 0.3.9
was added and reacted at 60° C. for 5 hours, and as a result of infrared analysis, it was confirmed that the free isocyanate groups had completely disappeared.

By adding 400 g of styrene, a curable resin CF''l was obtained with a reddish brown color and a viscosity of 4.7 poise.

100 parts of resin [:F] +328F1 as a hardening agent
．． The system containing 5 parts and 0.3 parts of cobalt naphthenate is 18
After forming the r-layer in minutes, heat was rapidly generated, and the maximum temperature reached 159°C.

The physical properties of the molded article were as follows.

Bending strength 15.91 J/ram2 Charpy impact value 3.1 kgc%/α20 Tsukwell hardness M-115 Heat deformation temperature 126°C Example 7 Production of curable resin [G] Equipped with a stirrer, reflux condenser, and thermometer Transfer the entire amount of isocyanate adduct (M) to a 31 Mitsuro flask,
Unsaturated hydroxyl compound [IV
] was added.

Dibutyltin dilaurate 3I and 0.3 g of benzoquinone were added and reacted at 60° C. for 5 hours. As a result of infrared analysis, it was confirmed that free isocyanate groups had completely disappeared.

By adding 622 g of styrene, a curable resin (G) was obtained with a reddish brown color and a viscosity of 3.8 poise.

+328E1.5 as a curing agent to 100 parts of resin [G]
The system to which 0.2 parts of cobalt naphthenate was added rapidly generated heat after moleization in 19 minutes, and the maximum exothermic temperature reached 161°C.

The properties of the cast product were as follows.

Bending strength 15.3 kg 7w + 2 Charpy impact value 2.7 kg Bivalent 20 Kukuwell Hardness M-115 Heat deformation temperature 133°C Example 8 Production of curable resin CH) Add 920p of isocyanate adduct (XI) to a Tulo flask.
, Vinyl ester resin used in Example 3 (, ■) t
760 g, 0.11 gudibenzoquinone preparation, 60
After heating to ℃, add 1 g of dibutyltin dilaurate,
After heating at 0° C. for 3 hours, infrared analysis confirmed that free isocyanate groups had completely disappeared.

By adding 520 g of styrene, a reddish-brown curable resin CH) with a viscosity of 22.6 poise was obtained.

A resin prepared by adding 1.5 parts of +328E and 0.3 parts of cobalt naphthenate to 100 parts of resin (H) rapidly generated heat after being made into a mol in 14 minutes, and the maximum exothermic temperature reached 154°C.

The heat distortion temperature of the cured resin is 129℃, and the bending strength is 14.9.
It was Yuj2.

Example 9 Preparation of epoxy resin - α-naphthol adduct group] In a 21-three flask equipped with a stirrer, a reflux condenser, and a thermometer, 260 g of Union Carbide's ERL-4221 and 280 g of α-naphthol were added as epoxy resins. ,9,) Riphenylphosphine2. ! 7, raise the temperature to 150-160℃, cool to 160℃ if necessary.
After reacting at .degree. C. for 8 hours, infrared analysis confirmed that free epoxy groups had disappeared.

Next, at a temperature of around 120°C, P-methylstyrene 460,
! 9 was added, and an epoxy resin-α-naphthol adduct] was obtained in the form of a pale reddish brown liquid.

440 g of inphorone diisocyanate and p-methylstyrene 2609 were further added to the total amount of Epoquin resin - α-naphthol adduct, and after heating to 60°C, dibutyltin tholaurate 39 was added. was added and heated to 60°C for 6 hours, it was observed that the isocyanate value was reduced by almost half.

The obtained isocyanate adduct was pale reddish brown and liquid.

Preparation of an unsaturated hydroxyl compound In a 11-three flask equipped with a stirrer, a reflux condenser, and a thermometer, add 300 g of phenyl glycidyl ether, 144 g of acrylic acid, and 1.5 g of liphenylphosphine.
, 0.11 of hydroquinone was charged, and the reaction was carried out at 120 to 125°C for 5 hours, and the acid value became 4.1, so 156 g of p-methylstyrene was added to obtain a light yellowish brown unsaturated monohydroxyl compound. Ta.

Preparation of curable resin [J] A 31-meter flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with the entire amount of the isocyanate adduct (1) and the unsaturated hydroxyl compound (dibutyltin dilaure) 2F. After adding 0.1.9 ml of benzoquinone and reacting at 60° C. for 5 hours, infrared analysis showed that free isocyanate groups had completely disappeared.

A system in which 1.5 parts of +328E and 0.3 parts of copal naphthenate were added to 100 parts of resin [J] was glued in 32 minutes.
It rapidly generated heat and reached a maximum exothermic temperature of 154°C.

The properties of the cured resin were as follows.

Bending strength 10.7 kv2 Charpy impact value 1.9 kgcrIVcrn20 Tsukwell hardness M-115 Heat deformation temperature 129°C Example 10 Production of unsaturated hydroxyl compound 11 Mitsuro flask equipped with a stirrer, reflux condenser, and thermometer , allyl glycidyl ether 228g, acrylic acid 144.9, triphenylphosphine 1.5J,
Hydroquinone 0.1.9 is charged, 120-125℃
After reacting for 5 hours, the acid value was 7.4, so p-
128 g of methylstyrene was added to obtain a pale yellow-brown unsaturated hydroxyl compound.

In a 31-meter flask equipped with a stirrer, a reflux condenser, and a thermometer, the entire amount of the isocyanate adduct and the unsaturated hydroxyl compound were charged, and 2 g of diptyltin dilaurate and 0.1 g of lapenzoquinone were added. After reacting at 60° C. for 5 hours, infrared analysis showed that free isocyanate groups had completely disappeared.

A system in which 100 parts of resin CK), 1.5 parts of +328E and 0.3 parts of cobalt naphthenate were added became dull in 29 minutes and rapidly generated heat, reaching a maximum exothermic temperature of 159°C.

The properties of the cured resin were as follows.

Bending strength 11.9 kg/2 Charpy impact value 2.1 kgcrrV/crn20
Tsukwell Hardness: M-115 Heat Deformation Temperature: 132°C Separately, a coating film coated on a Bonderite-treated steel plate to a thickness of 0.1 mm became a tack-free coating film in about 1 hour after gluing in 35 minutes. Ta.

The coating film hardness after being left at room temperature for 3 days was 2H to 3H and could be polished.

Example 11 Preparation of unsaturated hydroxyl resin layer Into a 11-three flask equipped with a stirrer, reflux condenser, and thermometer, 260 g of ERL-4221, 228 g of allyl glycidel ether, 288 g of acrylic acid, 2.5 g of triphenylphosphine, and hydroquinone were added. 0.
29 was charged and reacted at 120°C to 125°C for 5 hours, the acid value became 9.2, so 224g of p-methylstyrene was added.
In addition, an unsaturated hydroxyl resin layer was obtained in the form of a pale reddish brown liquid.

Production of curable resin CL) 31 Cenoξ equipped with stirrer, reflux condenser and thermometer
In a rubble flask, add the entire amount of isocyanate adduct CXIV) and 500 g of unsaturated hydroxyl resin [XIV1'[l (styrene solution)] and react at 60°C for 3 hours, then add 2 g of dibutyltinnolaurate and react for further 5 hours. As a result of infrared analysis, it was observed that free isocyanate groups had disappeared.

Next, 550 g of p-methylstyrene was added to obtain a curable resin (CL) in the form of a reddish brown liquid with a viscosity of 31 poise.

100 parts of resin [L], ≠328E from Kayaku Nouri Co., Ltd.
The system containing 1 part of cobalt naphthenate and 0.5 parts of cobalt naphthenate slowly heated up after kelizing in 33 minutes, and the maximum exothermic temperature was 149.
℃ reached.

The physical properties of the cured resin were as follows.

Bending strength 11.4 kg/van
2 Charpy impact value 1.9 kh ~ 20 Tsukwell hardness M-116 heat distortion temperature
Separately, a coating film coated at 128° C. to a thickness of 0.1 on a pinprite-treated steel plate became a tank-free coating film in about 1 hour after curing in 35 minutes.

The coating film hardness after being left at room temperature for 3 days was 2H to 3H and could be polished.

〔Effect of the invention〕

The curable resin having the novel structure of the present invention is easy to synthesize, and can be cured by lanocal curing.
A cured product with better physical properties than vinyl ester resins, especially heat resistance and mechanical strength, can be obtained.
It is extremely useful for various applications such as paints, adhesives, molding materials, and FRP.

Claims (1)

[Claims] An epoxy resin that shares two or more hydroxyl groups and allyloxymethylene groups in each molecule obtained by addition reaction of monohydric phenols to the epoxy groups of an epoxy resin having two or more epoxy groups in one molecule. A phenol adduct and a diisocyanate are combined in the presence of a radically polymerizable monomer and a polymerization inhibitor such that the number of isocyanate groups in the diisocyanate is substantially 2 per equivalent of hydroxyl group in the adduct.
An isocyanate addition resin having two or more isocyanate groups and an allyloxymethylene group in each molecule is produced by an addition reaction in such a manner that the amounts are equivalent to each other. 1. A method for producing a curable resin, which comprises reacting an unsaturated hydroxyl compound or resin that shares at least one unsaturated group with a hydroxyl group.