JPH0364530B2 - - Google Patents

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 FRP.

[Conventional technology]

Currently, unsaturated polyester resins and vinyl ester resins (epoxy acrylate resins) are typical as radical-curable resins that can be cured at room temperature, and are used in a wide range of fields by 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℃, and it is used for applications that require higher temperatures. I can't do that.
Although there are special highly reactive resins that are heat resistant and have a heat distortion temperature of 130 to 150℃, in many cases other physical properties such as mechanical strength are insufficient, making them problematic for practical use. This sometimes occurred.

[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. We have discovered a method for producing a radically curable resin having a structure, and have arrived at the method of the present invention.

[Means for solving problems]

That is, the method for producing a curable resin of the present invention includes 1
Epoxy resin-phenol that shares two or more hydroxyl groups and allyloxymethylene groups in each molecule obtained by addition reaction of monovalent phenols to the epoxy groups of an epoxy resin having two or more epoxy groups in the molecule. The adduct and the diisocyanate are mixed in the presence of a radically polymerizable monomer and a polymerization inhibitor such that the amount of isocyanate groups in the diisocyanate is substantially 2 equivalents per 1 equivalent of hydroxyl group in the adduct. to produce an isocyanate addition resin having two or more isocyanate groups and allyloxymethylene groups in each molecule, and then to the addition resin, each having one or more inorganic groups in one molecule. It is characterized by reacting an unsaturated hydroxyl compound or resin that shares a saturated group and a hydroxyl group.

[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 (A) that shares two or more hydroxyl groups and allyloxymethylene groups in each molecule Isocyanate addition resin (B) that shares two or more isocyanate groups and allyloxymethylene groups in each molecule Unsaturated hydroxyl compounds that share one or more unsaturated groups and hydroxyl groups in each molecule It is known that vinyl ester resins are reacted with diisocyanates to bond 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 percent) of diisocyanate is reacted with a vinyl ester, 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 gels and the resin cannot be synthesized successfully.

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

(b) Physical properties improve.

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 each having two or more hydroxyl groups and allyloxymethylene groups in one molecule used as the first component in the method of the present invention (hereinafter sometimes referred to as component (A))
In this method, monovalent phenols are reacted with an epoxy resin having two or more epoxy groups in one molecule so that the epoxy groups and phenolic hydroxyl groups become substantially equimolar, and the epoxy groups are converted into alcoholic hydroxyl groups. It is produced by converting and introducing an allyloxymethylene group.

At this time, as a reaction catalyst, quaternary ammonium salts, aliphatic tertiary amines, trisdimethylaminophenol, salts of secondary amines, sulfonium salts, phosphonium salts, triphenylphosphine, etc. It is necessary to use the necessary amount (generally 0.1 to 1 phr) of a substance that promotes the reaction.

The reaction takes place smoothly 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.

For example, as a diglycidyl ether type of bisphenol A, Epicote 827828 from Yuka Shell Co., Ltd.
Examples include Dow's DER-330331332 and Ciba's GY-257.

A typical example of a novolak glycidyl ether type epoxy resin is DEN-431438 from Dow.

Although there are many types of cycloaliphatic epoxy resins in the literature, in practice only ERL-4221 from Union Carbide is commercially available, and this can also be used in the present invention.

In addition, as a special epoxy resin, a biphenyl type resin called YX-4000 manufactured by Yuka Shell Co., Ltd. can also be used.

A diglycidyl ether type epoxy resin using bisphenol F instead of bisphenol A, ie, Epicote 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 phenols to be reacted with the epoxy resin are not particularly limited, except that they are monovalent phenols. An example is the following.

Phenol, o-cresol, m-cresol, p-cresol, 2,3 xylenol, 2,
4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, para-isopropylphenol, para-
Shary-butylphenol, paraoctylphenol, paranonylphenol, paraphenylphenol, paracumylphenol, α-naphthol, β-naphthol, 2,5-dibromophenol, 2,6-di-t-butyl-1-hydroxy Toluene, 2,6-di-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, mixture of 2,4 tolylene diisocyanate and 2,6 tolylene diisocyanate, diphenylmethane diisocyanate, paraphenylene diisocyanate,
1,5-naphthylene diisocyanate, 1,6 hexamethylene diisocyanate, isophorone 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, can be carried out in the presence of a radically polymerizable monomer and a polymerization inhibitor. This has the advantage that gelation, which tends to occur when diisocyanates are used, is prevented and the reaction can be easily controlled. Also,
The use of a polymerizable monomer has the advantage that it can be used for curing as it is without problems such as solvent recovery when using a solvent.

The radically polymerizable monomers that can be used in the present invention include component (A), component (B), and component (A).
It dissolves the addition reactant (isocyanate addition resin) with component (B), and is selected from the viewpoint of improving the hardness and heat resistance of the cured product after curing.At the same time, the curable resin of the present invention is Since it is a solid, it is inconvenient to mold and harden it as it is, so it is used to melt it and make it easier to handle.

Practically preferable radically polymerizable monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-
Butyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate,
Phenoxyethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, phenoxyethyl acrylate,
(Meth)acrylic acid esters such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, etc. Examples include aromatic vinyl compounds such as styrene, vinyl toluene, etc. 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 used must be at least the amount that dissolves the three components mentioned above, and although the amount varies depending on the type of individual monomer, it is usually added to 100 parts by weight of the solid resin. It is used in a range of 0.1 to 2 times the

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

Components (A) and (B) are reacted in such a ratio that the isocyanate groups in component (B) are substantially 2 equivalents per 1 equivalent of hydroxyl groups in component (A), 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, each molecule of the produced isocyanate-added resin contains 2
The isocyanate group will be shared through one or more allyloxymethylene groups and a urethane bond.

The unsaturated hydroxyl compound or resin (hereinafter sometimes referred to as component (C)) that shares one or more unsaturated groups and hydroxyl group in each molecule used as the third component in the method of the present invention is:
Acrylic acid or methacrylic acid (hereinafter referred to as (meth)acrylic acid) is added to a saturated or unsaturated monoepoxy compound or epoxy resin having one epoxy group in one molecule so that the epoxy group and carboxyl group are substantially It is produced by reacting so that the equivalent amount is obtained.

Examples of saturated monoepoxy compounds include phenyl glycidyl ether, cresyl glycidyl ether, 2,5 dibromo cresyl glycidyl ether, styrene oxide, propylene oxide, ethylene oxide, butylene oxide, butyl glycidyl ether, and the like.

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

The epoxy resins used in the production of component (C) are of course of the types mentioned above, but the types are expanded further, and the types with one or more hydroxyl groups, i.e., those with molecular weight
Types ranging from 350 to 2500 are also available.

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 phenols and the epoxy resin described above is used as a catalyst.

At this time, it is necessary to use a polymerization inhibitor such as polyhydric phenols to prevent gelation 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, it goes without saying that a commercially available vinyl ester resin (epoxy acrylate), which is a reaction product of an epoxy resin and (meth)acrylic acid, can also be used as the component (C).

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

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

The reaction between the isocyanate-added resin and component (C) can be smoothly carried out in the radically polymerizable monomer used in the above reaction. At that time, a radically polymerizable monomer and a polymerization inhibitor are added as necessary. Furthermore, component (C) may be used alone, or two or more kinds of compounds or resins may be used in combination. When using two or more types of component (C), saturated or unsaturated monoepoxy compounds or epoxy resins can be simultaneously produced by using two or more types of epoxy resins when reacting with (meth)acrylic acid. 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, examples will be shown below to help understand the present invention.

Example 1 Production of epoxy resin-phenol adduct [] 1 equipped with a stirrer, reflux condenser, and thermometer
In a three-necked flask, 360 g of Epicote 827 (produced by Yuka Ciel Epoxy Co., Ltd.) as an epoxy resin, 188 g of phenol, and 1.5 g of trimethylbenzylammonium chloride are charged and the temperature is raised. When the temperature exceeds 120°C, heat is generated rapidly.

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

The epoxy resin-phenol adduct [] cooled to room temperature was pale yellowish brown and syrup-like.

Production of isocyanate adduct [] Weighed 550 g of adduct [], 250 g of styrene, and 0.01 g of parabenzoquinone into a similar device, and
After heating and dissolving at ~70°C, 350 g of 2,4-tolylene diisocyanate was added and reacted at 60°C for 5 hours. As a result of analysis by di-n-butylamine-hydrochloric acid titration method, the isocyanate group-containing system was From 4%
It was observed that the rate had decreased by almost half to 1.8%.

250 g of styrene was added to obtain an isocyanate adduct [] in the form of a pale yellowish brown liquid.

Production of unsaturated hydroxyl compound [ ] 1 with a stirrer, reflux condenser, and thermometer
Into a three-necked flask, charge 300 g of phenyl glycidyl ether, 172 g of methacrylic acid, 2 g of triphenylphosphine, and 0.2 g of hydroquinone.
When the reaction was heated to ~130°C for 3 hours, the acid value became 4.1, so 260 g of styrene was added to produce an unsaturated monohydroxyl compound (styrene solution).

Production of curable resin [A] Add unsaturated monohydroxyl compound [] (styrene solution) 730 to the total amount of isocyanate adduct []
Transfer g to a three-necked 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, 585 g of styrene was added to obtain a curable resin [A] having a reddish brown color and a viscosity of 5.4 poise.

A system in which 100 parts of resin [A], 1.5 parts of #328E from Kayaku Nouri Co., Ltd. as a hardening agent, and 0.3 parts of cobalt naphthenate were mixed together gelled in 22 minutes and rapidly generated heat, reaching a maximum temperature of 160°C. did.

The physical properties of the cured resin were as follows.

Bending strength 16.7Kg/mm ² Heat deformation temperature 121℃ Rockwell hardness M-113 Shallie impact value 3Kg/cm ^2Example 2 Production of unsaturated hydroxyl compound [] 1 equipped with a stirrer, reflux condenser, and thermometer
Glycidyl methacrylate in a three-necked flask
284g, methacrylic acid 172g, triphenylphosphine 2g, hydroquinone 0.2g, 120~
When heated and stirred at 130° C. for 5 hours, the acid value became 11, so 244 g of styrene was added to produce an unsaturated monohydroxyl compound (styrene solution).

Production of curable resin [B] Add 700 g of unsaturated hydroxyl compound [] (styrene solution) to the total amount of isocyanate adduct []
Transfer to a three-necked 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.

Further, 600 g of styrene was added to obtain a curable resin [B] having a reddish brown color and a viscosity of 3 poise.

A system in which 100 parts of resin [B] was mixed with 1.5 parts of #328E from Kayaku Nouri Co., Ltd. as a hardening agent and 0.3 parts of cobalt naphthenate gelled in 15 minutes and rapidly generated heat, reaching a maximum temperature of 161°C. Reached.

The physical properties of the molded resin are as follows: bending strength: 14.6 kg/mm ² ; heat distortion temperature: 131°C; Rockwell hardness: M-115; Charpy impact value: 2.7 kg/cm ² ; it is clear that it is hard, but has high heat resistance and strength. It was done.

Production of isocyanate adduct [] In a similar device, 350 g of epoxy resin-phenol adduct [], 150 g of styrene, and 0.01 g of parabenzoquinone were weighed, and after heating and dissolving at 60 to 70°C, 2,4 - After adding 220 g of tolylene diisocyanate and reacting at 60°C for 5 hours, analysis by di-n-butylamine-hydrochloric acid titration revealed that the isocyanate group was reduced by almost half from 3.8% to 1.6%. It was done.

130 g of styrene was added to obtain an isocyanate adduct [] in the form of a pale yellowish brown liquid.

Production of vinyl ester resin [ ] 1 with a stirrer, reflux condenser, and thermometer
In a three-necked flask, 360 g of the above-mentioned Epicote 827 as an epoxy resin, 172 g of methacrylic acid, 0.2 g of hydroquinone, and 1.5 g of trimethylbenzylammonium chloride were charged and reacted for 3 hours with vigorous stirring at 120 to 130°C, the acid value was
It became 5.9.

230 g of styrene was added, and vinyl ester resin [] was obtained in the form of a reddish brown liquid.

Production of curable resin [C] 2 equipped with a stirrer, reflux condenser, and thermometer
Isocyanate adduct in a three-necked flask []
When the temperature reached 60℃, 2g of dibutyltin dilaurate was added and reacted at 60℃ for 3 hours. As a result of infrared analysis, free isocyanate groups completely disappeared. Was.

Add 410g of styrene to hardenable resin [C]
was obtained with a reddish brown color and a viscosity of 9.7 poise.

A system consisting of 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 gelled in 29 minutes and rapidly generated heat to give a cured resin.

Its properties were: bending strength: 16.7 Kg/mm ² bending modulus: 460 Kg/mm ² Sharpie impact value: 3.7 Kg cm/cm ² heat distortion temperature: 127°C Rockwell hardness: M-113.

Comparative example 1 Vinyl ester resin []760g in the same device
174g of 2,4-tolylene diisocyanate
(containing equimolar isocyanate groups as the isocyanate adduct []) and 1.6 g of dibutyltin dilaurate at 60°C resulted in gelation after about 3 minutes, and a practically usable resin could not be obtained.

Example 4 Production of isocyanate adduct [].

2 equipped with a stirrer, reflux condenser, and thermometer.
In a separable flask, 550 g of the epoxy resin-phenol adduct produced in Example 1 was added.
After preparing 330 g of hexamethylene diisocyanate, 420 g of styrene, 0.2 g of parabenzoquinone, and 4.5 g of dibutyltin dilaurate and making a homogeneous solution,
The reaction was carried out 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.

Production of unsaturated hydroxy compound [ ] 1 equipped with a stirrer, reflux condenser, and thermometer
Add 150 g of phenyl glycidyl ether, 86 g of methacrylic acid, 0.5 g of triphenylphosphine, and 0.05 g of hydroquinone to a separable flask and react at 120-130°C for 3 hours.
8.1, 164 g of styrene was added, and an unsaturated hydroxy compound [] (styrene solution) was obtained in the form of a pale reddish brown liquid.

Production of curable resin (D) 3 with stirrer, reflux condenser and thermometer
In a three-necked flask, add 1300 g of isocyanate adduct and 760 g of vinyl ester resin.
g, 400 g of unsaturated monohydroxy compound []
After adding 0.2 g of parabenzoquinone and 5 g of dibutyltin dilaurate and reacting at 60°C for 8 hours, infrared analysis confirmed that free isocyanate groups had completely disappeared.

By adding 500 g of styrene, a curable resin (D) was obtained with a reddish brown color and a viscosity of 7.1 poise.

A mixed system in which 1.5 parts of #328E and 0.3 parts of cobalt naphthenate were added to 100 parts of resin (D) gelled 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 16.9Kg/mm ² Shalpy impact value 3.9Kg/cm ² Heat distortion temperature 119℃ Rockwell hardness M-113 Example 5 Production of unsaturated hydroxyl resin [ ] 1 with a stirrer, reflux condenser, and thermometer
In a three-neck flask, as an epoxy resin, add 370 g of bisphenol A diglycidyl ether with an epoxy equivalent of about 185, and 142 g of glycidyl methacrylate.
g, 258 g of methacrylic acid, 2.5 g of benzyldimethylamine and 0.3 g of hydroquinone and reacted for 4 hours at 125-130℃ in an air stream, the acid value was
8.1, 230 g of styrene was added to obtain a reddish-brown liquid unsaturated hydroxyl resin.

Production of isocyanate adduct [] 3 equipped with a stirrer, reflux condenser, and thermometer
Weigh out 540 g of epoxy resin-phenol adduct [], 260 g of styrene, and 0.01 g of parabenzoquinone into a separable flask, make a homogeneous solution, add 350 g of 2,4-tolylene diisocyanate, and heat at 60°C. After reacting for 5 hours, it was estimated that the isocyanate concentration was reduced by almost half as a result of infrared analysis.

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

Production of curable resin [E] To this, add the entire amount of unsaturated hydroxyl resin [] (styrene solution), further add 5 g of dibutyltin dilaurate and 0.3 g of parabenzoquinone, and react at 60-65°C for 5 hours. As a result of infrared analysis, it was confirmed that free isocyanate groups had completely disappeared.

By adding 1170 g of styrene, a curable resin [E] was obtained with a reddish brown color and a viscosity of 5.9 poise.

To 100 parts by weight of resin [E],
The system containing 1 part of 328E and 0.2 part of cobalt naphthenate gelled 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/mm ^2Heat distortion temperature 136℃ Rockwell hardness M-116 Shalpy impact value 2.4Kgcm/ ^cm 2Example 6 Production of epoxy resin-xylenol adduct [XI] Equipped with a stirrer, reflux condenser, and thermometer I did 2
A three-necked flask was charged with 360 g of DEN-431, 270 g of 2,6-xylenol, and 2 g of benzyldimethylamine as a novolak type epoxy resin, and reacted at 150 to 160°C for 3 hours. As a result of infrared analysis, free epoxy groups were It was recognized that it had disappeared.

Furthermore, 370 g of styrene and 0.1 g of hydroquinone were added to obtain an epoxy resin-xylenol adduct [XI] in the form of a pale reddish brown liquid.

Production of isocyanate adduct [XII] To the entire amount of adduct [XI] cooled to around room temperature, 500 g of diphenylmethane diisocyanate and 330 g of styrene were further added, and the mixture was heated and reacted at 60°C for 5 hours. The same analysis as in 1 revealed that the isocyanate value was reduced by almost half.

Isocyanate adduct [XI] was obtained in a pale reddish brown liquid state.

Production of curable resin [F] 3 equipped with a stirrer, reflux condenser, and thermometer
Transfer the entire amount of isocyanate adduct [XI] to a three-neck flask, then add 288 g of 2-hydroxypropyl methacrylate, 3 g of dibutyltin dilaurate, and 0.3 g of benzoquinone, and react at 60°C for 5 hours. As a result of infrared analysis, free isocyanate was detected. It was observed that the nato groups had completely disappeared.

Add 400g of styrene to hardenable resin [F]
was obtained with a reddish brown color and a viscosity of 4.7 poise.

Add 1.5 parts of #328E as a hardening agent to 100 parts of resin [F].
The system containing 0.3 parts of cobalt naphthenate rapidly generated heat after gelling in 18 minutes, reaching a maximum temperature of 159°C.

The physical properties of the molded article were as follows.

Bending strength 15.9Kg/mm ² Shalpy impact value 3.1Kgcm/cm ² Rockwell hardness M-115 Heat distortion temperature 126℃ Example 7 Production of curable resin [G] Equipped with a stirrer, reflux condenser, and thermometer 3
The entire amount of the isocyanate adduct [XI] was transferred to a three-necked flask, and the entire amount of the unsaturated hydroxyl compound [] synthesized in Example 2 was added.

Dibutyltin dilaurate 3g, benzoquinone
After adding 0.3 g and reacting at 60° C. for 5 hours, infrared analysis showed that free isocyanate groups had completely disappeared.

Add 622g of styrene to hardenable resin [G]
was obtained with a reddish brown color and a viscosity of 3.8 poise.

Add 1.5 parts of #328E as a hardening agent to 100 parts of resin [G].
The system containing 0.2 parts of cobalt naphthenate rapidly generated heat after gelling in 19 minutes, and the maximum exothermic temperature was 161°C.
reached.

The properties of the cast product were as follows.

Bending strength 15.3Kg/mm ² Shalpy impact value 2.7Kgcm/cm ² Rockwell hardness M-115 Heat distortion temperature 133℃ Example 8 Production of curable resin [H] Equipped with a stirrer, reflux condenser, and thermometer 3
In a three-necked flask, 920 g of isocyanate adduct [XI], 760 g of the vinyl ester resin [] used in Example 3, and 0.1 g of parabenzoquinone were charged, and after heating to 60°C, 1 g of dibutyltin dilaurate was added. After heating for 3 hours at °C, infrared analysis confirmed that free isocyanate groups had completely disappeared.

By adding 520 g of styrene, a curable resin [H] having a reddish brown color and 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 gelling 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
It was 14.9Kg/ ^mm2 .

Example 9 Epoxy resin-α-naphthol adduct []
Production of 2 units equipped with a stirrer, reflux condenser, and thermometer
In a three-necked flask, add 260 g of Union Carbide's ERL-4221 as an epoxy resin, α-
Naphthol 280g, triphenylphosphine 2g
was charged, heated to 150 to 160°C, cooled if necessary, and reacted at 160°C for 8 hours. As a result of infrared analysis, it was confirmed that free epoxy groups had disappeared.

Next, p-methylstyrene 460 at a temperature of around 120℃
g was added, and an epoxy resin-α naphthol adduct [] was obtained in the form of a light reddish brown liquid.

Production of isocyanate adduct [] To the total amount of epoxy resin-α naphthol adduct [], 440 g of isophorone diisocyanate,
Add 260g of p-methylstyrene and heat to 60°C, then add 3g of dibutyltin dilaurate and heat to 60°C.
It was observed that the isocyanate value was reduced by approximately half upon heating to 6 hours at .degree.

The obtained isocyanate adduct [] was pale reddish brown and liquid.

Production of unsaturated hydroxyl compound [ ] 1 with a stirrer, reflux condenser, and thermometer
In a three-necked flask, charge 300 g of phenyl glycidyl ether, 144 g of acrylic acid, 1.5 g of triphenylphosphine, and 0.1 g of hydroquinone.
After reacting at ~125°C for 5 hours, the acid value became 4.1, so 156 g of p-methylstyrene was added to obtain a pale yellowish brown unsaturated monohydroxyl compound [ ].

Production of curable resin [J] 3 equipped with a stirrer, reflux condenser, and thermometer
In a three-necked flask, add isocyanate adduct [
] and the unsaturated hydroxyl compound [
], dibutyltin dilaurate 2
Add g and 0.1 g of parabenzoquinone and heat to 60℃ for 5 minutes.
After reacting for a period of time, infrared analysis revealed that free isocyanate groups had completely disappeared.

A system in which 1.5 parts of #328E and 0.3 parts of cobalt naphthenate were added to 100 parts of resin [J] gelled in 32 minutes.
It rapidly generated heat, reaching a maximum temperature of 154°C.

The properties of the cured resin were as follows.

Bending strength 10.7Kg/mm ² Shalpy impact value 1.9Kgcm/cm ² Rockwell hardness M-115 Heat distortion temperature 129℃ Example 10 Production of unsaturated hydroxyl compound [ ] 1 equipped with a stirrer, reflux condenser, and thermometer
Allyl glycidyl ether in a three-necked flask.
228g, acrylic acid 144g, triphenylphosphine 1.5g, hydroquinone 0.1g, 120~
After reacting at 125° C. for 5 hours, the acid value became 7.4, so 128 g of p-methylstyrene was added to obtain a pale yellowish brown unsaturated hydroxyl compound [ ].

Production of curable resin [K] 3 equipped with a stirrer, reflux condenser, and thermometer
In a three-necked flask, add isocyanate adduct [
] and the unsaturated hydroxyl compound [
], dibutyltin dilaurate 2
Add g and 0.1 g of parabenzoquinone and heat to 60℃ for 5 minutes.
After reacting for a period of time, infrared analysis revealed that free isocyanate groups had completely disappeared.

A system containing 100 parts of resin [K], 1.5 parts of #328E, and 0.3 parts of cobalt naphthenate gelled in 29 minutes.
It rapidly generated heat and reached a maximum exothermic temperature of 159°C.

The properties of the cured resin were as follows.

Bending strength 11.9Kg/mm ² Shyalpy impact value 2.1Kgcm/cm ² Rockwell hardness M-115 Heat deformation temperature 132℃ Separately, a coating film applied to a thickness of 0.1 mm on a bonderite-treated steel plate was applied for 35 minutes. After gelation at about 1
It becomes a tack-free coating over time.

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

Example 11 Production of unsaturated hydroxyl resin
In a three-neck flask, add 260 g of ERL-4221, 228 g of allyl glycidyl ether, 288 g of acrylic acid,
After charging 2.5 g of triphenylphosphine and 0.2 g of hydroquinone and reacting at 120°C to 125°C for 5 hours, the acid value reached 9.2, so 224 g of p-methylstyrene was added and unsaturated hydroxyl resin []
was obtained as a light reddish brown liquid.

Production of curable resin [L] 3 equipped with a stirrer, reflux condenser, and thermometer
In a separable flask, put the total amount of isocyanate adduct [] and unsaturated hydroxyl resin []
After adding 500g of (styrene solution) and reacting at 60℃ for 3 hours, 2g of dibutyltin dilaurate was added and
After reacting for a period of time, infrared analysis revealed that free isocyanate groups disappeared.

Next, 550 g of p-methylstyrene was added to obtain a curable resin [L] in the form of a reddish brown liquid with a viscosity of 3.1 poise.

To 100 parts of resin [L], #328E from Kayaku Nouri Co., Ltd.
The system containing 1 part of cobalt naphthenate and 0.5 part of cobalt naphthenate is 33
After gelling in minutes, it generates heat slowly and the maximum exothermic temperature is
The temperature reached 149℃.

The physical properties of the cured resin were as follows.

Bending strength 11.4Kg/mm ² Shalpy impact value 1.9Kgcm/cm ² Rockwell hardness M-116 Heat deformation temperature 128℃ Separately, a coating film coated to a thickness of 0.1mm on a bonderite-treated steel plate was cured in 35 minutes. Approximately 1 after gelation
It becomes a tack-free coating over time.

The hardness of the coating film 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
It is easy to synthesize, and by radical curing, a cured product with physical properties superior to vinyl ester resins, especially heat resistance and mechanical strength, can be obtained. It is extremely useful for various uses such as wood and FRP.

Claims (1)

[Claims] 1 Epoxy resin that shares two or more hydroxyl groups and allyloxymethylene groups in each molecule obtained by addition reaction of monovalent 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 so that the isocyanate group of the diisocyanate is substantially 2 equivalents per 1 equivalent of hydroxyl group of the adduct. An isocyanate addition resin having two or more isocyanate groups and an allyloxymethylene group in one molecule is produced by an addition reaction such that the addition reaction is performed so that the isocyanate addition resin shares two or more isocyanate groups and allyloxymethylene groups in one molecule, and then the addition resin is given one or more of each in one molecule. A method for producing a curable resin, which comprises reacting an unsaturated hydroxyl compound or resin that shares an unsaturated group with a hydroxyl group.