JP2001288243A - Urea-modified epoxy resin compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive urea-modified epoxy resin compound which does not pollute the environment. SOLUTION: This compound is prepared by epoxidizing a compound represented by the formula: (B)p-Z-(A)q, wherein Z is -(CH2)m-, wherein m is 0 or a positive integer or a group represented by formula I or II; A and B are each CH2=CH-, CH2=CH-CH2-, -OCH=CH2, -O-CH2-CH=CH2, -OCH2-CH2- CH=CH2- or a group represented by formula III; and p and q are each 0 or a positive integer with a peroxide and reacting the resultant epoxy compound with urea.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a urea-modified epoxy resin compound which is eco-friendly because it uses low-cost starting materials, does not use bisphenol A and epichlorohydrin, and is environmentally friendly. And its foam.

[0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urea-modified epoxy formed by reacting a compound represented by the following structural formula with an epoxidized compound using a peroxide and urea, and this urea-modified epoxy resin. The present invention relates to a urea-modified epoxy resin foam formed by adding a blowing agent to urea.

More specifically, it does not release bisphenol A, an environmental hormone, or epichlorohydrin, a chlorine compound, has a short afterflame time upon combustion, has a low smoke emission amount, has excellent fire protection and heat insulation properties, and has excellent urea properties. Modified epoxy resin compounds are mainly useful as adhesives, fixing agents, paints, electronic components, and building materials, and urea-modified epoxy resin compound foams are useful for building materials, automotive, electric, various opportunities, and packaging materials. Urea-modified epoxy resin compounds and foams thereof.

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[0004]

2. Description of the Related Art A conventional epoxy resin is bisphenol A.
It contains bisphenol A, which is reported in the media as an environmental hormone, because it is synthesized using epichlorohydrin as a starting material, and epichlorohydrin is a volatile chloro compound. Could be destroyed. Further, since conventional epoxy resins burn very well, it is necessary to add a flame retardant to make them flame-retardant. However, most of the flame retardants currently used are compounds containing chromium and bromide.Epoxy resins containing these flame retardants will not emit flames in the event of a fire, but will release chloro and bromide atoms and destroy the environment. There were drawbacks. JP-A-63-154751 discloses an epoxy resin.

Embedded image It is described that a monoamine compound represented by the following formula is reacted. Further, JP-A-6-184511 discloses that
With epoxy resin

Embedded image The reaction of a secondary or tertiary amine compound represented by the following formula is described.

[0005]

Bisphenol A, which is a conventional raw material for epoxy resin, is feared to affect the ecosystem as an environmental hormone, and epichlorohydrin is a volatile compound containing a chlorine atom. There was a problem of air pollution. Another problem is that the price is high. Furthermore, since conventional epoxy resins burn well, it was necessary to add a flame retardant to make them flame-retardant. However, flame retardants having halogen atoms such as chlorine and bromine are widely used. Epoxy resins to which these flame retardants have been added do not emit flames in the event of fire, but have the problem of destructing the environment by emitting halogen atoms such as chlorine and bromine.

[0006]

In order to solve the above-mentioned problems, the present invention provides an epoxidation method using a compound represented by the following structural formula and a peroxide.

Embedded image It is an object of the present invention to provide an epoxy resin which does not contain environmental hormone substances and volatile chloro compounds. In addition, this epoxy resin

Embedded image It has been argued that the modification by the method reduces the after-flame time during combustion without adding a flame retardant.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the urea-modified epoxy resin compound according to the present invention will be described in detail.

[0008]

Embedded image Compounds represented by the above structural formula (1) include dicyclopentadiene, ethylidene norbornene, norbornadiene,
Butadiene, pentadiene, octadiene, nonadiene, decadiene, divinylheptane, divinyloctane, divinylnonane and the following structural formula

Embedded image And the like.

The peroxide used in the present invention includes hydrogen peroxide, peracetic acid, methyl acetoacetic acid peroxide,
Acetyl acetone peroxide, methyl cyclohexanone peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, ditertiary butyl peroxide, acetyl peroxide, dilauroyl peroxide, benzoyl peroxide, tertiary Organic peroxides such as butyl peroxybenzoate can also be used.

The double bond portion of the compound represented by the structural formula (1) can be easily synthesized into an epoxy resin compound using the above-mentioned peroxide. The method is carried out by conventional means of organic synthesis.

For example, in the case of dicyclopentadiene of the structural formula (1),

Embedded image It is considered that an epoxy compound and an epoxy resin as described above have been synthesized. It is believed that other compounds are undergoing similar reactions. The molecular weight of the epoxy resin is preferably 50,000 or less. The reason for this is that if the molecular weight of the epoxy resin is increased, the flame retardant performance that appears when modified with urea becomes worse. Next, when the epoxy resin obtained as described above is reacted with urea, it is considered that a block-type urea-modified epoxy resin is formed. Taking dicyclopentadiene as an example,

Embedded image It is considered that the structural formula is as follows. It is believed that other compounds are undergoing similar reactions. At this time, the molar ratio of urea to the epoxidized compound is 90% to 90%.
Preferably, it is 5%. The reason is that when the molar ratio of urea is 90% or more, the physical properties of the urea-modified epoxy resin become brittle, and when it is 5% or less, the flame-retardant effect becomes very poor. The urea-modified epoxy resin thus obtained preferably has a molecular weight of 100 to 300,000. The reason is that if the molecular weight is 100 or less, the strength of the epoxy resin becomes extremely poor, and if the room temperature is high, the monomer smells, or if the molecular weight is 300,000 or more, the workability at the time of use deteriorates. is there.

Further, a catalyst may be used in the reaction for obtaining an epoxy resin compound using the above-mentioned organic peroxide.
Suitable catalysts include, for example, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, lithium hydroxide, ammonium hydroxide, sodium hydrogen sulfate, sodium sulfate, barium hydroxide, anhydrous copper sulfate, and the like.

In the above synthesis reaction of the urea-modified epoxy resin compound, the reaction may be carried out in a solvent, if necessary. As the solvent, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, decalin, N-
Any one or more of methylpyrrolidone, dimethylformamide, dimethylsulfoxide, dimethylacetamide, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, etc. It can be used selectively. Of course, the solvent is not limited to these.

The double bond portion of the compound represented by the structural formula (1) is epoxidized using the above-mentioned peroxide, and simultaneously reacted with urea while performing ring-opening polymerization to form a urea-modified epoxy resin. The method of obtaining is described in detail.

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With respect to the compound having a double bond, the peroxide is used in an amount of 0.5 mol to 10 mol, preferably 1.5 mol.
Mol to 4 mol of the above-mentioned compound as a catalyst with respect to the peroxide is added in an amount of 0.01 mol to 2 mol, preferably 0.05 mol to 1.2 mol. The ring-opening polymerization is performed while the reaction is being carried out. The heating temperature is 10 ° C to 180 ° C, preferably 20 ° C to 150 ° C.
C, more preferably 40C to 120C. Next, a method of obtaining the urea-modified epoxy resin by reacting the above epoxy compound with urea will be described in detail. The use amount of urea to the epoxy compound is 90% to 5%, preferably 80% to 10%.
%, And the amount of urea used is desirably 10% or more in order to keep the afterflame time to 7 seconds or less. The temperature at which the epoxy compound is reacted with urea is 20 ° C to 260 ° C, preferably 40 ° C to 180 ° C, more preferably 60 ° C to 1 ° C.
50 ° C is good. In the above reaction, if necessary, a catalyst such as triethylamine, pyridine, dimethylaminophenol or methylethylimidazole may be used. The use amount is preferably 0.1% to 5%.

In the above reaction, a solvent may be used if necessary. As the solvent, for example, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, benzene, toluene,
Any one or more of xylene, decalin, N-methylpyrrolidone, dimethylformamide, cimethylsulfoxide, dimethylacetamide, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, etc. may be arbitrarily selected and used. You can do it. Of course, the solvent is not limited to these.

In the above reaction, the reaction may be carried out in an atmosphere of an inert gas such as nitrogen gas, argon gas or carbon dioxide gas.

In the above reaction, when a solvent is used, after completion of the reaction, the pressure is reduced while a rotary evaporator, a distillation apparatus, an ester reaction apparatus, a polymer polymerization apparatus,
Distillation is performed using a device such as a drum dryer, a vacuum dryer, or a spray dryer.

The urea-modified epoxy resin compound obtained as described above may be cured using a curing agent. Preferred curing agents are phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, dihydrophthalic anhydride, tetrahydrophthalic anhydride, methylphthalic anhydride, methyldihydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic acid Acid anhydrides, amino compounds represented by the following structural formulas (1) to (60)

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Embedded image

Embedded image

Embedded image And phenolic resins are used. The molecular weight of the phenol resin is preferably 200,000 or less.
The reason is that when the molecular weight becomes larger than 200,000, the urea-modified epoxy compound cured with the phenol resin becomes hard and brittle.

With respect to 100 parts by weight of the urea-modified epoxy resin, the amount of the curing agent used is 30 parts by weight to 90 parts by weight for an acid anhydride, 1 part to 60 parts by weight for an amino compound, and 60 parts by weight for an phenol resin. Is preferably 40 to 80 parts by weight. The preferred curing temperature is 7 for acid anhydrides.
0 ° C to 220 ° C, 10 ° C to 190 ° for amino compounds
C., and in the case of a phenol resin, the temperature is preferably from 50.degree.

Next, a method for forming the urea-modified epoxy resin compound foam according to the present invention will be described in detail. Foams used for molding foams include, for example, chlorofluorocarbon (alternative fluorocarbon, 1416, etc.), carbodiimide, nitrogen gas,
1 out of hydrocarbons (pentane, cyclopentane), etc.
More than one species can be arbitrarily selected and used. Of course, the foaming agent is not limited to these.

Further, the foaming agent is added before, during, or after the reaction of the compound represented by the following structural formula (1) with the epoxidized compound using a peroxide and urea. May be added at any time, but it is easier to control the foam, especially when added after the reaction,
Although it is preferable, it is more preferable to add a foaming agent when curing the reaction product of the epoxidized compound and urea using a curing agent.

Embedded image

The amount of the foaming agent is preferably 1 to 50 parts by weight, based on 100 parts by weight of the urea-modified epoxy resin.
The foaming temperature can be arbitrarily selected as long as it is in the range of 0 to 300 ° C. However, from the viewpoint of easy control of the reaction, the temperature is preferably 20 ° C to 190 ° C.

Next, the method for obtaining the urea-modified epoxy resin compound and the foam thereof according to the present invention will be described in detail with reference to specific examples.

[0025]

Example 1 120 g of ethylidene norbornene and 2 g of ammonium hydroxide were added to 500 g of toluene, transferred to a reaction vessel, and purged with nitrogen gas, and 100 cc of 50% hydrogen peroxide solution was added dropwise over 30 minutes while heating to 80 ° C. The mixture was reacted for 5 hours while stirring. The molecular weight of the thus obtained ethylidene norbornene epoxy resin compound measured by gel permeation chromatography was 6,200. Next, 300 g of methyl ethyl ketone and 60 g of urea were added to the reaction product, and the temperature was raised to 95 ° C. in a nitrogen atmosphere with stirring, and the reaction was carried out for 8 hours. Next, the solvent was distilled off at 60 ° C. while reducing the pressure to 5 mmHg using a rotary evaporator. The resulting reactant had a viscosity of 52,000 cps (25
° C). Epoxy equivalent is 10
3 (g / eq), molecular weight was 82,000.

[0026]

Example 2 80 g of dicyclopentadiene, 10 g of divinylbenzene, 2 g of potassium hydroxide and 600 g of xylene
g was added to the reaction vessel, and peracetic acid 7 was added while heating the temperature to 70 ° C. while flowing argon gas through a gas introduction tube.
After dropping 0 g over 1 hour and reacting for 9 hours while stirring, the mixture is washed with water, left standing for 30 minutes, the separated aqueous phase is discarded, and the xylene phase is taken out. The molecular weight of the thus obtained dicyclopentadiene / hexadiene / divinylbenzene ternary coepoxy resin compound was measured by gel permeation chromatography (GCP) to be 13,000.

Next, methyl ethyl ketone 4 was added to the above reaction product.
After adding 20 g and 54 g of urea, the temperature was raised to 98 ° C. in an argon gas atmosphere with stirring, and the reaction was carried out for 12 hours. And 5 using a rotary evaporator
The solvent was distilled off at 80 ° C. under reduced pressure of mmHg. The resulting reaction was a light brown solid. When heated to 80 ° C., it melted and had a viscosity of 2200 cps (80 ° C.).
The epoxy equivalent was 92 (g / eq), and the molecular weight measured by GPC (gel permeation chromatography) was 121,000.

[0028]

Example 3 To 100 g of the urea-modified ethylidene norbornene epoxy resin compound obtained in Example 1 was added 54 g of a phenol resin having a molecular weight of 7200 as a curing agent, and the mixture was mixed well.
Heating to 1 ° C. for 1 hour gave a brown solid. The Shore A hardness of this solid was 92, and the maximum elongation was 21%.

[0029]

Example 4 100 g of urea-modified ethylidene norbornene epoxy resin compound obtained in Example 1 and a molecular weight of 72
54 g of phenolic resin and 21 g of carbodiimide
Was added to a mixed solvent of 300 g of toluene and 300 g of methyl ethyl ketone, heated to 80 ° C. for 40 minutes, pre-cured while stirring, and the solvent was distilled off under reduced pressure of 1 mmHg using a rotary evaporator. In order to form a foam from the urea-modified ethylidene norbornene epoxy resin compound phenol resin precured product containing the foaming agent, the mold temperature may be 185 ° C. and heating may be performed for 25 minutes.

[0030]

Embodiment 5 For Embodiments 3 and 4, JIS-A-13
Table 1 shows the results of the quasi-nonflammability test (surface test) specified in No. 21. Further, for reference, in addition to the above examples, examples of a phenol resin foam as Reference Example 1 and examples of an isocyanurate resin foam as Reference Example 2 will be shown.

[0031]

[Table 1]

As described above, according to the urea-modified epoxy resin compound and the foam thereof according to the present invention, the after-flame time at the time of combustion is almost zero, and the fire resistance and fire resistance are excellent. The amount of smoke generated during combustion is small, and the environment can be considered.
It does not generate formalin, a harmful air pollutant, or epichlorohydrin, a chlorine compound, during the reaction. Does not release bisphenol A, an environmental hormone.

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[Procedure amendment]

[Submission date] April 6, 2000 (200.4.6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

[Title of the Invention] Urea-modified epoxy resin compound

[Claims]

[ Formula 1 ]

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a urea-modified epoxy resin compound which is eco-friendly because it uses low-cost starting materials, does not use bisphenol A and epichlorohydrin, and is environmentally friendly. And its foam.

[0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urea-modified epoxy formed by reacting a compound represented by the following structural formula with an epoxidized compound using a peroxide and urea, and this urea-modified epoxy resin. The present invention relates to a urea-modified epoxy resin foam formed by adding a blowing agent to urea.

[ Formula 2 ]

More specifically, it does not release bisphenol A, an environmental hormone, or epichlorohydrin, a chlorine compound, has a short afterflame time upon combustion, has a low smoke emission amount, has excellent fire protection and heat insulation properties, and has excellent urea properties. Modified epoxy resin compounds are mainly useful as adhesives, fixing agents, paints, electronic components, and building materials, and urea-modified epoxy resin compound foams are useful for building materials, automotive, electric, various opportunities, and packaging materials. Urea-modified epoxy resin compounds and foams thereof.

[0004]

2. Description of the Related Art A conventional epoxy resin is bisphenol A.
It contains bisphenol A, which is reported in the media as an environmental hormone, because it is synthesized using epichlorohydrin as a starting material, and epichlorohydrin is a volatile chloro compound. Could be destroyed. Further, since conventional epoxy resins burn very well, it is necessary to add a flame retardant to make them flame-retardant. However, most of the flame retardants currently used have compounds containing chromium and bromide.Epoxy resins containing these flame retardants will not emit flames in the event of a fire, but will release chloro and bromide atoms and destroy the environment. There were drawbacks. JP-A-63-154751 discloses an epoxy resin.

[Formula 3] It is described that a monoamine compound represented by the following formula is reacted. Further, JP-A-6-184511 discloses that
With epoxy resin

[Of 4] The reaction of a secondary or tertiary amine compound represented by the following formula is described.

[0005]

Bisphenol A, which is a conventional raw material for epoxy resin, is feared to affect the ecosystem as an environmental hormone, and epichlorohydrin is a volatile compound containing a chlorine atom. There was a problem of air pollution. Another problem is that the price is high. Furthermore, since conventional epoxy resins burn well, it was necessary to add a flame retardant to make them flame-retardant. However, flame retardants having halogen atoms such as chlorine and bromine are widely used. Epoxy resins to which these flame retardants have been added do not emit flames in the event of fire, but have the problem of destructing the environment by emitting halogen atoms such as chlorine and bromine.

[0006]

In order to solve the above-mentioned problems, the present invention provides an epoxidation method using a compound represented by the following structural formula and a peroxide.

[Of 5] It is an object of the present invention to provide an epoxy resin which does not contain environmental hormone substances and volatile chloro compounds. In addition, this epoxy resin

[Omitted] It has been argued that the modification by the method reduces the after-flame time during combustion without adding a flame retardant.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the urea-modified epoxy resin compound according to the present invention will be described in detail.

[0008]

[Omitted] Compounds represented by the above structural formula (1) include dicyclopentadiene, ethylidene norbornene, norbornadiene,
Butadiene, pentadiene, octadiene, nonadiene, decadiene, divinylheptane, divinyloctane, divinylnonane and the following structural formula

[Of 8] And the like.

The peroxide used in the present invention includes hydrogen peroxide, peracetic acid, methyl acetoacetic acid peroxide,
Acetyl acetone peroxide, methyl cyclohexanone peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, ditertiary butyl peroxide, acetyl peroxide, dilauroyl peroxide, benzoyl peroxide, tertiary Organic peroxides such as butyl peroxybenzoate can also be used.

The double bond portion of the compound represented by the structural formula (1) can be easily synthesized into an epoxy resin compound using the above-mentioned peroxide. The method is carried out by conventional means of organic synthesis.

For example, in the case of dicyclopentadiene of the structural formula (1),

[Omitted] It is considered that an epoxy compound and an epoxy resin as described above have been synthesized. It is believed that other compounds are undergoing similar reactions. The molecular weight of the epoxy resin is preferably 50,000 or less. The reason for this is that if the molecular weight of the epoxy resin is increased, the flame retardant performance that appears when modified with urea becomes worse. Next, when the epoxy resin obtained as described above is reacted with urea, it is considered that a block-type urea-modified epoxy resin is formed. Taking dicyclopentadiene as an example,

[Of 10] It is considered that the structural formula is as follows. It is believed that other compounds are undergoing similar reactions. At this time, the molar ratio of urea to the epoxidized compound is 90% to 90%.
Preferably, it is 5%. The reason is that when the molar ratio of urea is 90% or more, the physical properties of the urea-modified epoxy resin become brittle, and when it is 5% or less, the flame-retardant effect becomes very poor. The urea-modified epoxy resin thus obtained preferably has a molecular weight of 100 to 300,000. The reason is that if the molecular weight is 100 or less, the strength of the epoxy resin becomes extremely poor, and if the room temperature is high, the monomer smells, or if the molecular weight is 300,000 or more, the workability at the time of use deteriorates. is there.

Further, a catalyst may be used in the reaction for obtaining an epoxy resin compound using the above-mentioned organic peroxide.
Suitable catalysts include, for example, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, lithium hydroxide, ammonium hydroxide, sodium hydrogen sulfate, sodium sulfate, barium hydroxide, anhydrous copper sulfate, and the like.

In the above synthesis reaction of the urea-modified epoxy resin compound, the reaction may be carried out in a solvent, if necessary. As the solvent, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, decalin, N-
Any one or more of methylpyrrolidone, dimethylformamide, dimethylsulfoxide, dimethylacetamide, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, etc. It can be used selectively. Of course, the solvent is not limited to these.

The double bond portion of the compound represented by the structural formula (1) is epoxidized using the above-mentioned peroxide, and simultaneously reacted with urea while performing ring-opening polymerization to form a urea-modified epoxy resin. The method of obtaining is described in detail.

[0015]

[Of 11] 0.5 to 10 moles, preferably 1.5 to 4 moles, of the above-mentioned peroxide is added to the compound having a double bond.
The reaction is carried out in an amount of from 01 mol to 2 mol, preferably from 0.05 mol to 1.2 mol. Heating temperature is 10
C. to 180C, preferably 20C to 150C, more preferably 40C to 120C. Next, a method of obtaining the urea-modified epoxy resin by reacting the above epoxy compound with urea will be described in detail. The amount of urea used for the epoxy compound is preferably 90% to 5%, and more preferably 80% to 10%, and the amount of urea is desirably 10% or more in order to reduce the afterflame time to 7 seconds or less. The temperature at which the epoxy compound is reacted with urea is 20 ° C. to 260 ° C., preferably 40 ° C.
C. to 180C, more preferably 60C to 150C. In the above reaction, if necessary, a catalyst such as triethylamine, pyridine, dimethylaminophenol,
Methyl ethyl imidasol or the like may be used. The use amount is preferably 0.1% to 5%.

In the above reaction, a solvent may be used if necessary. As the solvent, for example, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, benzene, toluene,
Any one or more of xylene, decalin, N-methylpyrrolidone, dimethylformamide, cimethylsulfoxide, dimethylacetamide, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate and the like can be arbitrarily selected and used. You can do it. Of course, the solvent is not limited to these.

In the above reaction, the reaction may be carried out in an atmosphere of an inert gas such as nitrogen gas, argon gas or carbon dioxide gas.

In the above reaction, when a solvent is used, after completion of the reaction, the pressure is reduced while a rotary evaporator, a distillation apparatus, an ester reaction apparatus, a polymer polymerization apparatus,
Distillation is performed using a device such as a drum dryer, a vacuum dryer, or a spray dryer.

The urea-modified epoxy resin compound obtained as described above may be cured using a curing agent. Preferred curing agents are phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, dihydrophthalic anhydride, tetrahydrophthalic anhydride, methylphthalic anhydride, methyldihydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic acid Acid anhydrides, amino compounds represented by the following structural formulas (1) to (60)

[Of 12]

[Of 13]

[Of 14]

[Of 15] And phenolic resins are used. The molecular weight of the phenol resin is preferably 200,000 or less.
The reason is that when the molecular weight becomes larger than 200,000, the urea-modified epoxy compound cured with the phenol resin becomes hard and brittle.

With respect to 100 parts by weight of the urea-modified epoxy resin, the amount of the curing agent used is 30 parts by weight to 90 parts by weight for an acid anhydride, 1 part to 60 parts by weight for an amino compound, and 60 parts by weight for an phenol resin. Is preferably 40 to 80 parts by weight. The preferred curing temperature is 7 for acid anhydrides.
0 ° C to 220 ° C, 10 ° C to 190 ° for amino compounds
C., and in the case of a phenol resin, the temperature is preferably from 50.degree.

Next, a method for forming the urea-modified epoxy resin compound foam according to the present invention will be described in detail. Foams used for molding foams include, for example, chlorofluorocarbon (alternative fluorocarbon, 1416, etc.), carbodiimide, nitrogen gas,
1 out of hydrocarbons (pentane, cyclopentane), etc.
More than one species can be arbitrarily selected and used. Of course, the foaming agent is not limited to these.

Further, the foaming agent is added before, during, or after the reaction of the compound represented by the following structural formula (1) with the epoxidized compound using a peroxide and urea. May be added at any time, but it is easier to control the foam, especially when added after the reaction,
Although it is preferable, it is more preferable to add a foaming agent when curing the reaction product of the epoxidized compound and urea using a curing agent.

[Of 16]

The amount of the foaming agent is preferably 1 to 50 parts by weight, based on 100 parts by weight of the urea-modified epoxy resin.
The foaming temperature can be arbitrarily selected as long as it is in the range of 0 to 300 ° C. However, from the viewpoint of easy control of the reaction, the temperature is preferably 20 ° C to 190 ° C.

Next, the method for obtaining the urea-modified epoxy resin compound and the foam thereof according to the present invention will be described in detail with reference to specific examples.

[0025]

Example 1 120 g of ethylidene norbornene and 2 g of ammonium hydroxide were added to 500 g of toluene, transferred to a reaction vessel, and purged with nitrogen gas, and 100 cc of 50% hydrogen peroxide solution was added dropwise over 30 minutes while heating to 80 ° C. The mixture was reacted for 5 hours while stirring. The molecular weight of the thus obtained ethylidene norbornene epoxy resin compound measured by gel permeation chromatography was 6,200. Next, 300 g of methyl ethyl ketone and 60 g of urea were added to the reaction product, and the temperature was raised to 95 ° C. in a nitrogen atmosphere with stirring, and the reaction was carried out for 8 hours. Next, the solvent was distilled off at 60 ° C. while reducing the pressure to 5 mmHg using a rotary evaporator. The resulting reactant had a viscosity of 52,000 cps (25
° C). Epoxy equivalent is 10
3 (g / eq), molecular weight was 82,000.

[0026]

Example 2 80 g of dicyclopentadiene, 10 g of divinylbenzene, 2 g of potassium hydroxide and 600 g of xylene
g was added to the reaction vessel, and the peracetic acid 7
After dropping 0 g over 1 hour and reacting for 9 hours while stirring, the mixture is washed with water, left standing for 30 minutes, the separated aqueous phase is discarded, and the xylene phase is taken out. Dicyclopentadiene / hexadiene / divinylbenne thus obtained
The molecular weight of the Zenko epoxy resin compound measured by gel permeation chromatography (GCP) was 13,000.

Next, methyl ethyl ketone 4 was added to the above reaction product.
After adding 20 g and 54 g of urea, the temperature was raised to 98 ° C. in an argon gas atmosphere with stirring, and the reaction was carried out for 12 hours. And 5 using a rotary evaporator
The solvent was distilled off at 80 ° C. under reduced pressure of mmHg. The resulting reaction was a light brown solid. When heated to 80 ° C., it melted and had a viscosity of 2200 cps (80 ° C.).
The epoxy equivalent was 92 (g / eq), and the molecular weight measured by GPC (gel permeation chromatography) was 121,000.

[0028]

Example 3 To 100 g of the urea-modified ethylidene norbornene epoxy resin compound obtained in Example 1 was added 54 g of a phenol resin having a molecular weight of 7,200 as a curing agent, and the mixture was mixed well.
Heating to 1 ° C. for 1 hour gave a brown solid. The Shore A hardness of this solid was 92, and the maximum elongation was 21%.

[0029]

Example 4 100 g of urea-modified ethylidene norbornene epoxy resin compound obtained in Example 1 and a molecular weight of 72
54 g of phenolic resin and 21 g of carbodiimide
Was added to a mixed solvent of 300 g of toluene and 300 g of methyl ethyl ketone, heated to 80 ° C. for 40 minutes, pre-cured while stirring, and the solvent was distilled off under reduced pressure of 1 mmHg using a rotary evaporator. In order to form a foam from the urea-modified ethylidene norbornene epoxy resin compound phenol resin precured product containing the foaming agent, the mold temperature may be 185 ° C. and heating may be performed for 25 minutes.

[0030]

Embodiment 5 For Embodiments 3 and 4, JIS-A-13
Table 1 shows the results of the quasi-nonflammability test (surface test) specified in No. 21. Further, for reference, in addition to the above examples, examples of a phenol resin foam as Reference Example 1 and examples of an isocyanurate resin foam as Reference Example 2 will be shown.

[Table 1]

[0031]

As described above, according to the urea-modified epoxy resin compound and the foam thereof according to the present invention, the after-flame time at the time of combustion is almost zero, and the fire resistance and fire resistance are excellent. The amount of smoke generated during combustion is small, and the environment can be considered.
It does not generate formalin, a harmful air pollutant, or epichlorohydrin, a chlorine compound, during the reaction. Does not release bisphenol A, an environmental hormone.

Claims (9)

[Claims] 1. A urea-modified epoxy resin compound characterized by reacting a compound represented by the following structural formula with a compound epoxidized using a peroxide and urea. Embedded image Embedded image 2. The urea-modified epoxy resin compound according to claim 1, wherein the mole% of urea relative to the epoxidized compound is 90% to 5%. 3. The epoxidized compound has a molecular weight of 50,
2. The epoxidized compound according to claim 1, which has a molecular weight of 000 or less. 4. The urea-modified epoxy resin compound according to claim 1, wherein the molecular weight is from 100 to 300,000. 5. The urea-modified epoxy resin compound according to claim 1, which is a block copolymer. 6. The urea-modified epoxy resin compound according to claim 1, wherein a phenol resin is used as a curing agent. 7. The phenolic resin according to claim 6, having a molecular weight of 200,000 or less. 8. The urea-modified epoxy resin compound according to claim 1, wherein the after-flame time is 7 seconds or less. 9. The compound represented by the structural formula according to claim 1 is reacted with an epoxidized compound using a peroxide and urea, and the foaming material is reacted before, during or after the reaction. A urea-modified epoxy resin compound foam formed by adding and foaming at any time after the step (a).