JPS5991117A - Thermosettable epoxy resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting epoxy resin composition, a method for curing the same, and a cured product obtained by the method.

Epoxy resin, that is, an average of one or more 1.
Those containing 2-epoxide groups are known to be cured by reaction with various groups of substances to form crosslinked, infusible, insoluble products with industrially useful properties.

U.S. Patent No. 33869-6 describes the following formula (wherein R is a divalent group selected from the group consisting of a methyl-substituted phenylene group, a methylene diphenylene group, a dimethoxydiphenylene group, and a dimethyldiphenylene group). represents a group, R1 represents a -CHs group or a -CH, CTTtOT (group, . represents an integer of 2 to 5, X represents 10CHs, -C14, 18,CHs or -N
The curing of epoxy resins with urea compounds represented by O2) is described.

This patent also states that the curing effect of these curing agents is promoted by adding dicyandiamide, stearic hydrazide, adipic dihydrazide, succinimide or cyanoacetamide to the curable composition.

The patent addresses the drawbacks of conventional curable epoxy resin compositions, including the need for relatively high temperatures and relatively long curing times when using curing agents such as dicyandiamide; The use of the above-mentioned urea compounds overcomes the fact that the use of more reactive curing agents or accelerators results in incomplete curing at room temperature and is therefore not sufficiently latent. .

U.S. Pat. No. 5,660,516 describes that 1-cyano-3-(lower alkyl)quanidine accelerates the curing of epoxy resins by bisurea compounds represented by formulas (1) to (2).

Urea compounds represented by the above formula, especially N-(4-10
loofenyl) -N', N'-dimethylurea and 2
．． 4-bis(N,N-dimethylureido)toluene is
Alone, along with dicyandiamide as a growth accelerator,
It is also used commercially with dicyandiamide to cure epoxy resins, as an accelerator for the curing of epoxy resins.

However, as there is a growing need for curable compositions that have a long shelf life at room temperature but cure rapidly at moderately high temperatures (e.g. 100°C), alternatives to the above-mentioned urea compounds have emerged. Things are being explored.

We have found that certain phenolic urine compounds meet these more stringent requirements well.

Therefore, the present invention (at epoxy resin and (bl　effective bone Formula V: (OH)y (During the ceremony.

R2 is -NHt, Not, -Cl, -B
r or an alkyl group having 1 to 10 carbon atoms;
p represents zero, 1 or 2, X and y each represent zero or 1, and the sum of x+y is 1.

Furthermore, the present invention also provides a method for curing an epoxy resin, characterized by heating the thermosetting composition of the present invention, and a cured epoxy resin obtained by the method.

Preferably, when R2 represents -Not, -C/ or -CH1, p represents zero or 1, and when each R1 represents -C7, %p represents 2.

Particularly desirable compounds of formula V are N-(5-hydroxyphenyl)-N', N'--)l fluorurea,
N-(4,6-dichloro-3-hydroxyphenyl)-
N', N'-dimethylurea, N-(4-hydroxyphenyl)-N', N'-dimethylurea, N-(4-hydroxy-2-methylphenyl)-N'.

■-Dimethylurea, N-(4-hydroxy-5-nitrophenyl)-N', N'-dimethylurea! HiN-(3
, 5-cyclo-4-hydroxyphenyl)-N', N
'-dimethylurea.

The composition may include a thermoset amount of (b). That is, urea of formula V is the only curing agent. In such cases, 3 to 25, preferably 5 to 20 parts by weight (bl) per 100 parts by weight of epoxy resin (al) are usually used.

Hydroxyphenylureas of formula V are generally known or can be prepared by known methods.

A convenient method of preparation is described in British Patent No. 999862, in which:

An m-stratified p-hydroxyphenylurea of formula V has been prepared as an intermediate for its propardyl ether to be used as a herbicide.

An aminophenol represented by the formula ■: (OH)y (wherein R'', p + x and y have the same meanings as shown above) is represented by the formula ■: (wherein, X is a halogen atom, preferably is a chlorine atom).

This reaction is usually carried out in the presence or in the presence of an organic or inorganic base, in an organic solvent, at room temperature or elevated temperature.

Another convenient method is to react the aminophenol of the formula with phosgene in an aromatic highly polar solvent to obtain the isocyanophenol, which is then reacted with dimethylamine to obtain the desired ureidophenol. (U.S. Pat. No. 5,488,576, in which these products are described as intermediates for ureidophenol carbamates to be used as herbicides, and H. Alrich et al., Synthesis, 21979, No. 4, 277). -page 279, and H. Ulrichet al.
, S3'nthesis, 1979/164
, 277-279).

Hydroxyphenylureas of formula V in which p represents 1 or 2 can be prepared from other compounds of formula V by known methods. For example, a compound represented by formula V in which p represents zero is nitrified or halogenated to obtain a compound in which p represents 1 and 2 and R2 represents a nitro group or a halogen atom. A corresponding amino compound can be obtained by reducing a compound represented by formula (3) in which R1 represents a nitro group.

We have found that dicyandiamide, melamine, carboxylic acid hydrazides, and some intermediate compounds also promote heat curing of epoxy resins by urea compounds of Formula V.

Therefore, the present invention further provides (cl
A heat curing accelerator selected from cyanoacetamide, 1-cyano-5 (lower alkyl)guanidine containing one or more lower alkyl groups having up to 3 carbon atoms, a salt of imidasol oyohycarboxylic acid and a tertiary amine. Including.

(b) and (c) are the amounts that together result in the heat curing of (&), and typically they contain a total of 5 to 25 parts by weight per 100 parts by weight of epoxy resin (al).

Thermosetting compositions according to the invention are also provided.

Furthermore, we have found that the urea compound of formula V accelerates the thermal curing of epoxy resins by dicyandiamide, melamine, carboxylic acid hydrazide and some fine compounds.

Therefore, the present invention further provides a larger amount of (calculated based on the heavy electric current of (dl (bl),
dicyandiamide, melamine, carboxylic acid hydrazide,
Heat curing for epoxy resins selected from succinimide, cyanoacetamide, 1-cyano-5-(lower alkyl)guanyline containing one or more lower alkyl groups of up to 3 carbon atoms, imidazole and tertiary amine salts of carboxylic acids epoxy resin (d) and (bl taken together) in a thermosetting amount, typically in a total of 5 to 25 parts by weight per 100 parts by weight of epoxy resin (a). 1 A thermosetting composition according to the present invention is also provided.

The epoxy resins used in these compositions have the formula ■: (wherein) directly bonded to one or more oxygen, nitrogen, or sulfur atoms.

When R represents a hydrogen atom or a methyl group, R3 and R6 each represent a hydrogen atom.

When R4 represents a hydrogen atom, R3 and ns together represent -CHzCHz -
A compound containing at least two groups represented by (representing a group) is desirable.

Examples of such resins include resins obtained by reacting a compound containing two or more carboxylic acid groups per molecule with shrimp chlorohydrin, glycerol dichlorohydrin, or β-methyl shrimp chlorohydrin in the presence of an alkali. Mention may be made of polyglycidyl and poly(β-methylglycidyl) esters such as aliphatic polycarboxylic acids such as Schereric acid.

From succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or dimerized linoleic acid; also tetrahydrophthalic acid, 4-methylnato-2hydrophthalic acid, From cycloaliphatic polycarboxylic acids such as hexahydrophthalic acid and 4-methylhexahydrophthalic acid; and from aromatic polycarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.

Yet another example is the reaction of a compound containing at least two free alcoholic and/or phenolic hydroxyl groups per molecule with the appropriate shrimp chlorohydrin under alkaline conditions.

Alternatively, polyglycidyl and poly(
β-methylglycidyl) ether. These ethers include ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane-1,2-diol and poly(oxypropylene) glycol, propane-1,3-diol, butane-1,
--Diol, poly(oxytetramethylene) glycol, pentane-1,5-diol.

Hexane-1,6-diol, Hexane-2,4゜6-
Doriol, glycerol, 1,1.1-)limethylolpropane, pentaerythritol.

From acyclic alcohols such as sorbitol, and polyevichlorohydrin; also resorcinol, quinitol, bis(4-hydroxycyclohexyl)methane,
2,2-bis(4-hydroxycyclohexyl)propane, O! From cycloaliphatic alcohols such as H1゜1-bis(hydroxymethyl)cyclohex-3-ene: also N
, N-bis(2-hydroxyethyl)aniline and p
, p'-bis(2-hydroxyferur2))diphenylmethane. Well, these are.

From mononuclear phenols such as resorcinol and hydroquinone, also bis(4-hydroxyphenyl)methane, 4. /-dihydro-tetraxydiphenyl, bis(Δ-hydroxyphenyl)sulfone, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(
4-hydroxyphenyl)propane, 2,2-bis(3
, 5-sif-mo-4-hydroxyphenyl)propane and formaldehyde, acetaldehyde.

Aldehydes such as chloral, furfuraldehyde, phenol itself and chlorine or carbon atoms such as 4-chlorophenol, 2-methylphenol, 4-g-tributylphenol! ! It can be made from polynuclear phenols such as novolacs formed from phenols such as phenols substituted on the ring by an alkyl group.

For example, poly(N-glycidyl) compounds.

amines containing at least two amino-hydrogen atoms such as aniline, n-butylamine, bis(-monoaminophenyl)methane, m-xylene diamine and bis(4-methylaminophenyl)methane and epichlorohydrin. What was obtained by dehydrochlorinating the reaction product; triglycidyl isocyanurate; and ethylene urea and 1.3
- Cyclic alkylene ureas, such as propylene urea, and N,N'-diglycidyl derivatives of hydantoins, such as 5,5-dimethylhydantoin.

An example of a poly(S-glycidyl) compound is ethane-1,2-
dithiols and di-S-glycidyl derivatives of dithiols such as bis(4-mercaptomethylphenyl)ether.

An example of an epoxy resin having a group represented by the formula ■ where R3 and R8 are both K and represents a group represented by the formula: -CHtCHz- is bis(2,3-
epoxycyclobentyl) ether, 2,3-epoxycyclopertyl glycidyl ether and 1,2-bis(2,3-epoxycyclopentyloxy)ethane.

Epoxy resins with 1,2-epoxide groups attached to different types of heteroatoms can be used.

For example, N, N, O-)liglycidyl derivatives of 4-agnophenol, glycidyl ether of salicylic acid, etc.
Glycidyl esters, N-glycidyl-N-(2-glycidyloxyprobyl)-5,5-dimethylhydantoin and 2-glycidyloxy-1,3-bis(5,5
-dimethyl-1-glycidylhydantoin-3-yl)
It's propane.

Mixtures of epoxy resins may be used if desired.

Preferred epoxy resins are polyglycidyl ethers, polyglycidyl esters, N,N-diglycidylhydantoins and poly(N-glycidyl) derivatives of aromatic amines. Particularly desirable resins include 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, or formaldehyde and a 7-enol or one chlorine atom or one C1-C9 alkyl group. made from a phenol substituted on the ring by

The polyglycidyl ether of novolak, bis(4
-(diglycidylamino)phenyl)methane, and p
-(diglycidylamino)phenylglycidyl ether.

When the accelerator (e) or the primary curing agent (d) is a carboxylic acid hydrazide, stearic acid hydrazide, oxalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide or isophthalic acid dihydrazide are preferred.

Accelerator (c) or main curing agent (d) is 1-cyano-5
- (lower alkyl)guanidine, 3-methyl, 3.3-dimethyl or 3.3-diethyl compounds are preferred ◎ When the accelerator (e) or main curing agent (d) is imidazole , 2-phenylimidazole.

N-methylimidazole or Fi2-ethyl-4-methylimidazole is preferred.

When the accelerator (e) or the primary curing agent (d) is a salt of a carboxylic acid and a tertiary amine, 2°4.6-)lith(
Salts with Mannieh bases such as dimethylaminomethyl)phenol are preferred.

Normally, the promoter (e) is present in a ratio of 10 to 50 parts by weight per 100 parts by weight of urea (h);
) When used as an accelerator for the lr curing agent (e), it is present in a ratio of 25 to 75 parts by weight per 100 parts by weight of (d).

This new composition additionally contains suitable plasticizers such as dibutyl phthalate and dioctyl phthalate, inert diluents such as tar and bitemene and so-called reactive diluents.

In particular, monoepoxides such as n-butyl glycidyl ether, isooctyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, glycidyl esters of mixtures of tertiary aliphatic monocarboxylic acids, glycidyl acrylate and glycidyl methacrylate may be included. Yet again. Fillers, reinforcing materials.

Polymeric tougheners such as polyether sulfones, phenoxy resins and butadiene-acrylonitrile rubber 1 may contain additives such as colorants, flow modifiers, flame retardants and mold release agents.

Suitable extenders, fillers and reinforcements include, for example:

Glass fiber, carbon fiber, aromatic polyamide fiber, barochini, mica-1 quartz powder, calcium carbonate, cellulose,
They are kaolin, Wu J-7 gamma stonite, cotetraidal silica with a large specific surface area, powdered poly(vinyl chloride), and powdered polyolefin hydrocarbons such as polyethylene and polypropylene.

The curable composition of the present invention is a resin for coating.

Impregnation and casting resins, powder coatings, molding compositions, putty and sealing compounds.

It can be used in potting and insulating compounds in the electrical industry, especially as primers for adhesives and adhesives ◎ The composition of the invention
It is preferable to heat and cure at a temperature in the range of 130°C to 130°C. Usually, heating for 30 to 120 minutes is sufficient for curing.

The present invention will be explained below with reference to Examples. Parts are parts by weight.

The urea compounds used in these examples were prepared as follows.

N-(3-hydroxyphenyl)-N,N-dimethylurea m-aminophenol (10 g) and N,N-dimethylcarbamoyl chloride (7,,n2p)? Dissolved in tetrahydrofuran (65 ml) and heated the solution at 30°C for 4 hours.
Stir for an hour. The solvent is evaporated under reduced pressure and the solid residue is suspended in water. This mixture was filtered, thoroughly washed with water, dried in a desiccator, and then dried using Koffler's pliers (T(o)
N-(3-hydroxyphenyl)-N,N-dimethylurea is obtained which melts (decomposes) at 198°C as measured on a florbench (U.S. Pat. No. 348B376 states that the melting point is 194-197°C). Yes)・N
-(3-Hydroxyphenyl)-N,N-dimethylurea (4,5,9) is dissolved in glacial acetic acid (100 m/) at 55°C and the solution is cooled to 30°C. Gaseous chlorine (177g
) into the solution and after the chlorine has been added, the mixture is stirred for a further 1 hour at 30° C. and then concentrated under reduced pressure at 80° C. until a residue begins to form. The mixture is cooled to 10° C. and, after filtration, the residue is washed thoroughly with water. This residue was recrystallized from isopropanol to give N-(
A, 6-dichloro-3-hydroxyphenyl)-N, N
-Dimethylurea (155N) is obtained. Melting point: 208℃ (
Disassembly).

N-(,If-hydroxyphenyl)-i,i-dimethylurea This is prepared as described in UK Patent No. 999982, i.e. p-aminophenol (3op), dimethylcarbamoyl chloride (g
aII), sodium bicarbonate (28,9), and dehydrated acetone (6oomz) are stirred and heated at reflux for 3 hours. The mixture is filtered while hot, and the filtrate is left overnight to cool. The formed crystals are separated by filtration and have a melting point of 20 as measured on a Ko-fler bench.
Obtain the desired urea at 5°C (decomposition) (British Patent No. 99)
No. 9802 specification states that the melting point is 250-206°C).

This material was prepared by replacing p-agunophenol with an equimolar amount of 4-amino-3-methylphenol.

-Make in the same manner as above. It melts (decomposes) at 245°C.

This material is made as described above, substituting an equimolar amount of 1-amino-2,6-dichlorophenol for p-aminophenol. It melts (decomposes) at 196°C.

H, Alrich et al. (H, U/r tah 4J:
4-Hydroxy-3-nitrophenyl isocyanate (15,51) prepared from 4-amino-2-nitrophenol and phosgene as described in ) was dissolved in 100 p of a 29% by weight dimethylamino solution in toluene. and the mixture is stirred at room temperature for 2 hours. Evaporate under reduced pressure to obtain a residue.

N-(-monohydroxy-3-nitrophenyl)-N with a melting point of 142 DEG C. by recrystallization from water.

N-dimethylurea is obtained.

"Epoxy resin!" is 1,2 equivalent of 5.16 per kg
- represents a polyglycidyl ether of 2,2-bis(4-hydroxyphenyl)furopane with an epoxide content and a viscosity of 24.5 pa at 21°C.

[Epoxy resin UJ hull kg weight 7.8-8.2
Represents a tetrakis(N-glycidyl) derivative of bis(4-aminophenyl)methane with an equivalent amount of epoxide-containing fLt- The gelation time is approximately a, and the mixture of 1p is placed on a metal block heated to a constant temperature, and the mixture is gelled. Observe the time required for the reaction to occur.Example 1 1100 parts of epoxy resin, 13 parts of N-(3-hydroxyphenyl)-N,N-dimethylurea and asbeth) 1
- A mixture of 5 parts of commercially available chicken broth is prepared in a three-roll mixer.

Gelation time Ifi: 22°C minutes at 120°C, 30 days at 40°C ◎ Example 2 Replaced with 15.5 parts of urea fN-(4,6-dichloro-3-hydroxyphenyl)-N,N-dimethylurea 〇The gelation time is 30°C minutes at 120°C and 30 days or more at 40°C.

Example 3 This example shows that the thermal curing of an epoxy resin by urea of Formula V is accelerated by the use of dicyandiamide.

Commercially available thixotropic agent 5 containing 1100 parts of epoxy resin, 10 parts of N-(3-hydroxyphenyl)-N,N-dimethylurea, 2 parts of dicyandiamide and asbestos.
This result is comparable to the gelation time obtained in Example 1 using a large amount of urea (13 parts). An example is the preparation of the following composition using urea of formula V. Values indicate parts by weight Oa b Epoxy resin 1 100 100 Dicyandiamide 77 Thixotropic agent
66N-(3-Hydroxyphenyl)-N,N-dimethylurea 40 (Thixotropic agent consists of 5 parts finely divided silica and 1 part glycerol) A sample of the composition was heated to 120<0>C. raJ gelled in 24 minutes, but rbJ did not gel even after heating for 150 minutes at the end of the experiment.

Example 5 A mixture of 1100 parts of epoxy resin, 113 parts of N-(4-hydroxydiphenyl)-i,i-dimethyl urine, and 5 parts of a commercially available thixotropic agent containing asbestos is prepared in a three-roll mixer.

The gelation time of the mixture with is 27 minutes at 120°C and 280 minutes at 40°C.

Example 6 The same procedure as in Example 5 is carried out in place of 14 parts of urea'1rN-(+-hydroxy-2-methylphenyl)-N,N-dimethylurea. Gelation time was 25 minutes at 120°C, -0
℃ for 24 days.

Example 7 The same procedure as in Example 5 is carried out in place of urea'1N-(,5,5-dichloro-4-hydroxyphenyl)-N,N-dimethylurea 1115.

Gelation time: 11,120°C for 32°C minutes, and 40°C for 30 days.

EXAMPLE The Japanese example shows that the thermal curing of an epoxy resin by urea of formula (1) is accelerated by the use of dicyandiamide.

Example 5 is carried out in the same manner as in Example 5, except that the mixture further includes 2 parts of dicyandiamide.

The gelation time at 120°C is reduced from 27 minutes to 16 minutes.

Example 9 This example shows that the use of urea represented by formula V accelerates the thermal curing of the epoxy resin by dicyandiamide.

The following composition was manufactured by vf4. Values represent parts by weight.

Epoxy resin 11oo1o.

Dicyandiamide 7 Athixotrope 66N-(4-Hydroxyphenyl) (The thixotrope consists of 5 parts finely divided silica and 1 part glycerol) A sample of the composition is heated to 120°C. raJ gels in 21 minutes, but "bJIIi remained gelled even at the end of the 150-minute heating experiment" Example 10 Urine F'tN-(4-Human 4-xy-3-nitrophenyl)
The same procedure as in Example 5 is carried out, except that 16.2 parts of -i,i-dimethylurea are used. Gelation time H: 33 minutes at 120°C, 40
℃ for 18 days or more.

Example 11 Epoxy resin... and N-(4-hydroxyphenyl)-N
, N-dimethylurea is prepared to contain (1) 2 parts (II) s parts (ii Dio parts) of urea per 100 parts of resin. The gelation times of the mixture at various temperatures are as follows: be.

Temperature During gelation time (II) (iiD13
0℃ 14 minutes 9 minutes 7 minutes 110℃ -
6 minutes 27 minutes 22 minutes 100℃ 70 minutes
55 minutes 45 minutes 90℃ 180 minutes 96 minutes 88 minutes 40℃ 〉18th 15th 1
Day 0 Example 12 In this example, one component is heat cured when the bond is formed.

1100 parts of epoxy resin, aluminum powder (British standard Br1tish 5 standard 410, 2
00 mesh), 5 parts of a commercially available thixotropic agent containing asbestos and either N-(3-hydroxyphenyl>-N,i-dimethylurea or N-(4-hydroxyphenyl>-i,*-dimethylurea) A mixture of 13 parts of
“2L73 Allad (Alelad) J (
AI! cJad is a registered trademark) using an aluminum alloy sheet that has been degreased and washed with dilute acid water.
．． 54c1rLXt27cr! Make a layered seam for one L piece.

This mixture is cured by heating at 120° C. for 1 hour. The shear strength of the adhesive is 28.4 MPa for the composition containing the 3-hydroxy isomer and 292 MPa for the composition containing the 4-hydroxy isomer.

Example 13 This example shows that hydrazide promotes the curing of an epoxy resin by urea represented by formula (2).

The following composition is prepared on a three roll mill. Addition of adipic acid hydrazide is seen to shorten gelation time without affecting shelf life.

b Epoxy resin 1 100 100N-(
4-Hydroxyphenyl) -N,N-dimethylurea 1010 Thixotropic agent 4″ 22 Adipic acid hydrazide 40 Gel time 120°C 13 minutes 215 minutes 100
°C 70 minutes 80 minutes Shelf life at 40°C 〉18 days〉18 days Tatami Commercial product containing asbestos Example 14 This example shows that urea represented by formula (■) accelerates the curing of epoxy resin by adipic acid hydrazide. 〇Prepare the following composition in a three-roll mill.

Values represent parts〇a b Epoxy resin 1 100 100 Adipic acid hydrazide 22.5 22.5 Thixotropic bi 22N-(4-hydroxyphenyl) -N,N-dimethylurea 5.60 Gelation time 120°C 11 minutes 180 minutes 100℃
65 minutes > 390 minutes Shelf life at 40°C > 18 days > 18 days Tatami Commercial product containing asbestos Example 15 In this example, the glass transition temperature of a cured epoxy resin containing urea represented by formula 1 was differentially scanned. Calorie method (differential scale)
O epoxy resin measured by calorimetry )! 100 parts, 5 parts of a thixotropic agent containing asbestos and N-(4-hydroxyphenyl)-N,N-dimethylurea or N-(3-hydroxyphenyl)-N,N
- Prepare a composition containing 13 parts of either dimethylurea. A sample of the O-group acid is cured at 120° C. for 1 hour.

Both exhibit a glass transition temperature of 105°C Patent applicant ChipperGeigie Akchengesellschaft

Claims (9)

[Claims] (1) (al epoxy resin and (bl) Effective amount of formula V: (OI()y (wherein, R2 is -NT(,, -No, -C/, -Rr t carbon atoms 1 to 10 , p represents zero, 1 or 2, X and y each represent zero or 1, and the sum of x+7 is 1). (2) R'' represents -No, -cl! or -CH5, p represents zero or 1, or R2 represents -(J and p represents 2) Claim 1 Compositions as described. (3) (b) is N-(3-hydroxyphenyl)-N'
, N'-dimethylurea, N-(4,6-dichloro-3-
hydroxyphenyl)-N', N'-dimethylurea, N
-(4-hydroxyphenyl) -N', N'-dimethylurea, N-'(4-hydroxy-2-methylphenyl)-N', N'-dimethylurea, N-(4-hydroxy-3-dimethylurea) trophenyl)-y, W-dimethylurea or N-(3,s-dichloro-4-hydroxyphenyl)
-N',N'-dimethylurea
Compositions as described in Section. (4) A composition according to any one of the preceding claims, comprising a thermosetting amount of (b). (5) The composition according to claim 4, wherein the BL of (a) is 3 to 2511 (parts by weight) per 100 Leno. (6) Furthermore, (C) dicyandiamide, carboxylic acid hydrazide,
Succinimide, cyanoacetamide, 1-cyano-3-( containing one or more lower alkyl groups of up to 3 carbon atoms)
(lower alkyl) guanidine, imidazole and salts of carboxylic acids with tertiary amines (calculated on the weight of bl) The composition according to item 1. (7) Furthermore. (dl Dicyataimide, carboxylic acid hydrazide, succinimide, cyanoacetamide, 1-cyano-5-(lower alkyl)guanidine containing one or more lower alkyl groups of up to 3 carbon atoms, imidazole, and salts of carboxylic acids and tertiary amines A thermosetting agent selected from (bl
Composition according to any one of claims 1 to 3, comprising a greater amount, calculated on the weight, of . (8) Formula ■ directly bonded to one or more oxygen, nitrogen or sulfur atoms: (In the formula. If R4 represents a hydrogen atom or a methyl group, R3 and R11 each represent a hydrogen atom, or R'
When represents a hydrogen atom, R3 and R's together form 10HICH! −
The composition according to any one of claims 1 to 7, which contains at least two a3 groups. (9) The composition according to claim 8, wherein (a) is a polyglycidyl ether, a polyglycidyl ester, an N,N'-diglycidylhydantoin, or a poly(N-glycidyl) derivative of an aromatic amine. 0 (a3 Epoxy resin and (bl Effective amount of formula V: (OH))r (wherein R1 is -NHt*NO2+ Cl*Br
or represents an alkyl group having 1 to 10 carbon atoms, p
represents zero, 1 or 2, X and y each represent zero or 1, and the sum of x+V is 1). A method of curing epoxy resin characterized by heating it to .