Europaisches Patentamt

3 European Patent Office ® Publication number: 0 1 3 8 4 6 5

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EUROPEAN PATENT A P P L I C A T I O N

© Application number: 84306576.4 © Int. CI.*: C 08 G 59/18, C 08 G 5 9 / 4 2 ,

C08G 59/40, C 08 G 5 9 / 6 4 ,
^
© Date of filing: 27.09.84 C 08 G 59/50, C 08 G 5 9 / 5 8 ,
C08G 59/66

© Priority. 30.09.83 JP 182528/83 @ Applicant: AJINOMOTO CO., INC., 5-8,

Kyobashi 1-chome, Chuo-ku, Tokyo 104 (JP)

@ Inventor: Hirose, Takeshi, No. 2-20-8, Kannon-cho

Kawasakl-ku, Kawasaki-shi Kanagawa-ken (JP)
Inventor: Ito, Nobuo, No. 26 4-5 Ikusawa Oisomachl,

Duiienn oo/ i / Nakahara-ku, Kawasakf-shl Kanagawa-ken (JP)

Inventor: Takeuchl, Kojl, No. 806-40, Kamislrane-cho
Asahi-ku, Yokohama-shl Kanagawa-ken (JP)

@ Representative : Bond, Bentley George et al, HASELTINE

LAKE &CO. Hazlitt House 28 Southampton Buildings
@ Designated Contracting States: DE FR GB Chancery Lane, London, WC2A 1AT (GB)

@ Latent curing agents for epoxy resins.

An addition product obtained by reacting (a) a polyfunctional
epoxy compound, (b) a compound having at least one functional
group of OH group, NH2 group, NH group and SH group together
with a tertiary amino group in the molecule and (c) a carboxylic
acid anhydride are good curing agents for epoxy resin. The curing
agents are useful in formulating novel storable one-package,
heat-curable epoxy resin-based compositions.
 The present invention relates to a latent curing

agent for epoxy resins. More particularly, it relates to

a latent curing agent for epoxy resins which causes rapid

curing at moderate elevated temperature and which gives

epoxy resin composition having excellent storage stability

at ropm temperature.

One-pack type epoxy resins are preferable to the

conventional two-pack type ones because the former are free

of misformulation and can be used continuously. One-pack

type epoxy resins require a so-called latent curing agent

which does not react with epoxy compounds at room

temperature, but on heating, reacts with epoxy compounds

to effect curing.

Heretofore, several latent curing agents have

been proposed. Representative examples are boron

trifluoride-amine adduct, dicyandiamide, and dibasic acid

dihydrazide. The first one is hard to treat owing to its

high hygroscopic property and it affects adversely

the physical properties of the cured resin. The latter

two are useful in formulating epoxy resin compositions

having excellent storage stability but full curing by means

of these compound could be achieved only by heating at higher

temperature than 150°C_for a long time. To save energy

and not to damage sur rounding components, rapid curing at

a low temperature is required.

It is known that an amine type curing agent can

be improved in workability by converting it into an adduct

 -2-
with an epoxy resin. It has recently been disclosed that
an
an adduct obtained by the reaction oftimidazole compound

with an epoxy compound is a comparatively good latent curing

agent (See U.S. Patent No. 4,066,625.) For example, an

adduct obtained by the reaction of 2-ethyl-4-methylimidazole

with Epon 834 (bisphenol A type epoxy resin; a product of

Shell Chemical Co., epoxy equivalent 230~270) has a

softening temperature of 100 to 125°C. But as, in general,a

formulated resin having good reactivity is poor in storage

stability, or having good storage stability is poor in

reactivity, the range of good reaction ratio is very narrow.

Epoxy resin composition incorporating an adduct obtained

by the reaction of 1 equivalent of epoxy group in Epon 834

for 1 equivalent of secondary amino group of 2-ethyl-4-

methylimidazole is cured at 100°C for thirty minutes, but

is poor in storage stability (4 days at 35°C, 2 days at

40°C). Epoxy resin composition incorporating an adduct

obtained by the reaction of 2 equivalent of Epon 834 for

1 equivalent of 2-ethyl-4-methylimidazole has good storage

stability (> 14 days at 35°C) but is poor in reactivity.

These adducts perform curing at a low temperature when they

are used with other curing agents, so they are superior to

an adduct of aliphatic amine with an epoxy compound as

latent curing agents, but they are insufficient as latent

curing agents which perform curing at 100 ~ 130°C and are

superior in storage stability.

It is known that an adduct obtained by the

reaction of N-methylpiperazine with an epoxy compound can

be used as a latent curing agent (See U.S. Patent No.

4,268,656). But, this adduct alone cannot be effective

as a latent curing agent, but only when used with a n o t h e r curing agent.

In short, an adduct of an aliphatic amine and

an epoxy compound cannot improve the storage stability very

much. In the case of specific amine compound, an adduct

of the two compounds, an amine compound and an epoxy

compound, which satisfy both the reactivity and storage

stability as a latent curing agent for one-pack type epoxy

resin is rare.

We h a v e carried out a series of researches in

order to develop a latent curing agent which performs curing

at a low temperature and is superior in storage stability.

As the result, it has been found that it is possible to

obtain a latent curing agent which is superior to the

above-mentioned adduct of an amine type curing agent and

an epoxy compound. Such a latent curing agent is an adduct

obtained by reacting a compound having active hydrogen

together with a tertiary amino group in the molecule, an

epoxy compound and a carboxylic acid anhydride.

In other words, the addition of the third

compound, carboxylic acid anhydride, improvesthe storage

stability without impairing the reactivity. It is possible

to obtain a latent curing agent which performs curing at

a low temperture and is superior in storage stability.

And, by the addition of a carboxylic acid anhydride, it

is possible to show the superiority as a latent curing over

the wide range of the reaction ratio of an amine compound

to an epoxy compound.

The active hydrogen of the compound having a

tertiary amino group is not only -NH2 group and -NH group

but also -OH group and SH g r o u p .

That is, it has been found that an addition

product obtained by reacting (a) a polyfunctional epoxy

compound, (b) a compound having at least one functional

group of -OH group, -NH2 group, -NH group and -SH group

together with a tertiary amino group in the molecule and

(c) a carboxylic acid anhydride is the latent curing agent

that meets the object of this invention.

A detailed description will be given in the

following with respect to the latent curing agent of this

invention.

The polyfunctional epoxy compound as a raw

material of the latent curing agent of this invention may

be any compound having two or more epoxy groups in the

molecule. It includes, for example, polyglycidyl ether

obtained by reacting a polyhydric phenol (such as bisphenol

A, bisphenol F, catechol, resorcinol) or a polyhydric

alcohol (such as glycerin and polyethylene glycol) with

epichlorohydrin; glycidyl ether ester obtained by reacting

a hydroxycarboxylic acid (such as hydroxybenzoic acid and

S-hydroxynaphthoic acid) with epichlorohydrin; polyglycidyl

ester obtained from a polycarboxylic acid such as

terephthalic acid; glycidylamine compound obtained from

4,4'-diaminodiphenylmethane and m-aminophenol; and

epoxidized novolak and epoxidized polyolefin.

The compound having at least one functional group

of OH g r o u p , N H 2 group, NH g r o u p and SH g r o u p together with

a tertiary amino group in the molecule, which is reacted

with the above-mentioned polyfunctional epoxy compound,

may be represented by the following formula:

where X is -OH group, -NH2 group, -NH group, or -SH group;

R1 and R2 a r e C1-20 alkyl groups, C2-20 alkenyl groups,

and aromatic hydrocarbon groups such as phenyl group and

benzyl group, with or without substituent such as oxygen,

halogen, and functional group as represented by X mentioned

above; and R3 is a divalent residue of R1 or R2. R1 and

R2 may connect with each other to form a ring, or R1, R2

and R3 may connect with one another to form a ring. The

compounds with tertiary amino groups contained in the

heterocyclic ring as represented by the following formula

(2) are also effective:

where R4, R5, R6 and R7 are hydrogen atoms, the groups

defined by R1 and R21 or the functional groups defined by

X in the above; and R7 is a hydrogen atom or at least one

of R4, R51 R6, and R7 contains the functional group

represented by X.

The representative examples of the compound having

at least one functional group of -OH, -NH2, -NH and -SH

together with a tertiary amino group are listed below:

2-Dimethylaminoethanol, 1-methyl-2-dimethyl-

aminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol,

2-diethylaminoethanol, 1-butoxymethyl-2-dimethylamino-

ethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole,

1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole,

1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole,

1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole,

1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline,

1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline,

2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethyl-

aminomethyl)phenol, N-β-hydroxyethyl morpholine,

2-dimethylaminoethylamine, 3-dimethylamino-n-propylamine,

2-diethylaminoethylamine, 3-diethylamino-n-propylamine,

N-methylpiperazine, imidazole, 2-methylimidazole,

2-ethylimidazole, 2-ethyl-4-methylimidazole,

2-isopropylimidazole, 2-undecylimidazole, 2-octadecyl-

imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole,

2-dimethylaminoethanethiol, methimazole, 2-mercapto-

benzoimidazole, 2-mercaptobenzothiazole and the like.

The examples of the carboxylic acid anhydride

are listed below:

Succinic anhydride, phthalic anhydride, tetrahydro

phthalic anhydride, methyl tetrahydro phthalic anhydride,

hexahydro phthalic anhydride, methyl hexahydro phthalic

anhydride, methyl nadic anhydride, dodecenylsuccinic

anhydride, pyromellitic dianhydride, 5-(2,5-diketo-

tetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic

anhydride and the l i k e .

To p r o d u c e an addition compound which is the

latent curing agent of this invention, components (a), (b)

and (c) are reacted in a ratio of 0.4 m 2 equivalent,

preferably 0.5 m 1.5 equivalent of active hydrogen in

component (b) and 0.25 ~ 2.5 equivalent, preferably 0.7 ~

2.0 equivalent of component (c), carboxylic acid anhydride,

for 1 equivalent of epoxy group in component (a).

If the equivalent number of component (b) is less

than 0.4 equivalent for 1 equivalent of epoxy group in

component (a), epoxy resins incorporated with such an

addition product is slow in curing.

If the equivalent number of component (b) is more

than 2 equivalent for 1 equivalent of epoxy group in

component (a), the resulting addition product has a low

softening point and cannot be readily crushed. Epoxy resins

incorporated with such an addition product is poor in

storage stability.

If the equivalent number of component (c) is less

than 0.25 equivalent for 1 equivalent of epoxy group in

component (a), the effect of component (c) cannot appear.

If the equivalent number of component (c) is more

than 2.5 equivalent for 1 equivalent of epoxy group, the

addition product has a low softening point and epoxy resins

incorporated with such a product is poor in storage

stability.

Two or more compounds may be mixed for each of

components (a), (b), and (c), so long as they are used in

quantities as specified above.

The latent curing agent of this invention can

be easily obtained by thoroughly mixing components (a),

(b), and (c), gelling them at room temperature or at an

elevated temperature, reacting at 80 to,150°C, cooling,

solidifying, and crushing. It can also be prepared by

performing addition reaction in a solvent such as

tetrahydrofuran, dioxane, and methyl ethyl ketone, removing

the solvent, and crushing the solid.

The latent curing agent of this invention can

be used in combination with a known curing agent such as

acid anhydride, dicyandiamide, dibasic acid hydrazide,

guanamine, and melamine. The latent curing agent of this

invention can be applied to a variety of known epoxy resins

having two or more epoxy groups in one molecule. The latent

curing agent of this invention should be used in an amount

of 0.5 to 40 parts by weight for 100 parts by weight of

epoxy resin. If the quantity is less than 0.5 part by

weight, satisfactory curing performance is not attained;

and using more than 40 parts by weight impairs t h e

performance of the cured product.

The representative examples of epoxy resins to

be cured b y the latent curing agent of the invention are

those based on glycidyl ethers of polyhydric phenols such

as 2,2-bis(4-hydroxyphenyl)-propane (Bisphenol A),

resorcinol, hydroquinone, pyrocatechol, saligenine,

Bisphenol F and phenolformamide resin.

If necessary, other curing agents, cure

accelerator and fillers may be employed in combination with

the curing agent of the present invention.

The following examples illustrate the preparation

of the latent curing agents and their use as a curing agent

the
for epoxy resin. The abbreviations of raw materials employed

in the examples are as follows.

(a) Polyfunctional epoxide

Epon 828 (a product of Shell Chemical Co.)

Bisphenol A type epoxy resin

epoxy equivalent 184 ~ 194

Epon 1001 (a'product of Shell Chemical Co.)

Bisphenol A type epoxy resin

epoxy equivalent 450 ~ 500

Epon 807 (a product of Shell Chemical Co.)

Bisphenol F type epoxy resin

epoxy equivalent 166 m 175

 Epon 834 (a product of Shell Chemical Co.)

Bisphenol A type epoxy resin

epoxy equivalent 230 ~ 270

(b) Organic compounds having at least one functional group selected

From OH group, NH2 group, NH g r o u p and SH g r o u p together

a
with a tertiary amino group in the molecule

DMAE 2-Dimethylaminoethanol

PG-MZ 1-(2-Hydroxy-3-phenoxypropyl)-2-

methylimidazole

DMP-30 2,4,6-Tris(dimethylaminomethyl)phenol

DMP-10 2-(Dimethylaminomethyl)phenol

DMAPA 3-Dimethylamino-n-propylamine

MZ 2-Methylimidazole

EMZ 2-Ethyl-4-methylimidazole

SMZ Methimazole

(c) Carboxylic acid anhydride

PA Phthalic anhydride

MTHPA Methyl tetrahydro phthalic anhydride

MHHPA Methyl hexahydro phthalic anhydride

DDSA Dodecenylsuccinic anhydride

EXPA 5-(2,5-diketotetrahydrofuryl)-3-methyl-3-

cyclohexene-1,2-dicarboxylic anhydride

Example 1

Preparation of addition product of Epon 828, DMAE a n d

MHHPA

38 Gram (0.2 equivalent) of Epon 828 were

sufficiently mixed with 8.4 g (0.5 equivalent) of MHHPA

at room temperature, and to the mixture was added 8.9 g

(0.1 equivalent) of DMAE. The temperature was raised

gradually under stirring. When the viscosity started to

increase, the temperature was maintained at 80°C for thirty

minutes, and further maintained at 100°C for an hour.

The reaction mixture was cooled to room temperature whereby

brown-red solid was obtained. This product was ground to

a powder and is referred to as sample No. 2.

Example 2

Preparation of addition product of Epon 828, EMZ a n d

PA

15 Gram (0.1 equivalent) of PA a n d 10 g of methyl

ethyl ketone as solvent were m i x e d . The mixture was heated

at 60°C, and there were a d d e d 11 g (0.1 equivalent) of EMZ. The

there
mixture was stirred to a slurry were a d d e d 19 g ( 0 . 1

equivalent) Epon 828, and the temperature was raised

gradually under stirring. When the reaction started at

approximately 80°C, heating was stopped. After stirring

the mixture to be viscous,it was cheated at 100°C for an hour,

and heated at 120°C under reduced pressure to remove methyl

ethyl ketone. The reaction mixture was cooled to room

temperature whereby pale yellowish solid was obtained.

is
This product was ground to a powder andkreferred to as

sample No. 15.

The sample No. and softening temperature of other

addition products prepared by similar manner as in Examples 1 a n d 2

.
are shown in Table 1.
 Eexample 3

Reactivity, storage stability and glass transition

temperature of the formulated epoxy resin composition were

evaluated.

Formulation

1. Evaluation of the reactivity

1) Onset temperature (Ti) and peak temperature (Tp) were

measured by differential thermal analysis (DTA)

Sample weight : about 10 mg

Standard material: a-A1203

Heating rate : 5°C/min.

2) The sample was put into a Geer's oven maintained

to the prescribed temperature and the resulted cured

resin was observed as toits appearance.

2. Storage stability

The sample was put into a Geer's oven set to

30°C and the day required for the sample to become non-

fluid was measured.

3. Glass transition temperature (T.g.)

T.g. of the cured resin was measured with a

thermal mechanical analysis apparatus (TMA, a product of

Rigaku Corporation) by TMA p e n e t r a t i o n method.

Raising rate of temperature: 10°C/min.

 Load : 10 g

Diameter of needle : 1 mm

The results obtained are summarized in Table 2.

Furthermore, a series of adducts obtained by the

reaction of Epon 834 as component (a); EMZ as component

(b) and MHHPA as component (c) was evaluated varying the

reaction ratio of components (b) and (c) to component (a).

Softening temperature of the adduct, reactivity, storage

stability and glass transition temperature of the formulated

epoxy resin composition were evaluated. The results

obtained are summarized in Table 3. And, adducts of the

two compounds, amine compounds and epoxy compounds, were

evaluated as latent curing agent for comparison. The

results are summarized in Table 4.

As shown in Table 2, the addition product of the

present invention is superior latent curing agent because

it showed greatly improved storage stability in comparison

with compound having an active hydrogen atom and tertiary

amino group (control) alone. Further, as shown in Table

3 and Table 4, the addition product of the present invention

is superior latent curing agent because it showed improved

storage stability in comparison with the adduct of the two

of an amine compound and an epoxy compound, and it is

possible to obtain a superior latent curing agent over the

wide range of reaction ratio of amine compound.

Example 4

Reactivity and storage stability of the

 .
combination system of the latent curing agent of the present

invention and dibasic acid hydrazide were estimated.

The formulation is shown below and the results

are shown in Table 4.

Formulation

It will be understood from the comparison of Table

2 with Table 4 that the latent curing agent of the present

invention exerts synergistic effect in reactivity in

combination with adipic dihydrazide.

Example 5

The storage stability and curing of the

combination system of the latent curing agent of the present

invention and the known latent curing agent were estimated.

T h e formulation and the result are shown in Table 6.

As shown in Table 6, the epoxy system containing

the known latent curing agent above did not entirely cure

at 120°C for 1 hour. However, the combination system of

the latent curing agent and the known latent curing agent

caused complete curing at 120°C for 1 hour.

Example 6

The reactivity and the storage stability of the

combination system of the latent curing agent and acid

anhydride were estimated. The formulation is shown below

and the results are shown in Table 7.

Formulation

As shown in Table 7, the addition product of the

present invention is superior latent curing accelerator

because it showed greatly improved storage stability and

similar reactivity in comparison with amine type

accelerator.
 1. A latent curing agent for an epoxy resin,
characterised in that the latent curing agent is

an adduct obtained by reacting (a) polyfunctional

epoxy compound, (b) a compound containing at least
one active hydrogen atom and at least one tertiary
amino group, and (c) a carboxylic acid anhydride.
2. A latent curing agent as claimed in claim
1, wherein the active hydrogen atom of component
(b) is present as the group -OH, the group -NH2,
the group -NH or the group -SH.
3. A latent curing agent as claimed in claim
2, wherein component (b) is a compound having the

general formula:

wherein X is the group -OH, the group -NH2, the

group -NH or the group -SH; wherein R1 and R2 are

the same or different and each is a C 1 t o C20 a l k y l
group, a C2 to C20 alkenyl group or an a r o m a t i c
group (which alkyl, alkenyl or aromatic groups
optionally contain one or more substituents such
as -O-, =O, -halogen, -OH, -NH2, -NH and -SH);
wherein R3 is a C1 to C20 alkylene group, a C2
to C20 alkenylene group or a divalent aromatic
group (which alkylene, alkenylene or aromatic groups
optionally contain one or more substituents such
as -0-, =0, -halogen, -OH, -NH2, -NH and -SH);
wherein, in the alternative, R1 and R2 are connected
together to form a divalent hydrocarbyl group
(optionally containing one or more substituents
such as -O-, =O, -halogen, -OH, -NH2, -NH and -SH);
wherein, in the alternative, R1 and R2 and R3 are
connected together to form a quadruvalent hydrocarbyl
group (optionally containing one or more substituents
such as -0-, =O, -halogen, -OH, -NH2, -NH and -SH).
 4. A latent curing agent as claimed in claim
2, wherein component (b) is a compound having the
general formula:

wherein R4, R5, R6 and R7 are the same or different

and each is a hydrogen atom, the group -OH, the

group -NH2, the group -NH, the group -SH,

a C 1 t o C20 a l k y l group, a C2 t o C20 a l k e n y l g r o u p
or an a r o m a t i c group (which a l k y l , alkenyl or a r o m a t i c
groups optionally contain one or more substituents
such as -O-, =O, -halogen, -NH2, -NH a n d - S H ) ;
-OH,
wherein, in t h e a l t e r n a t i v e , a n y two of R4, R 5 ,

R 6 a n d R7 a r e c o n n e c t e d t o g e t h e r to form a d i v a l e n t
hydrocarbyl group (optionally containing one or
more substituents such as -O-, =O, -halogen, -OH,

-NH2, -NH and -SH); wherein, in the alternative,

any three R4, R5, R6 a n d R7 a r e c o n n e c t e d t o g e t h e r
of
to form a trivalent hydrocarbyl group (optionally
containing one or more substituents such as -O-,
=0, -halogen, -OH, -NH2, -NH and -SH).
5. A latent curing agent as claimed in any
of claims 1 to 4, wherein component (a) is a
polyglycidyl ether preferably obtained by reacting a polyhydric
phenol or a polyhydric alcohol with epichlorohydrin;
a glycidyl ether ester preferably btained by reacting a
hydroxycarboxylic acid with epichlorohydrin a
polyglycidyl ester obtained from a polycarboxylic
acid; a glycidylamine compound obtained from
4,4'-diaminodiphenylmethane and m-aminophenol;
an epoxidized novolak; or an epoxidized polyolefin.
6. A latent curing agent as claimed in any
of claims 1 to 5, wherein component (c) is succinic
anhydride, phthalic anhydride, tetrahydro phthalic
anhydride, methyl tetrahydro phthalic anhydride,
hexahydro phthalic anhydride, methyl hexahydro
phthalic anhydride, methyl nadic anhydride,
dodecenylsuccinic anhydride, pyromellitic
dianhydride, or 5-(2,5-diketotetrahydrofuryl)-3-
methyl-3-cyclohexene-1,2-dicarboxylic anhydride.
7. A latent curing agent as claimed in any
of claims 1 to 6, wherein component (b) is used
in an amount of from 0.4 to 2 equivalents of active
hydrogen per 1 equivalent of epoxy group in

component (a), and wherein component (c) is used

in an amount of from 0.25 to 2.5 equivalents per
1 equivalent of epoxy group in component ( a ) .
8. A latent curing agent as claimed in any
of claims 1 to 7, obtained by mixing components
(a), (b) and (c), gelling the mixture, allowing
the mixture to react at a temperature of from 80
to 150°C, cooling the mixture and allowing it to
solidify, and crushing the solidified mixture.
9. A curable composition comprising (i)
an epoxy resin containing two or more epoxy groups,
and (ii) a latent curing agent as claimed in any
of claims 1 to 8.

10. A cured composition comprising (i)

an epoxy resin containing two or more epoxy groups,

and (ii) a latent curing agent as claimed in any

of claims 1 to 8.